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2021 Volume 37 Issue 6
2021, 37(6): 200803
doi: 10.3866/PKU.WHXB202008030
Abstract:
S-scheme heterojunction is a major breakthrough in the field of photocatalysis. In this study, NiS2 and MoSe2 were prepared by a typical solvothermal method, and compounded by an in situ growth method to construct an S-scheme heterojunction. The obtained composite showed excellent performance in photocatalytic hydrogen evolution; the hydrogen production rate was approximately 7 mmol·h-1·g-1, which was 2.05 times and 2.44 times those of pure NiS2 and MoSe2, respectively. Through a series of characterizations, it was found that NiS2 and MoSe2 coupling can enhance the light absorption intensity, which is vital for the light reaction system. The efficiency of electron-hole pair separation is also among the important factors restricting photocatalytic reactions. Compared with pure NiS2 and MoSe2, NiS2/MoSe2 exhibited a higher photocurrent density, lower cathode current, and lower electrochemical impedance, which proves that the NiS2/MoSe2 complex can effectively promote photogenerated electron transfer. Simultaneously, the lower emission intensity of fluorescence indicated effective inhibition of electron-hole recombination in the NiS2/MoSe2 complex, which is favorable for the photocatalytic hydrogen evolution reaction. Further, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that MoSe2 is an amorphous sample surrounded by the NiS2 nanomicrosphere, which greatly increased the contact area between the two, thus increasing the active site of the reaction. Secondly, as a photosensitizer, Eosin Y (EY) effectively enhanced the absorption of light by the catalyst in the photoreaction system. Meanwhile, during sensitization, electrons were provided to the catalyst, which effectively improved the photocatalytic reaction efficiency. The establishment of S-scheme heterojunctions contributed to improving the redox capacity of the reaction system and was the most important link in the photocatalytic hydrogen reduction of aquatic products. It was also the main reason for the improvement of the hydrogen evolution effect in this study. The locations of the conduction band and valence band of NiS2 and MoSe2 were determined by Mott-Schottky plots and photon energy curves, and further proved the establishment of the S-scheme heterojunction. This work provides a new reference for studying the S-scheme heterojunction to effectively improve the photocatalytic hydrogen production efficiency. ![]()
S-scheme heterojunction is a major breakthrough in the field of photocatalysis. In this study, NiS2 and MoSe2 were prepared by a typical solvothermal method, and compounded by an in situ growth method to construct an S-scheme heterojunction. The obtained composite showed excellent performance in photocatalytic hydrogen evolution; the hydrogen production rate was approximately 7 mmol·h-1·g-1, which was 2.05 times and 2.44 times those of pure NiS2 and MoSe2, respectively. Through a series of characterizations, it was found that NiS2 and MoSe2 coupling can enhance the light absorption intensity, which is vital for the light reaction system. The efficiency of electron-hole pair separation is also among the important factors restricting photocatalytic reactions. Compared with pure NiS2 and MoSe2, NiS2/MoSe2 exhibited a higher photocurrent density, lower cathode current, and lower electrochemical impedance, which proves that the NiS2/MoSe2 complex can effectively promote photogenerated electron transfer. Simultaneously, the lower emission intensity of fluorescence indicated effective inhibition of electron-hole recombination in the NiS2/MoSe2 complex, which is favorable for the photocatalytic hydrogen evolution reaction. Further, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that MoSe2 is an amorphous sample surrounded by the NiS2 nanomicrosphere, which greatly increased the contact area between the two, thus increasing the active site of the reaction. Secondly, as a photosensitizer, Eosin Y (EY) effectively enhanced the absorption of light by the catalyst in the photoreaction system. Meanwhile, during sensitization, electrons were provided to the catalyst, which effectively improved the photocatalytic reaction efficiency. The establishment of S-scheme heterojunctions contributed to improving the redox capacity of the reaction system and was the most important link in the photocatalytic hydrogen reduction of aquatic products. It was also the main reason for the improvement of the hydrogen evolution effect in this study. The locations of the conduction band and valence band of NiS2 and MoSe2 were determined by Mott-Schottky plots and photon energy curves, and further proved the establishment of the S-scheme heterojunction. This work provides a new reference for studying the S-scheme heterojunction to effectively improve the photocatalytic hydrogen production efficiency.
2021, 37(6): 200804
doi: 10.3866/PKU.WHXB202008047
Abstract:
The use of semiconductor photocatalysts (CdS, g-C3N4, TiO2, etc.) to generate hydrogen (H2) is a prospective strategy that can convert solar energy into hydrogen energy, thereby meeting future energy demands. Among the numerous photocatalysts, TiO2 has attracted significant attention because of its suitable reduction potential and excellent chemical stability. However, the photoexcited electrons and holes of TiO2 are easily quenched, leading to limited photocatalytic performance. Furthermore, graphene has been used as an effective electron cocatalyst in the accelerated transport of photoinduced electrons to enhance the H2-production performance of TiO2, owing to its excellent conductivity and high charge carrier mobility. For an efficient graphene-based photocatalyst, the rapid transfer of photogenerated electrons is extremely important along with an effectual interfacial H2-production reaction on the graphene surface. Therefore, it is necessary to further optimize the graphene microstructures (functionalized graphene) to improve the H2-production performance of graphene-based TiO2 photocatalysts. The introduction of H2-evolution active sites onto the graphene surface is an effective strategy for the functionalization of graphene. Compared with the noncovalent functionalization of graphene (such as loading Pt, MoSx, and CoSx on the graphene surface), its covalent functionalization can provide a strong interaction between graphene and organic molecules in the form of H2-evolution active sites that are produced by chemical reactions. In this study, carboxyl-functionalized graphene (rGO-COOH) was successfully modified via ring-opening and esterification reactions on the TiO2 surface by using an ultrasound-assisted self-assembly method to prepare a high-activity TiO2/rGO-COOH photocatalyst. The Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and thermogravimetric (TG) curves revealed the successful covalent functionalization of GO to rGO-COOH by significantly enhanced ―COOH groups in FTIR and increased peak area of carboxyl groups in XPS. A series of characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), XPS, and UV-Vis adsorption spectra, were performed to demonstrate the successful synthesis of TiO2/rGO-COOH photocatalysts. The experimental data for the hydrogen-evolution rate showed that the TiO2/rGO-COOH displayed an extremely high hydrogen-generation activity (254.2 μmol∙h−1∙g−1), which was 2.06- and 4.48-fold higher than those of TiO2/GO and TiO2, respectively. The enhanced photocatalytic activity of TiO2/rGO-COOH is ascribed to the carboxyl groups of carboxyl-functionalized graphene, which act as effective hydrogen-generation active sites and enrich hydrogen ions owing to their excellent nucleophilicity that facilitates the interfacial hydrogen production reaction of TiO2. This study provides novel insights into the development of high-activity graphene-supported photocatalysts in the hydrogen-generation field. ![]()
The use of semiconductor photocatalysts (CdS, g-C3N4, TiO2, etc.) to generate hydrogen (H2) is a prospective strategy that can convert solar energy into hydrogen energy, thereby meeting future energy demands. Among the numerous photocatalysts, TiO2 has attracted significant attention because of its suitable reduction potential and excellent chemical stability. However, the photoexcited electrons and holes of TiO2 are easily quenched, leading to limited photocatalytic performance. Furthermore, graphene has been used as an effective electron cocatalyst in the accelerated transport of photoinduced electrons to enhance the H2-production performance of TiO2, owing to its excellent conductivity and high charge carrier mobility. For an efficient graphene-based photocatalyst, the rapid transfer of photogenerated electrons is extremely important along with an effectual interfacial H2-production reaction on the graphene surface. Therefore, it is necessary to further optimize the graphene microstructures (functionalized graphene) to improve the H2-production performance of graphene-based TiO2 photocatalysts. The introduction of H2-evolution active sites onto the graphene surface is an effective strategy for the functionalization of graphene. Compared with the noncovalent functionalization of graphene (such as loading Pt, MoSx, and CoSx on the graphene surface), its covalent functionalization can provide a strong interaction between graphene and organic molecules in the form of H2-evolution active sites that are produced by chemical reactions. In this study, carboxyl-functionalized graphene (rGO-COOH) was successfully modified via ring-opening and esterification reactions on the TiO2 surface by using an ultrasound-assisted self-assembly method to prepare a high-activity TiO2/rGO-COOH photocatalyst. The Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and thermogravimetric (TG) curves revealed the successful covalent functionalization of GO to rGO-COOH by significantly enhanced ―COOH groups in FTIR and increased peak area of carboxyl groups in XPS. A series of characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), XPS, and UV-Vis adsorption spectra, were performed to demonstrate the successful synthesis of TiO2/rGO-COOH photocatalysts. The experimental data for the hydrogen-evolution rate showed that the TiO2/rGO-COOH displayed an extremely high hydrogen-generation activity (254.2 μmol∙h−1∙g−1), which was 2.06- and 4.48-fold higher than those of TiO2/GO and TiO2, respectively. The enhanced photocatalytic activity of TiO2/rGO-COOH is ascribed to the carboxyl groups of carboxyl-functionalized graphene, which act as effective hydrogen-generation active sites and enrich hydrogen ions owing to their excellent nucleophilicity that facilitates the interfacial hydrogen production reaction of TiO2. This study provides novel insights into the development of high-activity graphene-supported photocatalysts in the hydrogen-generation field.
2021, 37(6): 200908
doi: 10.3866/PKU.WHXB202009080
Abstract:
The growing frustration from facing energy shortages and unbalanced environmental issues has obstructed the long-term development of human society. Semiconductor-based photocatalysis, such as water splitting, transfers solar energy to storable chemical energy and is widely considered an economic and clean solution. Although regarded as a promising photocatalyst, the low specific surface area of g-C3N4 crucially restrains its photocatalytic performance. The macro-mesoporous architecture provides effective channels for mass transfer and full-light utilization and improved the efficiency of the photocatalytic reaction. Herein, g-C3N4 with an inverse opal (IO) structure was rationally fabricated using a well-packed SiO2 template, which displayed an ultrahigh surface area (450.2 m2·g-1) and exhibited a higher photocatalytic H2 evolution rate (21.22 μmol·h-1), almost six times higher than that of bulk g-C3N4 (3.65 μmol·h-1). The IO g-C3N4 demonstrates better light absorption capacity than bulk g-C3N4, primarily in the visible spectra range, owing to the multiple light scattering effect of the three-dimensional (3D) porous structure. Meanwhile, a lower PL intensity, longer emission lifetime, smaller Nyquist semicircle, and stronger photocurrent response (which synergistically give rise to the suppressed recombination of charge carriers) decrease the interfacial charge transfer resistance and boost the formation of photogenerated electron-hole pairs. Moreover, the existing N vacancies intensify the local electron density, helping increase the number of photoexcitons. The N2 adsorption-desorption test revealed the existence of ample mesopores and macropores and high specific surface area in IO g-C3N4, which exposes more active edges and catalytic sites. Optical behavior, electron paramagnetic resonance, and electrochemical characterization results revealed positive factors, including enhanced light utilization, improved photogenerated charge separation, prolonged lifetime, and fortified IO g-C3N4 with excellent photocatalytic performance. This work provides an important contribution to the structural design and property modulation of photocatalysts. ![]()
The growing frustration from facing energy shortages and unbalanced environmental issues has obstructed the long-term development of human society. Semiconductor-based photocatalysis, such as water splitting, transfers solar energy to storable chemical energy and is widely considered an economic and clean solution. Although regarded as a promising photocatalyst, the low specific surface area of g-C3N4 crucially restrains its photocatalytic performance. The macro-mesoporous architecture provides effective channels for mass transfer and full-light utilization and improved the efficiency of the photocatalytic reaction. Herein, g-C3N4 with an inverse opal (IO) structure was rationally fabricated using a well-packed SiO2 template, which displayed an ultrahigh surface area (450.2 m2·g-1) and exhibited a higher photocatalytic H2 evolution rate (21.22 μmol·h-1), almost six times higher than that of bulk g-C3N4 (3.65 μmol·h-1). The IO g-C3N4 demonstrates better light absorption capacity than bulk g-C3N4, primarily in the visible spectra range, owing to the multiple light scattering effect of the three-dimensional (3D) porous structure. Meanwhile, a lower PL intensity, longer emission lifetime, smaller Nyquist semicircle, and stronger photocurrent response (which synergistically give rise to the suppressed recombination of charge carriers) decrease the interfacial charge transfer resistance and boost the formation of photogenerated electron-hole pairs. Moreover, the existing N vacancies intensify the local electron density, helping increase the number of photoexcitons. The N2 adsorption-desorption test revealed the existence of ample mesopores and macropores and high specific surface area in IO g-C3N4, which exposes more active edges and catalytic sites. Optical behavior, electron paramagnetic resonance, and electrochemical characterization results revealed positive factors, including enhanced light utilization, improved photogenerated charge separation, prolonged lifetime, and fortified IO g-C3N4 with excellent photocatalytic performance. This work provides an important contribution to the structural design and property modulation of photocatalysts.
2021, 37(6): 201002
doi: 10.3866/PKU.WHXB202010027
Abstract:
Photocatalytic reduction of CO2 to hydrocarbon compounds is a promising method for addressing energy shortages and environmental pollution. Considerable efforts have been devoted to exploring valid strategies to enhance photocatalytic efficiency. Among various modification methods, the hybridization of different photocatalysts is effective for addressing the shortcomings of a single photocatalyst and enhancing its CO2 reduction performance. In addition, metal-free materials such as g-C3N4 and black phosphorus (BP) are attractive because of their unique structures and electronic properties. Many experimental results have verified the superior photocatalytic activity of a BP/g-C3N4 composite. However, theoretical understanding of the intrinsic mechanism of the activity enhancement is still lacking. Herein, the geometric structures, optical absorption, electronic properties, and CO2 reduction reaction processes of 2D/2D BP/g-C3N4 composite models are investigated using density functional theory calculations. The composite model consists of a monolayer of BP and a tri-s-triazine-based monolayer of g-C3N4. Based on the calculated work function, it is inferred that electrons transfer from g-C3N4 to BP owing to the higher Fermi level of g-C3N4 compared with that of BP. Furthermore, the charge density difference suggests the formation of a built-in electric field at the interface, which is conducive to the separation of photogenerated electron-hole pairs. The optical absorption coefficient demonstrates that the light absorption of the composite is significantly higher than that of its single-component counterpart. Integrated analysis of the band edge potential and interfacial electronic interaction indicates that the migration of photogenerated charge carriers in the BP/g-C3N4 hybrid follows the S-scheme photocatalytic mechanism. Under visible-light irradiation, the photogenerated electrons on BP recombine with the photogenerated holes on g-C3N4, leaving photogenerated electrons and holes in the conduction band of g-C3N4 and the valence band of BP, respectively. Compared with pristine g-C3N4, this S-scheme heterojunction allows efficient separation of photogenerated charge carriers while effectively preserving strong redox abilities. Additionally, the possible reaction path for CO2 reduction on g-C3N4 and BP/g-C3N4 is discussed by computing the free energy of each step. It was found that CO2 reduction on the composite occurs most readily on the g-C3N4 side. The reaction path on the composite is different from that on g-C3N4. The heterojunction reduces the maximum energy barrier for CO2 reduction from 1.48 to 1.22 eV, following the optimal reaction path. Consequently, the BP/g-C3N4 heterojunction is theoretically proven to be an excellent CO2 reduction photocatalyst. This work is helpful for understanding the effect of BP modification on the photocatalytic activity of g-C3N4. It also provides a theoretical basis for the design of other high-performance CO2 reduction photocatalysts. ![]()
Photocatalytic reduction of CO2 to hydrocarbon compounds is a promising method for addressing energy shortages and environmental pollution. Considerable efforts have been devoted to exploring valid strategies to enhance photocatalytic efficiency. Among various modification methods, the hybridization of different photocatalysts is effective for addressing the shortcomings of a single photocatalyst and enhancing its CO2 reduction performance. In addition, metal-free materials such as g-C3N4 and black phosphorus (BP) are attractive because of their unique structures and electronic properties. Many experimental results have verified the superior photocatalytic activity of a BP/g-C3N4 composite. However, theoretical understanding of the intrinsic mechanism of the activity enhancement is still lacking. Herein, the geometric structures, optical absorption, electronic properties, and CO2 reduction reaction processes of 2D/2D BP/g-C3N4 composite models are investigated using density functional theory calculations. The composite model consists of a monolayer of BP and a tri-s-triazine-based monolayer of g-C3N4. Based on the calculated work function, it is inferred that electrons transfer from g-C3N4 to BP owing to the higher Fermi level of g-C3N4 compared with that of BP. Furthermore, the charge density difference suggests the formation of a built-in electric field at the interface, which is conducive to the separation of photogenerated electron-hole pairs. The optical absorption coefficient demonstrates that the light absorption of the composite is significantly higher than that of its single-component counterpart. Integrated analysis of the band edge potential and interfacial electronic interaction indicates that the migration of photogenerated charge carriers in the BP/g-C3N4 hybrid follows the S-scheme photocatalytic mechanism. Under visible-light irradiation, the photogenerated electrons on BP recombine with the photogenerated holes on g-C3N4, leaving photogenerated electrons and holes in the conduction band of g-C3N4 and the valence band of BP, respectively. Compared with pristine g-C3N4, this S-scheme heterojunction allows efficient separation of photogenerated charge carriers while effectively preserving strong redox abilities. Additionally, the possible reaction path for CO2 reduction on g-C3N4 and BP/g-C3N4 is discussed by computing the free energy of each step. It was found that CO2 reduction on the composite occurs most readily on the g-C3N4 side. The reaction path on the composite is different from that on g-C3N4. The heterojunction reduces the maximum energy barrier for CO2 reduction from 1.48 to 1.22 eV, following the optimal reaction path. Consequently, the BP/g-C3N4 heterojunction is theoretically proven to be an excellent CO2 reduction photocatalyst. This work is helpful for understanding the effect of BP modification on the photocatalytic activity of g-C3N4. It also provides a theoretical basis for the design of other high-performance CO2 reduction photocatalysts.
2021, 37(6): 201003
doi: 10.3866/PKU.WHXB202010030
Abstract:
Organic photocatalysts have attracted attention owing to their suitable redox band positions, low cost, high chemical stability, and good tunability of their framework and electronic structure. As a novel organic photocatalyst, PDI-Ala (N, N'-bis(propionic acid)-perylene-3, 4, 9, 10-tetracarboxylic diimide) has strong visible-light response, low valence band position, and strong oxidation ability. However, the low photogenerated charge transfer rate and high carrier recombination rate limit its application. Due to the aromatic heterocyclic structure of g-C3N4 and large delocalized π bond in the planar structure of PDI-Ala, g-C3N4 and PDI-Ala can be tightly combined through π–π interactions and N―C bond. The band structure of sulfur-doped g-C3N4 (S-C3N4) matched well with PDI-Ala than that with g-C3N4. The electron delocalization effect, internal electric field, and newly formed chemical bond jointly promote the separation and migration of photogenerated carriers between PDI-Ala and S-C3N4. To this end, a novel step-scheme (S-scheme) heterojunction photocatalyst comprising organic semiconductor PDI-Ala and S-C3N4 was prepared by an in situ self-assembly strategy. Meanwhile, PDI-Ala was self-assembled by transverse hydrogen bonding and longitudinal π–π stacking. The crystal structure, morphology, valency, optical properties, stability, and energy band structure of the PDI-Ala/S-C3N4 photocatalysts were systematically analyzed and studied by various characterization methods such as X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, ultraviolet visible diffuse reflectance spectroscopy, electrochemical impedance spectroscopy, and Mott-Schottky curve. The work functions and interface coupling characteristics were determined using density functional theory. The photocatalytic activities of the synthesized photocatalyst for H2O2 production and the degradation of tetracycline (TC) and p-nitrophenol (PNP) under visible-light irradiation are discussed. The PDI-Ala/S-C3N4 S-scheme heterojunction with band matching and tight interface bonding accelerates the intermolecular electron transfer and broadens the visible-light response range of the heterojunction. In addition, in the processes of the PDI-Ala/S-C3N4 photocatalytic degradation reaction, a variety of active species (h+, ·O2-, and H2O2) were produced and accumulated. Therefore, the PDI-Ala/S-C3N4 heterojunction exhibited enhanced photocatalytic performance in the degradation of TC, PNP, and H2O2 production. Under visible-light irradiation, the optimum 30%PDI-Ala/S-C3N4 removed 90% of TC within 90 min. In addition, 30%PDI-Ala/S-C3N4 displayed the highest H2O2 evolution rate of 28.3 μmol·h-1·g-1, which was 2.9 and 1.6 times higher than those of PDI-Ala and S-C3N4, respectively. These results reveal that the all organic photocatalyst comprising PDI-based supramolecular and S-C3N4 can be efficiently applied for the degradation of organic pollutants and production of H2O2. This work not only provides a novel strategy for the design of all organic S-scheme heterojunctions but also provides a new insight and reference for understanding the structure–activity relationship of heterostructure catalysts with effective interface bonding. ![]()
Organic photocatalysts have attracted attention owing to their suitable redox band positions, low cost, high chemical stability, and good tunability of their framework and electronic structure. As a novel organic photocatalyst, PDI-Ala (N, N'-bis(propionic acid)-perylene-3, 4, 9, 10-tetracarboxylic diimide) has strong visible-light response, low valence band position, and strong oxidation ability. However, the low photogenerated charge transfer rate and high carrier recombination rate limit its application. Due to the aromatic heterocyclic structure of g-C3N4 and large delocalized π bond in the planar structure of PDI-Ala, g-C3N4 and PDI-Ala can be tightly combined through π–π interactions and N―C bond. The band structure of sulfur-doped g-C3N4 (S-C3N4) matched well with PDI-Ala than that with g-C3N4. The electron delocalization effect, internal electric field, and newly formed chemical bond jointly promote the separation and migration of photogenerated carriers between PDI-Ala and S-C3N4. To this end, a novel step-scheme (S-scheme) heterojunction photocatalyst comprising organic semiconductor PDI-Ala and S-C3N4 was prepared by an in situ self-assembly strategy. Meanwhile, PDI-Ala was self-assembled by transverse hydrogen bonding and longitudinal π–π stacking. The crystal structure, morphology, valency, optical properties, stability, and energy band structure of the PDI-Ala/S-C3N4 photocatalysts were systematically analyzed and studied by various characterization methods such as X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, ultraviolet visible diffuse reflectance spectroscopy, electrochemical impedance spectroscopy, and Mott-Schottky curve. The work functions and interface coupling characteristics were determined using density functional theory. The photocatalytic activities of the synthesized photocatalyst for H2O2 production and the degradation of tetracycline (TC) and p-nitrophenol (PNP) under visible-light irradiation are discussed. The PDI-Ala/S-C3N4 S-scheme heterojunction with band matching and tight interface bonding accelerates the intermolecular electron transfer and broadens the visible-light response range of the heterojunction. In addition, in the processes of the PDI-Ala/S-C3N4 photocatalytic degradation reaction, a variety of active species (h+, ·O2-, and H2O2) were produced and accumulated. Therefore, the PDI-Ala/S-C3N4 heterojunction exhibited enhanced photocatalytic performance in the degradation of TC, PNP, and H2O2 production. Under visible-light irradiation, the optimum 30%PDI-Ala/S-C3N4 removed 90% of TC within 90 min. In addition, 30%PDI-Ala/S-C3N4 displayed the highest H2O2 evolution rate of 28.3 μmol·h-1·g-1, which was 2.9 and 1.6 times higher than those of PDI-Ala and S-C3N4, respectively. These results reveal that the all organic photocatalyst comprising PDI-based supramolecular and S-C3N4 can be efficiently applied for the degradation of organic pollutants and production of H2O2. This work not only provides a novel strategy for the design of all organic S-scheme heterojunctions but also provides a new insight and reference for understanding the structure–activity relationship of heterostructure catalysts with effective interface bonding.
2021, 37(6): 201005
doi: 10.3866/PKU.WHXB202010059
Abstract:
Sustainable photocatalytic H2 evolution has attracted extensive attention in recent years because it can address both energy shortage and environmental pollution issues. In particular, metal sulfide solid-solution photocatalysts have been widely applied in photocatalytic hydrogen generation owing to their excellent light harvesting properties, narrow enough band gap, and suitable redox potentials of conduction and valance bands. However, it is still challenging to develop low-cost and high-efficiency sulfide solid-solution photocatalysts for practical photocatalytic hydrogen evolution. Recently, 1D MnxCd1-xS nanostructures have shown superior light absorption, charge separation, and H2-evolution activity owing to their shortened diffusion pathway of carriers and high length-to-diameter ratios. Thus, 1D MnxCd1-xS nanostructures have been applied in photocatalytic H2 evolution. However, a single MnxCd1-xS photocatalyst still has some disadvantages for photocatalytic H2 evolution, such as the rapid recombination of photogenerated electron-hole pairs and low quantum efficiency. Herein, to further boost the separation of photogenerated charge carriers and H2-evolution kinetics, an in situ solvothermal method was used to synthesize the 1D/2D Schottky-based heterojunctions between the Mn0.2Cd0.8S nanorods (MCS NRs) and Ti3C2 MXene nanosheets (NSs). Furthermore, various characterization methods have been used to investigate the crucial roles and underlying mechanisms of metallic Ti3C2 MXene NSs in boosting the photocatalytic H2 evolution over the Mn0.2Cd0.8S nanorods. X-ray Diffraction (XRD), Transmission Electron Microscope (TEM), High Resolution Transmission Electron Microscopy (HRTEM), element mapping images, and X-ray Photoelectron Spectroscopy (XPS) results clearly demonstrate that hybrid low-cost Schottky-based heterojunctions have been successfully constructed for practical applications in photocatalytic H2 evolution. Additionally, the photocatalytic hydrogen evolution reaction (HER) was also carried out in a mixed solution of Na2SO3 and Na2S using as the sacrificial agents. The highest hydrogen evolution rate of the optimized 1D/2D Schottky-based heterojunction is 15.73 mmol·g-1·h-1, which is 6.72 times higher than that of pure MCS NRs (2.34 mmol·g-1·h-1). An apparent quantum efficiency of 19.6% was achieved at 420 nm. The stability measurements of the binary photocatalysts confirmed their excellent photocatalytic stability for practical applications. More interestingly, the UV-Vis diffuse reflection spectra, photoluminescence (PL) spectrum, transient photocurrent responses, and Electrochemical Impedance Spectroscopy (EIS) Nyquist plots clearly confirmed the promoted charge separation between the MCS NRs and Ti3C2 MXene NSs. The linear sweep voltammetry also showed that the loading of MXene cocatalysts could greatly decrease the overpotential of pure MCS NRs, suggesting that the 2D Ti3C2 NSs could act as an electronic conductive bridge to improve the H2-evolution kinetics. In summary, these results show that the 2D/1D hybrid Schottky-based heterojunctions between metallic Ti3C2 MXene NSs and MCS NRs can not only improve the separation of photogenerated electrons and holes but also decrease the H2-evolution overpotential, thus resulting in significantly enhanced photocatalytic H2 generation. We believe that this study will inspire new ideas for constructing low-cost Schottky-based heterojunctions for practical applications in photocatalytic H2 evolution. ![]()
Sustainable photocatalytic H2 evolution has attracted extensive attention in recent years because it can address both energy shortage and environmental pollution issues. In particular, metal sulfide solid-solution photocatalysts have been widely applied in photocatalytic hydrogen generation owing to their excellent light harvesting properties, narrow enough band gap, and suitable redox potentials of conduction and valance bands. However, it is still challenging to develop low-cost and high-efficiency sulfide solid-solution photocatalysts for practical photocatalytic hydrogen evolution. Recently, 1D MnxCd1-xS nanostructures have shown superior light absorption, charge separation, and H2-evolution activity owing to their shortened diffusion pathway of carriers and high length-to-diameter ratios. Thus, 1D MnxCd1-xS nanostructures have been applied in photocatalytic H2 evolution. However, a single MnxCd1-xS photocatalyst still has some disadvantages for photocatalytic H2 evolution, such as the rapid recombination of photogenerated electron-hole pairs and low quantum efficiency. Herein, to further boost the separation of photogenerated charge carriers and H2-evolution kinetics, an in situ solvothermal method was used to synthesize the 1D/2D Schottky-based heterojunctions between the Mn0.2Cd0.8S nanorods (MCS NRs) and Ti3C2 MXene nanosheets (NSs). Furthermore, various characterization methods have been used to investigate the crucial roles and underlying mechanisms of metallic Ti3C2 MXene NSs in boosting the photocatalytic H2 evolution over the Mn0.2Cd0.8S nanorods. X-ray Diffraction (XRD), Transmission Electron Microscope (TEM), High Resolution Transmission Electron Microscopy (HRTEM), element mapping images, and X-ray Photoelectron Spectroscopy (XPS) results clearly demonstrate that hybrid low-cost Schottky-based heterojunctions have been successfully constructed for practical applications in photocatalytic H2 evolution. Additionally, the photocatalytic hydrogen evolution reaction (HER) was also carried out in a mixed solution of Na2SO3 and Na2S using as the sacrificial agents. The highest hydrogen evolution rate of the optimized 1D/2D Schottky-based heterojunction is 15.73 mmol·g-1·h-1, which is 6.72 times higher than that of pure MCS NRs (2.34 mmol·g-1·h-1). An apparent quantum efficiency of 19.6% was achieved at 420 nm. The stability measurements of the binary photocatalysts confirmed their excellent photocatalytic stability for practical applications. More interestingly, the UV-Vis diffuse reflection spectra, photoluminescence (PL) spectrum, transient photocurrent responses, and Electrochemical Impedance Spectroscopy (EIS) Nyquist plots clearly confirmed the promoted charge separation between the MCS NRs and Ti3C2 MXene NSs. The linear sweep voltammetry also showed that the loading of MXene cocatalysts could greatly decrease the overpotential of pure MCS NRs, suggesting that the 2D Ti3C2 NSs could act as an electronic conductive bridge to improve the H2-evolution kinetics. In summary, these results show that the 2D/1D hybrid Schottky-based heterojunctions between metallic Ti3C2 MXene NSs and MCS NRs can not only improve the separation of photogenerated electrons and holes but also decrease the H2-evolution overpotential, thus resulting in significantly enhanced photocatalytic H2 generation. We believe that this study will inspire new ideas for constructing low-cost Schottky-based heterojunctions for practical applications in photocatalytic H2 evolution.
2021, 37(6): 201102
doi: 10.3866/PKU.WHXB202011022
Abstract:
In environment remediation, photocatalytic oxidation is a promising technique for removing organic pollutants. Compared to adsorption, biodegradation, and chemical oxidation, photocatalytic oxidation can eliminate organic pollutants completely, conveniently, and cheaply in an environmentally friendly manner. Visible-light-driven photocatalytic oxidation is particularly advisable because of the high proportion of visible light energy in solar energy. Bismuth oxyiodide (BiOI) is a promising visible-light-driven photocatalyst for the oxidization of pollutants, not only because of its narrow band gap, but also for its relatively low valence band (VB), which is adequate for photogenerated holes to oxidize a variety of organic compounds. However, the shortcomings of BiOI powder, such the difficulty of recycling it, its low surface area, and fast carrier recombination, limit its practical applications. Meanwhile, the flexibility and hierarchical structure of photocatalysts are particularly advisable because these properties are beneficial for the convenient operation, recycling, and performance improvement of these materials. Herein, based on an electro-spun polyacrylonitrile (PAN) nanofiber substrate, a hierarchical BiOI/PAN fiber was prepared through an in situ reaction. In the as-prepared BiOI/PAN fibers, BiOI flakes were aligned vertically and uniformly around the PAN fibers. BiOI nuclei generated from pre-introduced Bi(Ⅲ) in the PAN fiber act as seeds for the growth of BiOI nanoplates, which is crucial for the formation of a hierarchical structure. Such a hierarchical structure can improve both the light absorption and carrier generation of the BiOI/PAN fibers, as demonstrated by UV-Vis diffuse reflectance spectra and photoluminescence emission. Therefore, the BiOI/PAN fibers exhibited higher photocatalytic activity than BiOI powder. When the BiOI/PAN fibers were decorated with pre-prepared graphene quantum dots (GQDs), a GQD-modified BiOI/PAN fibrous composite (GQD-BiOI/PAN) was fabricated. The morphology of the obtained GQD-BiOI/PAN fibers was nearly the same as that of the BiOI/PAN fibers. A step-scheme (S-scheme) heterojunction was formed between the GQDs and BiOI, which was confirmed by the fabrication method, photoluminescence emission, reactive radical tests, and XPS analysis. This kind of S-scheme heterojunction can not only effectively suppress the recombination of photogenerated holes, but can also reserve the more reductive electrons on the lowest unoccupied molecular orbital of GQDs and the more oxidative holes on the VB of BiOI, for the photocatalytic degradation of phenol. Because of the fibrous hierarchical structure and S-scheme heterojunction, GQD-BiOI/PAN outperformed BiOI nanoparticles and BiOI/PAN nanofibers in the photocatalytic oxidation of phenol under visible light. In addition, because of tight bonding, GQD-BiOI/PAN can be tailored and operated by hand, which is convenient for recycling. During recycling, no obvious loss of sample or decrease in photocatalytic activity was observed. This work provides a new pathway for the fabrication of flexible photocatalysts and a new insight into the enhancement of photocatalysts. ![]()
In environment remediation, photocatalytic oxidation is a promising technique for removing organic pollutants. Compared to adsorption, biodegradation, and chemical oxidation, photocatalytic oxidation can eliminate organic pollutants completely, conveniently, and cheaply in an environmentally friendly manner. Visible-light-driven photocatalytic oxidation is particularly advisable because of the high proportion of visible light energy in solar energy. Bismuth oxyiodide (BiOI) is a promising visible-light-driven photocatalyst for the oxidization of pollutants, not only because of its narrow band gap, but also for its relatively low valence band (VB), which is adequate for photogenerated holes to oxidize a variety of organic compounds. However, the shortcomings of BiOI powder, such the difficulty of recycling it, its low surface area, and fast carrier recombination, limit its practical applications. Meanwhile, the flexibility and hierarchical structure of photocatalysts are particularly advisable because these properties are beneficial for the convenient operation, recycling, and performance improvement of these materials. Herein, based on an electro-spun polyacrylonitrile (PAN) nanofiber substrate, a hierarchical BiOI/PAN fiber was prepared through an in situ reaction. In the as-prepared BiOI/PAN fibers, BiOI flakes were aligned vertically and uniformly around the PAN fibers. BiOI nuclei generated from pre-introduced Bi(Ⅲ) in the PAN fiber act as seeds for the growth of BiOI nanoplates, which is crucial for the formation of a hierarchical structure. Such a hierarchical structure can improve both the light absorption and carrier generation of the BiOI/PAN fibers, as demonstrated by UV-Vis diffuse reflectance spectra and photoluminescence emission. Therefore, the BiOI/PAN fibers exhibited higher photocatalytic activity than BiOI powder. When the BiOI/PAN fibers were decorated with pre-prepared graphene quantum dots (GQDs), a GQD-modified BiOI/PAN fibrous composite (GQD-BiOI/PAN) was fabricated. The morphology of the obtained GQD-BiOI/PAN fibers was nearly the same as that of the BiOI/PAN fibers. A step-scheme (S-scheme) heterojunction was formed between the GQDs and BiOI, which was confirmed by the fabrication method, photoluminescence emission, reactive radical tests, and XPS analysis. This kind of S-scheme heterojunction can not only effectively suppress the recombination of photogenerated holes, but can also reserve the more reductive electrons on the lowest unoccupied molecular orbital of GQDs and the more oxidative holes on the VB of BiOI, for the photocatalytic degradation of phenol. Because of the fibrous hierarchical structure and S-scheme heterojunction, GQD-BiOI/PAN outperformed BiOI nanoparticles and BiOI/PAN nanofibers in the photocatalytic oxidation of phenol under visible light. In addition, because of tight bonding, GQD-BiOI/PAN can be tailored and operated by hand, which is convenient for recycling. During recycling, no obvious loss of sample or decrease in photocatalytic activity was observed. This work provides a new pathway for the fabrication of flexible photocatalysts and a new insight into the enhancement of photocatalysts.
2021, 37(6): 200806
doi: 10.3866/PKU.WHXB202008064
Abstract:
Titania (TiO2) has been among the most widely investigated and used metal oxides over the past years, as it has various functional applications. Extensive research into TiO2 and industrial interest in this material have been triggered by its high abundance, excellent corrosion resistance, and low cost. To improve the activity of TiO2 in heterogeneous catalytic reactions, noble metals are used to accelerate the reactions. However, in the case of nanoparticles supported on TiO2, the active sites are usually limited to the peripheral sites of the noble metal particles or at the interface between the particle and the support. Thus, highly dispersed single metal atoms are desired for the effective utilization of precious noble metals. The study of oxide-supported isolated atoms, the so-called single-atom catalysts (SACs), was pioneered by Zhang's group. The high dispersion of precious noble metals results helps reduce the cost associated with catalyst preparation. Because of the presence of active centers as single atoms, the deactivation of metal atoms during the reaction, e.g., by coking for large agglomerates, is retarded. The unique coordination environment of the noble metal center provides special sites for the reaction, consequently increasing the selectivity of the reaction, including the enantioselectivity and stereoselectivity. Hence, supported SACs can bridge homogenous and heterogeneous reactions in solution as they provide selective reaction sites and are recyclable. Moreover, owing to the high site homogeneity of the isolated metal atoms, SACs are ideal models for establishing the structure-activity relationships. The present review provides an overview of recent works on the synthesis, characterization, and photocatalytic applications of SACs (Pt1, Pd1, Ir1, Rh1, Cu1, Ru1) supported on TiO2. The preparation of single atoms on TiO2 includes the creation of surface defective sites, surface modification, stabilization by high-temperature shockwave treatment, and metal-ligand self-assembly. Conventional characterization methods are categorized as microscopic imaging and spectroscopic methods, such as aberration-corrected scanning transmission electron microscopy (STEM), scanning tunneling microscopy (STM), extended X-ray absorption fine structure analysis (EXAFS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). We attempted to address the critical factors that lead to the stabilization of single-metal atoms on TiO2, and elucidate the mechanism underlying the photocatalytic hydrogen evolution and CO2 reduction. Although many fascinating applications of TiO2-supported SACs in photocatalysis could only be addressed superficially and in a referencing manner, we hope to provide interested readers with guidelines based on the wide literature, and more specifically, to provide a comprehensive overview of TiO2-supported SACs.
Titania (TiO2) has been among the most widely investigated and used metal oxides over the past years, as it has various functional applications. Extensive research into TiO2 and industrial interest in this material have been triggered by its high abundance, excellent corrosion resistance, and low cost. To improve the activity of TiO2 in heterogeneous catalytic reactions, noble metals are used to accelerate the reactions. However, in the case of nanoparticles supported on TiO2, the active sites are usually limited to the peripheral sites of the noble metal particles or at the interface between the particle and the support. Thus, highly dispersed single metal atoms are desired for the effective utilization of precious noble metals. The study of oxide-supported isolated atoms, the so-called single-atom catalysts (SACs), was pioneered by Zhang's group. The high dispersion of precious noble metals results helps reduce the cost associated with catalyst preparation. Because of the presence of active centers as single atoms, the deactivation of metal atoms during the reaction, e.g., by coking for large agglomerates, is retarded. The unique coordination environment of the noble metal center provides special sites for the reaction, consequently increasing the selectivity of the reaction, including the enantioselectivity and stereoselectivity. Hence, supported SACs can bridge homogenous and heterogeneous reactions in solution as they provide selective reaction sites and are recyclable. Moreover, owing to the high site homogeneity of the isolated metal atoms, SACs are ideal models for establishing the structure-activity relationships. The present review provides an overview of recent works on the synthesis, characterization, and photocatalytic applications of SACs (Pt1, Pd1, Ir1, Rh1, Cu1, Ru1) supported on TiO2. The preparation of single atoms on TiO2 includes the creation of surface defective sites, surface modification, stabilization by high-temperature shockwave treatment, and metal-ligand self-assembly. Conventional characterization methods are categorized as microscopic imaging and spectroscopic methods, such as aberration-corrected scanning transmission electron microscopy (STEM), scanning tunneling microscopy (STM), extended X-ray absorption fine structure analysis (EXAFS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). We attempted to address the critical factors that lead to the stabilization of single-metal atoms on TiO2, and elucidate the mechanism underlying the photocatalytic hydrogen evolution and CO2 reduction. Although many fascinating applications of TiO2-supported SACs in photocatalysis could only be addressed superficially and in a referencing manner, we hope to provide interested readers with guidelines based on the wide literature, and more specifically, to provide a comprehensive overview of TiO2-supported SACs.
2021, 37(6): 200903
doi: 10.3866/PKU.WHXB202009030
Abstract:
Solar energy is the largest renewable energy source in the world and the primary energy source of wind energy, tidal energy, biomass energy, and fossil fuel. Photocatalysis technology is a sunlight-driven chemical reaction process on the surface of photocatalysts that can generate H2 from water, decompose organic contaminants, and reduce CO2 into organic fuels. As a metal-free polymeric material, graphite-like carbon nitride (g-C3N4) has attracted significant attention because of its special band structure, easy fabrication, and low costs. However, some bottlenecks still limit its photocatalytic performance. To date, numerous strategies have been employed to optimize the photoelectric properties of g-C3N4, such as element doping, functional group modification, and construction of heterojunctions. Remarkably, these modification strategies are strongly associated with the surface behavior of g-C3N4, which plays a key role in efficient photocatalytic performance. In this review, we endeavor to provide a comprehensive summary of g-C3N4-based photocatalysts prepared through typical surface modification strategies (surface functionalization and construction of heterojunctions) and elaborate their special light-excitation and response mechanism, photo-generated carrier transfer route, and surface catalytic reaction in detail under visible-light irradiation. Moreover, the potential applications of the surface-modified g-C3N4-based photocatalysts for photocatalytic H2 generation and reduction of CO2 into fuels are summarized. Finally, based on the current research, the key challenges that should be further studied and overcome are highlighted. The following are the objectives that future studies need to focus on: (1) Although considerable effort has been made to develop a surface modification strategy for g-C3N4, its photocatalytic efficiency is still too low to meet industrial application standards. The currently obtained solar-to‑hydrogen (STH) conversion efficiency of g-C3N4 for H2 generation is approximately 2%, which is considerably lower than the commercial standards of 10%. Thus, the regulation of the surface/textural properties and electronic band structure of g-C3N4 should be further elucidated to improve its photocatalytic performance. (2) Significant challenges remain in the design and construction of g-C3N4-based S-scheme heterojunction photocatalysts by facile, low-cost, and reliable methods. To overcome the limitations of conventional heterojunctions thoroughly, a promising S-scheme heterojunction photocatalytic system was recently reported. The study further clarifies the charge transfer route and mechanism during the catalytic process. Thus, the rational design and synthesis of g-C3N4-based S-scheme heterojunctions will attract extensive scientific interest in the next few years in this field. (3) First-principle calculation is an effective strategy to study the optical, electrical, magnetic, and other physicochemical properties of surface strategy modified g-C3N4, providing important information to reveal the charge transfer path and intrinsic catalytic mechanism. As a result, density functional theory (DFT) computation will be paid increasing attention and widely applied in surface-modified g-C3N4-based photocatalysts.
Solar energy is the largest renewable energy source in the world and the primary energy source of wind energy, tidal energy, biomass energy, and fossil fuel. Photocatalysis technology is a sunlight-driven chemical reaction process on the surface of photocatalysts that can generate H2 from water, decompose organic contaminants, and reduce CO2 into organic fuels. As a metal-free polymeric material, graphite-like carbon nitride (g-C3N4) has attracted significant attention because of its special band structure, easy fabrication, and low costs. However, some bottlenecks still limit its photocatalytic performance. To date, numerous strategies have been employed to optimize the photoelectric properties of g-C3N4, such as element doping, functional group modification, and construction of heterojunctions. Remarkably, these modification strategies are strongly associated with the surface behavior of g-C3N4, which plays a key role in efficient photocatalytic performance. In this review, we endeavor to provide a comprehensive summary of g-C3N4-based photocatalysts prepared through typical surface modification strategies (surface functionalization and construction of heterojunctions) and elaborate their special light-excitation and response mechanism, photo-generated carrier transfer route, and surface catalytic reaction in detail under visible-light irradiation. Moreover, the potential applications of the surface-modified g-C3N4-based photocatalysts for photocatalytic H2 generation and reduction of CO2 into fuels are summarized. Finally, based on the current research, the key challenges that should be further studied and overcome are highlighted. The following are the objectives that future studies need to focus on: (1) Although considerable effort has been made to develop a surface modification strategy for g-C3N4, its photocatalytic efficiency is still too low to meet industrial application standards. The currently obtained solar-to‑hydrogen (STH) conversion efficiency of g-C3N4 for H2 generation is approximately 2%, which is considerably lower than the commercial standards of 10%. Thus, the regulation of the surface/textural properties and electronic band structure of g-C3N4 should be further elucidated to improve its photocatalytic performance. (2) Significant challenges remain in the design and construction of g-C3N4-based S-scheme heterojunction photocatalysts by facile, low-cost, and reliable methods. To overcome the limitations of conventional heterojunctions thoroughly, a promising S-scheme heterojunction photocatalytic system was recently reported. The study further clarifies the charge transfer route and mechanism during the catalytic process. Thus, the rational design and synthesis of g-C3N4-based S-scheme heterojunctions will attract extensive scientific interest in the next few years in this field. (3) First-principle calculation is an effective strategy to study the optical, electrical, magnetic, and other physicochemical properties of surface strategy modified g-C3N4, providing important information to reveal the charge transfer path and intrinsic catalytic mechanism. As a result, density functional theory (DFT) computation will be paid increasing attention and widely applied in surface-modified g-C3N4-based photocatalysts.
2021, 37(6): 200903
doi: 10.3866/PKU.WHXB202009038
Abstract:
Recently, extensive studies have been carried out to synthesize spherical microassemblies with hollow interiors and specific surface functionalizations, which usually exhibit fascinating enhanced or emerging properties and have promising applications in catalysis, photocatalysis, energy conversion and storage, biomedical applications, etc. With particular emphasis on the results obtained mainly by the authors' research group, this review provides a brief summary of the recent progress on the fabrication and potential photocatalytic applications of fluorinated TiO2 porous hollow microspheres(F-TiO2 PHMs). The synthesis strategies for F-TiO2 PHMs include a simplified two-step templating method and template-free method based on the fluoride-mediated self-transformation(FMST) mechanism. Compared to the two-step templating method, the template formation, coating, and removal steps for the FMST method are programmatically proceeded in "black-box"-like one-pot reactions without additional manual steps. The four underlying steps involved in the fabrication of F-TiO2 PHMs through the FMST pathway, nucleation, self-assembly, surface recrystallization, and self-transformation, are presented. By controlling these four steps in the FMST pathway, F-TiO2 PHMs can be successfully fabricated with a high yield by a simple one-pot hydrothermal treatment. The multi-level microstructural characteristics(including the interior cavity and hierarchical porosity) and compositions of hollow TiO2 microspheres as well as the primary building blocks can be well tailored. The unique superstructures of the F-TiO2 PHM photocatalysts provide advantages for photocatalytic applications by improving the light harvesting, mass transfer, and membrane antifouling. In addition, the in situ-introduced surface fluorine species during the formation of F-TiO2 PHMs provide significant surface fluorination effects, which are not only favorable for the adsorption and activation of reactant molecules, but also beneficial for surface trapping and interfacial transfer of photo-excited electrons and holes. Moreover, the porous hollow superstructures exhibit considerably better compatibility and tolerance to guest modifications, and thus the photocatalytic performances of F-TiO2 PHMs can be increased by synergetic host and guest modifications, such as ion doping, group functionalization, and nanoparticle loading. The light-harvesting range and intensity can be increased, the charge recombination can be reduced, mass transfer and adsorption can be promoted, and the surface reactivity can be tuned by introducing specific surface functionalities or nanoparticular cocatalysts. Consequently, the entire photocatalytic process can be systematically modulated to optimize the overall photocatalytic performance. The as-prepared F-TiO2 PHMs typically integrate the merits of interior cavity, hierarchical porosity, and surface fluorination and are open to synergetic host-guest modifications, which provides abundant compositional/structural parameters and specific physicochemical properties for systematically modulating the interconnected photocatalytic processes and promising potential photocatalytic applications.
Recently, extensive studies have been carried out to synthesize spherical microassemblies with hollow interiors and specific surface functionalizations, which usually exhibit fascinating enhanced or emerging properties and have promising applications in catalysis, photocatalysis, energy conversion and storage, biomedical applications, etc. With particular emphasis on the results obtained mainly by the authors' research group, this review provides a brief summary of the recent progress on the fabrication and potential photocatalytic applications of fluorinated TiO2 porous hollow microspheres(F-TiO2 PHMs). The synthesis strategies for F-TiO2 PHMs include a simplified two-step templating method and template-free method based on the fluoride-mediated self-transformation(FMST) mechanism. Compared to the two-step templating method, the template formation, coating, and removal steps for the FMST method are programmatically proceeded in "black-box"-like one-pot reactions without additional manual steps. The four underlying steps involved in the fabrication of F-TiO2 PHMs through the FMST pathway, nucleation, self-assembly, surface recrystallization, and self-transformation, are presented. By controlling these four steps in the FMST pathway, F-TiO2 PHMs can be successfully fabricated with a high yield by a simple one-pot hydrothermal treatment. The multi-level microstructural characteristics(including the interior cavity and hierarchical porosity) and compositions of hollow TiO2 microspheres as well as the primary building blocks can be well tailored. The unique superstructures of the F-TiO2 PHM photocatalysts provide advantages for photocatalytic applications by improving the light harvesting, mass transfer, and membrane antifouling. In addition, the in situ-introduced surface fluorine species during the formation of F-TiO2 PHMs provide significant surface fluorination effects, which are not only favorable for the adsorption and activation of reactant molecules, but also beneficial for surface trapping and interfacial transfer of photo-excited electrons and holes. Moreover, the porous hollow superstructures exhibit considerably better compatibility and tolerance to guest modifications, and thus the photocatalytic performances of F-TiO2 PHMs can be increased by synergetic host and guest modifications, such as ion doping, group functionalization, and nanoparticle loading. The light-harvesting range and intensity can be increased, the charge recombination can be reduced, mass transfer and adsorption can be promoted, and the surface reactivity can be tuned by introducing specific surface functionalities or nanoparticular cocatalysts. Consequently, the entire photocatalytic process can be systematically modulated to optimize the overall photocatalytic performance. The as-prepared F-TiO2 PHMs typically integrate the merits of interior cavity, hierarchical porosity, and surface fluorination and are open to synergetic host-guest modifications, which provides abundant compositional/structural parameters and specific physicochemical properties for systematically modulating the interconnected photocatalytic processes and promising potential photocatalytic applications.
2021, 37(6): 201001
doi: 10.3866/PKU.WHXB202010017
Abstract:
Inspired by the photosynthesis of green plants, various artificial photosynthetic systems have been proposed to solve the energy shortage and environmental problems. Water photosplitting, carbon dioxide photoreduction, and nitrogen photofixation are the main systems that are used to produce solar fuels such as hydrogen, methane, or ammonia. Although conducting artificial photosynthesis using man-made semiconducting materials is an ideal and potential approach to obtain solar energy, constructing an efficient photosynthetic system capable of producing solar fuels at a scale and cost that can compete with fossil fuels remains challenging. Therefore, exploiting the efficient and low-cost photocatalysts is crucial for boosting the three main photocatalytic processes (light-harvesting, surface/interface catalytic reactions, and charge generation and separation) of artificial photosynthetic systems. Among the various photocatalysts developed, the Z-scheme heterojunction composite system can increase the light-harvesting ability and remarkably suppress charge carrier recombination; it can also promote surface/interface catalytic reactions by preserving the strong reductive/oxidative capacity of the photoexcited electrons/holes, and therefore, it has attracted considerable attention. The continuing progress of Z-scheme nanostructured heterojunctions, which convert solar energy into chemical energy through photocatalytic processes, has witnessed the importance of these heterojunctions in further improving the overall efficiency of photocatalytic reaction systems for producing solar fuels. This review summarizes the progress of Z-scheme heterojunctions as photocatalysts and the advantages of using the direct Z-scheme heterojunctions over the traditional type Ⅱ, all-solid-state Z-schemel, and liquid-phase Z-scheme ones. The basic principle and corresponding mechanism of the two-step excitation are illustrated. In particular, applications of various types of Z-scheme nanostructured materials (inorganic, organic, and inorganic-organic hybrid materials) in photocatalytic energy conversion and different controlling/engineering strategies (such as extending the spectral absorption region, promoting charge transfer/separation and surface chemical modification) for enhancing the photocatalytic efficiency in the last five years are highlighted. Additionally, characterization methods (such as sacrificial reagent experiment, metal loading, radical trapping testing, in situ X-ray photoelectron spectroscopy, photocatalytic reduction experiments, Kelvin probe force microscopy, surface photovoltage spectroscopy, transient absorption spectroscopy, and theoretical calculation) of the Z-scheme photocatalytic mechanism, and the assessment criteria and methods of the photocatalytic performance are discussed. Finally, the challenges associated with Z-scheme heterojunctions and the possible growing trend are presented. We believe that this review will provide a new understanding of the breakthrough direction of photocatalytic performance and provide guidance for designing and constructing novel Z-scheme photocatalysts. ![]()
Inspired by the photosynthesis of green plants, various artificial photosynthetic systems have been proposed to solve the energy shortage and environmental problems. Water photosplitting, carbon dioxide photoreduction, and nitrogen photofixation are the main systems that are used to produce solar fuels such as hydrogen, methane, or ammonia. Although conducting artificial photosynthesis using man-made semiconducting materials is an ideal and potential approach to obtain solar energy, constructing an efficient photosynthetic system capable of producing solar fuels at a scale and cost that can compete with fossil fuels remains challenging. Therefore, exploiting the efficient and low-cost photocatalysts is crucial for boosting the three main photocatalytic processes (light-harvesting, surface/interface catalytic reactions, and charge generation and separation) of artificial photosynthetic systems. Among the various photocatalysts developed, the Z-scheme heterojunction composite system can increase the light-harvesting ability and remarkably suppress charge carrier recombination; it can also promote surface/interface catalytic reactions by preserving the strong reductive/oxidative capacity of the photoexcited electrons/holes, and therefore, it has attracted considerable attention. The continuing progress of Z-scheme nanostructured heterojunctions, which convert solar energy into chemical energy through photocatalytic processes, has witnessed the importance of these heterojunctions in further improving the overall efficiency of photocatalytic reaction systems for producing solar fuels. This review summarizes the progress of Z-scheme heterojunctions as photocatalysts and the advantages of using the direct Z-scheme heterojunctions over the traditional type Ⅱ, all-solid-state Z-schemel, and liquid-phase Z-scheme ones. The basic principle and corresponding mechanism of the two-step excitation are illustrated. In particular, applications of various types of Z-scheme nanostructured materials (inorganic, organic, and inorganic-organic hybrid materials) in photocatalytic energy conversion and different controlling/engineering strategies (such as extending the spectral absorption region, promoting charge transfer/separation and surface chemical modification) for enhancing the photocatalytic efficiency in the last five years are highlighted. Additionally, characterization methods (such as sacrificial reagent experiment, metal loading, radical trapping testing, in situ X-ray photoelectron spectroscopy, photocatalytic reduction experiments, Kelvin probe force microscopy, surface photovoltage spectroscopy, transient absorption spectroscopy, and theoretical calculation) of the Z-scheme photocatalytic mechanism, and the assessment criteria and methods of the photocatalytic performance are discussed. Finally, the challenges associated with Z-scheme heterojunctions and the possible growing trend are presented. We believe that this review will provide a new understanding of the breakthrough direction of photocatalytic performance and provide guidance for designing and constructing novel Z-scheme photocatalysts.
2021, 37(6): 201103
doi: 10.3866/PKU.WHXB202011033
Abstract:
At present, more than 80% of the world's energy demand is fulfilled by the burning of fossil fuels, which has caused the production of a large amount of greenhouse gases, leading to global warming and damage to the environment. The high consumption of fossil fuels every year causes the energy crisis to become increasingly serious. Finding a sustainable and pollution-free energy source is therefore essential. Among all forms of energy sources, solar energy is preferred because of its cleanliness and inexhaustible availability. The energy provided by one year of sunlight is more than 100 times the total energy in known fossil fuel reserves worldwide; however, the extent of solar energy currently used by mankind each year is minute; thus developments in solar energy are imperative. To address the urgent need for a renewable energy supply and to solve environmental problems, a variety of technologies in the field of photocatalysis have been developed. Photocatalytic technology has attracted significant attention because of its superior ability to convert clean solar energy into chemical fuels. Among the photocatalytic materials emerging in an endless stream, perovskite oxide, with the general formula of ABO3, has great potential in the fields of solar cells and photocatalysis as each site can be replaced by a variety of cations. Furthermore, owing to its unique properties such as high activity, robust stability, and facile structure adjustment, perovskite oxide photocatalysts have been widely used in water decomposition, carbon dioxide reduction and conversion, and nitrogen fixation. In terms of carbon dioxide reduction, oxide perovskites can achieve precise band gap and band edge tuning owing to its long charge diffusion length and flexibility in composition. For the development and utilization of solar energy in the environmental field, perovskite oxide and its derivatives (layered perovskite oxide) are used as photocatalysts for water decomposition and environmental remediation. In terms of nitrogen fixation, the conventional Haber-Bosh process for ammonia synthesis, which has been widely used in the past, requires high temperature and high energy. Therefore, we summarize the recent advances in perovskite oxide photocatalysts for nitrogen fixation from the aspect of activating the adsorbed N2 by weakening the N\begin{document}$ \equiv $\end{document} ![]()
At present, more than 80% of the world's energy demand is fulfilled by the burning of fossil fuels, which has caused the production of a large amount of greenhouse gases, leading to global warming and damage to the environment. The high consumption of fossil fuels every year causes the energy crisis to become increasingly serious. Finding a sustainable and pollution-free energy source is therefore essential. Among all forms of energy sources, solar energy is preferred because of its cleanliness and inexhaustible availability. The energy provided by one year of sunlight is more than 100 times the total energy in known fossil fuel reserves worldwide; however, the extent of solar energy currently used by mankind each year is minute; thus developments in solar energy are imperative. To address the urgent need for a renewable energy supply and to solve environmental problems, a variety of technologies in the field of photocatalysis have been developed. Photocatalytic technology has attracted significant attention because of its superior ability to convert clean solar energy into chemical fuels. Among the photocatalytic materials emerging in an endless stream, perovskite oxide, with the general formula of ABO3, has great potential in the fields of solar cells and photocatalysis as each site can be replaced by a variety of cations. Furthermore, owing to its unique properties such as high activity, robust stability, and facile structure adjustment, perovskite oxide photocatalysts have been widely used in water decomposition, carbon dioxide reduction and conversion, and nitrogen fixation. In terms of carbon dioxide reduction, oxide perovskites can achieve precise band gap and band edge tuning owing to its long charge diffusion length and flexibility in composition. For the development and utilization of solar energy in the environmental field, perovskite oxide and its derivatives (layered perovskite oxide) are used as photocatalysts for water decomposition and environmental remediation. In terms of nitrogen fixation, the conventional Haber-Bosh process for ammonia synthesis, which has been widely used in the past, requires high temperature and high energy. Therefore, we summarize the recent advances in perovskite oxide photocatalysts for nitrogen fixation from the aspect of activating the adsorbed N2 by weakening the N
2021, 37(6): 200909
doi: 10.3866/PKU.WHXB202009097
Abstract:
The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO2 has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO2 nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO2 NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO2 NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO2 NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn2S4). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO2 NFs, we report a 2D/1D ZnIn2S4/TiO2 S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn2S4/TiO2 S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn2S4nanosheets decorated on 1D TiO2 NFs. The loading of ZnIn2S4 nanoplates on the TiO2 NFs could be easily controlled by adjusting the molar ratios of ZnIn2S4 precursors to TiO2 NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn2S4/TiO2 composites was significantly improved, and the obtained ZnIn2S4/TiO2 composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn2S4/TiO2= 0.5) sample was 8774 μmol·g-1·h-1, which is considerably higher than those of pure TiO2 NFs (3312 μmol·g-1·h-1) and ZnIn2S4nanoplates (3114 μmol·g-1·h-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn2S4 and TiO2 was proposed to interpret the enhanced HER activity of the ZnIn2S4/TiO2heterojunctionphotocatalysts. ![]()
The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO2 has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO2 nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO2 NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO2 NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO2 NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn2S4). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO2 NFs, we report a 2D/1D ZnIn2S4/TiO2 S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn2S4/TiO2 S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn2S4nanosheets decorated on 1D TiO2 NFs. The loading of ZnIn2S4 nanoplates on the TiO2 NFs could be easily controlled by adjusting the molar ratios of ZnIn2S4 precursors to TiO2 NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn2S4/TiO2 composites was significantly improved, and the obtained ZnIn2S4/TiO2 composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn2S4/TiO2= 0.5) sample was 8774 μmol·g-1·h-1, which is considerably higher than those of pure TiO2 NFs (3312 μmol·g-1·h-1) and ZnIn2S4nanoplates (3114 μmol·g-1·h-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn2S4 and TiO2 was proposed to interpret the enhanced HER activity of the ZnIn2S4/TiO2heterojunctionphotocatalysts.
2021, 37(6): 201002
doi: 10.3866/PKU.WHXB202010024
Abstract:
2021, 37(6): 201204
doi: 10.3866/PKU.WHXB202012043
Abstract:
