Login In
2019 Volume 40 Issue 1
2019, 40(1):
Abstract:
2019, 40(1): 1-3
doi: 10.1016/S1872-2067(18)63188-2
Abstract:
2019, 40(1): 4-22
doi: 10.1016/S1872-2067(18)63177-8
Abstract:
Catalysts play decisive roles in determining the energy conversion efficiencies of energy devices. Up to now, various types of nanostructured materials have been studied as advanced electrocatalysts. This review highlights the application of one-dimensional (1D) metal electrocatalysts in energy conversion, focusing on two important reaction systems-direct methanol fuel cells and water splitting. In this review, we first give a broad introduction of electrochemical energy conversion. In the second section, we summarize the recent significant advances in the area of 1D metal nanostructured electrocatalysts for the electrochemical reactions involved in fuel cells and water splitting systems, including the oxygen reduction reaction, methanol oxidation reaction, hydrogen evolution reaction, and oxygen evolution reaction. Finally, based on the current studies on 1D nanostructures for energy electrocatalysis, we present a brief outlook on the research trend in 1D nanoelectrocatalysts for the two clean electrochemical energy conversion systems mentioned above.
Catalysts play decisive roles in determining the energy conversion efficiencies of energy devices. Up to now, various types of nanostructured materials have been studied as advanced electrocatalysts. This review highlights the application of one-dimensional (1D) metal electrocatalysts in energy conversion, focusing on two important reaction systems-direct methanol fuel cells and water splitting. In this review, we first give a broad introduction of electrochemical energy conversion. In the second section, we summarize the recent significant advances in the area of 1D metal nanostructured electrocatalysts for the electrochemical reactions involved in fuel cells and water splitting systems, including the oxygen reduction reaction, methanol oxidation reaction, hydrogen evolution reaction, and oxygen evolution reaction. Finally, based on the current studies on 1D nanostructures for energy electrocatalysis, we present a brief outlook on the research trend in 1D nanoelectrocatalysts for the two clean electrochemical energy conversion systems mentioned above.
2019, 40(1): 23-37
doi: 10.1016/S1872-2067(18)63161-4
Abstract:
Electrochemical CO2 reduction reaction (CO2RR) powered by renewable electricity has emerged as the most promising technique for CO2 conversion, making it possible to realize a carbon-neutral cycle. Highly efficient, robust, and cost-effective catalysts are highly demanded for the near-future practical applications of CO2RR. Previous studies on atomically dispersed metal-nitrogen (M-Nx) sites constituted of earth abundant elements with maximum atom-utilization efficiency have demonstrated their performance towards CO2RR. This review summarizes recent advances on a variety of M-Nx sites-containing transition metal-centered macrocyclic complexes, metal organic frameworks, and M-Nx-doped carbon materials for efficient CO2RR, including both experimental and theoretical studies. The roles of metal centers, coordinated ligands, and conductive supports on the intrinsic activity and selectivity, together with the importance of reaction conditions for improved performance are discussed. The mechanisms of CO2RR over these M-Nx-containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.
Electrochemical CO2 reduction reaction (CO2RR) powered by renewable electricity has emerged as the most promising technique for CO2 conversion, making it possible to realize a carbon-neutral cycle. Highly efficient, robust, and cost-effective catalysts are highly demanded for the near-future practical applications of CO2RR. Previous studies on atomically dispersed metal-nitrogen (M-Nx) sites constituted of earth abundant elements with maximum atom-utilization efficiency have demonstrated their performance towards CO2RR. This review summarizes recent advances on a variety of M-Nx sites-containing transition metal-centered macrocyclic complexes, metal organic frameworks, and M-Nx-doped carbon materials for efficient CO2RR, including both experimental and theoretical studies. The roles of metal centers, coordinated ligands, and conductive supports on the intrinsic activity and selectivity, together with the importance of reaction conditions for improved performance are discussed. The mechanisms of CO2RR over these M-Nx-containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.
2019, 40(1): 38-42
doi: 10.1016/S1872-2067(18)63190-0
Abstract:
Developing efficient water oxidation catalysts (WOCs) with earth-abundant elements still remains a challenging task for artificial photosynthesis. Iron-based WOC is a promising candidate because it is economically cheap, little toxic and environmentally friendly. In this study, we found that the catalytic water oxidation activity on amorphous iron-based oxide/hydroxide (FeOx) can be decreased by an order of magnitude after the dehydration process at room temperature. Thermogravimetric analysis, XRD and Raman results indicated that the dehydration process of FeOx at room temperature causes the almost completely loss of water molecule with no bulk structural changes. Based on this finding, we prepared hydrated ultrasmall (ca. 2.2 nm) FeOx nanoparticles of amorphous feature, which turns out to be extremely active as WOC with turnover frequency (TOF) up to 9.3 s-1 in the photocatalytic Ru(bpy)32+-Na2S2O8 system. Our findings suggest that future design of active iron-based oxides as WOCs requires the consideration of their hydration status.
Developing efficient water oxidation catalysts (WOCs) with earth-abundant elements still remains a challenging task for artificial photosynthesis. Iron-based WOC is a promising candidate because it is economically cheap, little toxic and environmentally friendly. In this study, we found that the catalytic water oxidation activity on amorphous iron-based oxide/hydroxide (FeOx) can be decreased by an order of magnitude after the dehydration process at room temperature. Thermogravimetric analysis, XRD and Raman results indicated that the dehydration process of FeOx at room temperature causes the almost completely loss of water molecule with no bulk structural changes. Based on this finding, we prepared hydrated ultrasmall (ca. 2.2 nm) FeOx nanoparticles of amorphous feature, which turns out to be extremely active as WOC with turnover frequency (TOF) up to 9.3 s-1 in the photocatalytic Ru(bpy)32+-Na2S2O8 system. Our findings suggest that future design of active iron-based oxides as WOCs requires the consideration of their hydration status.
2019, 40(1): 43-51
doi: 10.1016/S1872-2067(18)63175-4
Abstract:
The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal-air battery devices. Herein, an efficient liquid exfoliation strategy was designed for producing silk-like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn-air batteries. Because of the unique silk-like morphology and interface nanocrystal structure, they can catalyze the oxygen evolution reaction (OER) efficiently with a low overpotential of 233 mV at j=10 mA cm-2. This is an improvement from the recently reported catalysts in 1.0 M KOH. Meanwhile, the oxygen reduction reaction (ORR) activity of the silk-like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half-wave potential of 640 mV. In addition, the reversible oxygen electrode activity of the silk-like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V, based on the potential of the OER and ORR. Further, the homemade rechargeable Zn-air batteries using FeS2/NiS2 hybrid nanocrystals as the air-cathode displayed a high open-circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h. The solid Zn-air batteries exhibited an excellent rechargeable performance for 15 h. This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.
The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal-air battery devices. Herein, an efficient liquid exfoliation strategy was designed for producing silk-like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn-air batteries. Because of the unique silk-like morphology and interface nanocrystal structure, they can catalyze the oxygen evolution reaction (OER) efficiently with a low overpotential of 233 mV at j=10 mA cm-2. This is an improvement from the recently reported catalysts in 1.0 M KOH. Meanwhile, the oxygen reduction reaction (ORR) activity of the silk-like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half-wave potential of 640 mV. In addition, the reversible oxygen electrode activity of the silk-like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V, based on the potential of the OER and ORR. Further, the homemade rechargeable Zn-air batteries using FeS2/NiS2 hybrid nanocrystals as the air-cathode displayed a high open-circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h. The solid Zn-air batteries exhibited an excellent rechargeable performance for 15 h. This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.
2019, 40(1): 52-59
doi: 10.1016/S1872-2067(18)63167-5
Abstract:
Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure-directing agents (OSDAs), which are chronically hazardous to humans and the environment. It is a growing trend to develop an eco-friendly and nuisanceless OSDA for zeolite synthesis. Herein, choline is employed as a non-toxic and green OSDA to synthesize high silica Y zeolite with SiO2/Al2O3 ratios of 6.5-6.8. The prepared Y zeolite samples exhibited outstanding (hydro)thermal stability at ultrahigh temperature owing to the higher SiO2/Al2O3 ratio. The XRF, SEM, 29Si-NMR and 13Na+ results suggested that choline plays a structure-directing role in the synthesis of Y zeolite, while the feed molar fraction of Na+ is a crucial determinant for the framework SiO2/Al2O3 ratio and the crystal morphology.
Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure-directing agents (OSDAs), which are chronically hazardous to humans and the environment. It is a growing trend to develop an eco-friendly and nuisanceless OSDA for zeolite synthesis. Herein, choline is employed as a non-toxic and green OSDA to synthesize high silica Y zeolite with SiO2/Al2O3 ratios of 6.5-6.8. The prepared Y zeolite samples exhibited outstanding (hydro)thermal stability at ultrahigh temperature owing to the higher SiO2/Al2O3 ratio. The XRF, SEM, 29Si-NMR and 13Na+ results suggested that choline plays a structure-directing role in the synthesis of Y zeolite, while the feed molar fraction of Na+ is a crucial determinant for the framework SiO2/Al2O3 ratio and the crystal morphology.
2019, 40(1): 60-69
doi: 10.1016/S1872-2067(18)63170-5
Abstract:
Constructing nanocomposites that combine the advantages of composite materials, nanomaterials, and interfaces has been regarded as an important strategy to improve the photocatalytic activity of TiO2. In this study, 2D-2D TiO2 nanosheet/layered WS2 (TNS/WS2) heterojunctions were prepared via a hydrothermal method. The structure and morphology of the photocatalysts were systematically characterized. Layered WS2 (~4 layers) was wrapped on the surface of TiO2 nanosheets with a plate-to-plate stacked structure and connected with each other by W=O bonds. The as-prepared TNS/WS2 heterojunctions showed higher photocatalytic activity for the degradation of RhB under visible-light irradiation, than pristine TiO2 nanosheets and layered WS2. The improvement of photocatalytic activity was primarily attributed to enhanced charge separation efficiency, which originated from the perfect 2D-2D nanointerfaces and intimate interfacial contacts between TiO2 nanosheets and layered WS2. Based on experimental results, a double-transfer photocatalytic mechanism for the TNS/WS2 heterojunctions was proposed and discussed. This work provides new insights for synthesizing highly efficient and environmentally stable photocatalysts by engineering the surface heterojunctions.
Constructing nanocomposites that combine the advantages of composite materials, nanomaterials, and interfaces has been regarded as an important strategy to improve the photocatalytic activity of TiO2. In this study, 2D-2D TiO2 nanosheet/layered WS2 (TNS/WS2) heterojunctions were prepared via a hydrothermal method. The structure and morphology of the photocatalysts were systematically characterized. Layered WS2 (~4 layers) was wrapped on the surface of TiO2 nanosheets with a plate-to-plate stacked structure and connected with each other by W=O bonds. The as-prepared TNS/WS2 heterojunctions showed higher photocatalytic activity for the degradation of RhB under visible-light irradiation, than pristine TiO2 nanosheets and layered WS2. The improvement of photocatalytic activity was primarily attributed to enhanced charge separation efficiency, which originated from the perfect 2D-2D nanointerfaces and intimate interfacial contacts between TiO2 nanosheets and layered WS2. Based on experimental results, a double-transfer photocatalytic mechanism for the TNS/WS2 heterojunctions was proposed and discussed. This work provides new insights for synthesizing highly efficient and environmentally stable photocatalysts by engineering the surface heterojunctions.
2019, 40(1): 70-79
doi: 10.1016/S1872-2067(18)63160-2
Abstract:
Metal-organic framework MIL-100(Fe) and g-C3N4 heterojunctions (MG-x, x=5%, 10%, 20%, and 30%, x is the mass fraction of MIL-100(Fe) in the hybrids) were facilely fabricated through ball-milling and annealing, and characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, UV-visible diffuse-reflectance spectrometry, and photoluminescence emission spectrometry. The photocatalytic activities of the series of MG-x heterojunctions toward Cr(VI) reduction and diclofenac sodium degradation were tested upon irradiation with simulated sunlight. The influence of different organic compounds (ethanol, citric acid, oxalic acid, and diclofenac sodium) as hole scavengers and the pH values (2, 3, 4, 6, and 8) on the photocatalytic activities of the series of MG-x heterojunctions was investigated. MG-20% showed superior photocatalytic Cr(VI) reduction and diclofenac sodium degradation performance than did the individual MIL-100(Fe) and g-C3N4 because of the improved separation of photoinduced electron-hole charges, which was clarified via photoluminescence emission and electrochemical data. Moreover, the MG-x exhibited good reusability and stability after several runs.
Metal-organic framework MIL-100(Fe) and g-C3N4 heterojunctions (MG-x, x=5%, 10%, 20%, and 30%, x is the mass fraction of MIL-100(Fe) in the hybrids) were facilely fabricated through ball-milling and annealing, and characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, UV-visible diffuse-reflectance spectrometry, and photoluminescence emission spectrometry. The photocatalytic activities of the series of MG-x heterojunctions toward Cr(VI) reduction and diclofenac sodium degradation were tested upon irradiation with simulated sunlight. The influence of different organic compounds (ethanol, citric acid, oxalic acid, and diclofenac sodium) as hole scavengers and the pH values (2, 3, 4, 6, and 8) on the photocatalytic activities of the series of MG-x heterojunctions was investigated. MG-20% showed superior photocatalytic Cr(VI) reduction and diclofenac sodium degradation performance than did the individual MIL-100(Fe) and g-C3N4 because of the improved separation of photoinduced electron-hole charges, which was clarified via photoluminescence emission and electrochemical data. Moreover, the MG-x exhibited good reusability and stability after several runs.
2019, 40(1): 80-94
doi: 10.1016/S1872-2067(18)63172-9
Abstract:
Exfoliation of bulk graphitic carbon nitride (g-C3N4) into two-dimensional (2D) nanosheets is one of the effective strategies to improve its photocatalytic properties so that the 2D g-C3N4 nanosheets (CN) have larger specific surface areas and more reaction sites. In addition, poly-o-phenylenediamine (PoPD) can improve the electrical conductivity and photocatalytic activity of semiconductor materials. Here, the novel efficient composite PoPD/AgCl/g-C3N4 nanosheets was first synthesized by a precipitation reaction and the photoinitiated polymerization approach. The obtained photocatalysts have larger specific surface areas and could achieve better visible-light response. However, silver chloride (AgCl) is susceptible to agglomeration and photocorrosion. The PoPD/AgCl/CN composite exhibits an extremely high photocurrent density, which is three times that of CN. Obviously enhanced photocatalytic activities of PoPD/AgCl/g-C3N4 are revealed through the photodegradation of tetracycline. The stability of PoPD/AgCl/CN is demonstrated based on four cycles of experiments that reveal that the degradation rate only decreases slightly. Furthermore,·O2- and h+ are the main active species, which are confirmed through a trapping experiment and ESR spin-trap technique. Therefore, the prepared PoPD/AgCl/CN can be considered as a stable photocatalyst, in which PoPD is added as a charge carrier and acts a photosensitive protective layer on the surface of the AgCl particles. This provides a new technology for preparing highly stable composite photocatalysts that can effectively deal with environmental issues.
Exfoliation of bulk graphitic carbon nitride (g-C3N4) into two-dimensional (2D) nanosheets is one of the effective strategies to improve its photocatalytic properties so that the 2D g-C3N4 nanosheets (CN) have larger specific surface areas and more reaction sites. In addition, poly-o-phenylenediamine (PoPD) can improve the electrical conductivity and photocatalytic activity of semiconductor materials. Here, the novel efficient composite PoPD/AgCl/g-C3N4 nanosheets was first synthesized by a precipitation reaction and the photoinitiated polymerization approach. The obtained photocatalysts have larger specific surface areas and could achieve better visible-light response. However, silver chloride (AgCl) is susceptible to agglomeration and photocorrosion. The PoPD/AgCl/CN composite exhibits an extremely high photocurrent density, which is three times that of CN. Obviously enhanced photocatalytic activities of PoPD/AgCl/g-C3N4 are revealed through the photodegradation of tetracycline. The stability of PoPD/AgCl/CN is demonstrated based on four cycles of experiments that reveal that the degradation rate only decreases slightly. Furthermore,·O2- and h+ are the main active species, which are confirmed through a trapping experiment and ESR spin-trap technique. Therefore, the prepared PoPD/AgCl/CN can be considered as a stable photocatalyst, in which PoPD is added as a charge carrier and acts a photosensitive protective layer on the surface of the AgCl particles. This provides a new technology for preparing highly stable composite photocatalysts that can effectively deal with environmental issues.
2019, 40(1): 95-104
doi: 10.1016/S1872-2067(18)63184-5
Abstract:
A series of V2O5-WO3/TiO2-ZrO2, V2O5-WO3/TiO2-CeO2, and V2O5-WO3/TiO2-CeO2-ZrO2 catalysts were synthesized to improve the selective catalytic reduction (SCR) performance and the K-poisoning resistance of a V2O5-WO3/TiO2 catalyst. The physicochemical properties were investigated by using XRD, BET, NH3-TPD, H2-TPR, and XPS, and the catalytic performance and K-poisoning resistance were evaluated via a NH3-SCR model reaction. Ce4+ and Zr4+ co-doping were found to enhance the conversion of NOx, and exhibit the best K-poisoning resistance owing to the largest BET-specific surface area, pore volume, and total acid site concentration, as well as the minimal effects on the surface acidity and redox ability from K poisoning. The V2O5-WO3/TiO2-CeO2-ZrO2 catalyst also presents outstanding H2O + SO2 tolerance. Finally, the in situ DRIFTS reveals that the NH3-SCR reaction over the V2O5-WO3/TiO2-CeO2-ZrO2 catalyst follows an L-H mechanism, and that K poisoning does not change the reaction mechanism.
A series of V2O5-WO3/TiO2-ZrO2, V2O5-WO3/TiO2-CeO2, and V2O5-WO3/TiO2-CeO2-ZrO2 catalysts were synthesized to improve the selective catalytic reduction (SCR) performance and the K-poisoning resistance of a V2O5-WO3/TiO2 catalyst. The physicochemical properties were investigated by using XRD, BET, NH3-TPD, H2-TPR, and XPS, and the catalytic performance and K-poisoning resistance were evaluated via a NH3-SCR model reaction. Ce4+ and Zr4+ co-doping were found to enhance the conversion of NOx, and exhibit the best K-poisoning resistance owing to the largest BET-specific surface area, pore volume, and total acid site concentration, as well as the minimal effects on the surface acidity and redox ability from K poisoning. The V2O5-WO3/TiO2-CeO2-ZrO2 catalyst also presents outstanding H2O + SO2 tolerance. Finally, the in situ DRIFTS reveals that the NH3-SCR reaction over the V2O5-WO3/TiO2-CeO2-ZrO2 catalyst follows an L-H mechanism, and that K poisoning does not change the reaction mechanism.
2019, 40(1): 105-113
doi: 10.1016/S1872-2067(18)63164-X
Abstract:
Cu2O is a promising photocatalyst, but it suffers from poor photocatalytic activity and stability, especially for Cu2O cubes. Herein, we report the deposition of CuO and Au nanodomains on Cu2O cubes to form dual surface heterostructures (HCs) to improve photocatalytic activity and stability. The apparent quantum efficiency of Au/CuO/Cu2O HCs was ca. 123 times that of pristine Cu2O. In addition, the Au/CuO/Cu2O HCs maintained nearly 80% of its original activity after eight cycles in contrast to five cycles for the Au/Cu2O material. Therefore, CuO and Au domains greatly improved the photocatalytic activity and stability of the Cu2O cubes due to the synergistic effect of the HCs.
Cu2O is a promising photocatalyst, but it suffers from poor photocatalytic activity and stability, especially for Cu2O cubes. Herein, we report the deposition of CuO and Au nanodomains on Cu2O cubes to form dual surface heterostructures (HCs) to improve photocatalytic activity and stability. The apparent quantum efficiency of Au/CuO/Cu2O HCs was ca. 123 times that of pristine Cu2O. In addition, the Au/CuO/Cu2O HCs maintained nearly 80% of its original activity after eight cycles in contrast to five cycles for the Au/Cu2O material. Therefore, CuO and Au domains greatly improved the photocatalytic activity and stability of the Cu2O cubes due to the synergistic effect of the HCs.
2019, 40(1): 114-123
doi: 10.1016/S1872-2067(18)63192-4
Abstract:
Molecular nitrogen is relatively inert and the activation of its triple bond is full of challenges and of significance. Hence, searching for an efficiently heterogeneous catalyst with high stability and dispersion is one of the important targets of chemical technology. Here, we report a Ba-K/Ru-MC catalyst with Ru particle size of 1.5-2.5 nm semi-embedded in a mesoporous C matrix and with dual promoters of Ba and K that exhibits a higher activity than the supported Ba-Ru-K/MC catalyst, although both have similar metal particle sizes for ammonia synthesis. Further, the Ba-K/Ru-MC catalyst is more active than commercial fused Fe catalysts and supported Ru catalysts. Characterization techniques such as high-resolution transmission electron microscopy, N2 physisorption, CO chemisorption, and temperature-programmed reduction suggest that the Ru nanoparticles have strong interactions with the C matrix in Ba-K/Ru-MC, which may facilitate electron transport better than supported nanoparticles.
Molecular nitrogen is relatively inert and the activation of its triple bond is full of challenges and of significance. Hence, searching for an efficiently heterogeneous catalyst with high stability and dispersion is one of the important targets of chemical technology. Here, we report a Ba-K/Ru-MC catalyst with Ru particle size of 1.5-2.5 nm semi-embedded in a mesoporous C matrix and with dual promoters of Ba and K that exhibits a higher activity than the supported Ba-Ru-K/MC catalyst, although both have similar metal particle sizes for ammonia synthesis. Further, the Ba-K/Ru-MC catalyst is more active than commercial fused Fe catalysts and supported Ru catalysts. Characterization techniques such as high-resolution transmission electron microscopy, N2 physisorption, CO chemisorption, and temperature-programmed reduction suggest that the Ru nanoparticles have strong interactions with the C matrix in Ba-K/Ru-MC, which may facilitate electron transport better than supported nanoparticles.
