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Molecular-based porous polymers with precise sites for photoreduction of carbon dioxide

Wei-Jia Wang ,  Kaihong Chen

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Citation:  Wei-Jia Wang, Kaihong Chen. Molecular-based porous polymers with precise sites for photoreduction of carbon dioxide[J]. Chinese Chemical Letters, 2025, 36(1): 109998. doi: 10.1016/j.cclet.2024.109998 shu

Molecular-based porous polymers with precise sites for photoreduction of carbon dioxide

English

  • 1. Introduction

    With the increasing energy shortage and environmental problems, finding clean and renewable energy sources to replace fossil fuels has become an urgent task [1,2]. Large-scale deployment of artificial systems that mimic natural photosynthesis could accomplish solar energy storage, CO2 sequestration, and recycling of carbon back into fuels for energy consumption, thereby relieving our dependency on fossil fuels [3-9]. In recent years, solar-driven photocatalytic CO2 reduction reaction (CO2RR) has attracted growing attention and is regarded as a renewable and sustainable strategy. The core of CO2 photocatalytic technology lies in the development of photocatalysts that can absorb light and efficiently convert CO2 into “solar fuels” including carbon monoxide (CO), formic acid (HCOOH), methanol (CH3OH), methane (CH4) and so on (Fig. 1) [10-17].

    Figure 1

    Figure 1.  CO2RR to product solar fuel molecules and the reaction mechanism from semiconductor catalysts.
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    Photocatalytic CO2 reduction reactions are complex multistep processes, and their efficiency is influenced by several factors (Fig. 2) [18-26]. Firstly, the critical starting step is the absorption of light with energy equal to or greater than the bandgap by semiconductor photocatalyst, which generates photogenerated electrons and holes. To maximize the utilization of solar energy, it is desirable to use photocatalysts that can absorb visible light. The band structure is also an important factor in determining whether the photocatalytic reduction of CO2 can occur. To mimic natural photosynthesis, water should be used as the hole scavenger, meaning the bandgap of photocatalyst should straddle both the potentials for CO2 reduction and water oxidation. Better separation of photogenerated electrons and holes can bring a higher surface photogenerated electron density in photocatalysts, which can effectively accelerate multi-electron reduction reaction. Additionally, surface catalytic active sites and/or cocatalysts can enhance separation of photogenerated carriers and promote surface redox reactions. The adsorption and desorption of reactants, intermediates, and products also play a key role in reaction efficiency and product selectivity. Strong adsorption ability of reactants and easy desorption of the target product can result in a high yield of the desired product.

    Figure 2

    Figure 2.  Main factors influencing the product selectivity of photocatalytic CO2 reduction reactions.
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    Currently, significant progress has been made in the development of novel photoreduction CO2 systems [27,28]. Particulate photocatalysts, including metal oxide, metal sulphide, metal (oxy)nitride, have demonstrated successful applications in photocatalytic CO2RR [29-42]. However, this process is hindered by low charge separation and migration efficiency, inevitable electron-hole recombination, and the inert nature of CO2 molecules [43,44]. As a result, the quantum yield and lifetime of photocatalysts are still far behind the need for practical applications. Compared with these photocatalysts, porous polymers (PPs) such as covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), and conjugated microporous polymers (CMPs), offer the potential for higher CO2RR efficiency while providing opportunities to explore the structure–property relationship at the molecular level [45-56]. Additionally, the large surface area of PPs facilitates mass transport and ion migration during the reaction. Due to the tunable structure and large surface area, PPs can also serve as supports to stabilize and synergistically enhance the activity of active sites.

    In this review, we present a perspective on PPs with structurally well-defined active metal sites for CO2 photocatalytic reduction (Fig. 3). We focus on gaining a deeper understanding of how well-defined active sites of PPs can influence optical properties, photogenerated charge separation and transport, and overall photocatalytic performance. Furthermore, this review aims to explore the multi-chemical microenvironment of PPs to improve performances, especially selectivity, and provide inspiration for novel tailored designs of future photocatalytic CO2RR systems that are more efficient and stable. Ultimately, these advancements will drive innovations and commercialization in photocatalysis.

    Figure 3

    Figure 3.  Classification of precise active sites effects of PPs in photocatalytic CO2RR for improving reaction reactivity.
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    2. Superiority of PPs in photocatalytic CO2RR

    2.1 Effective CO2 activation

    CO2 is an exceptionally stable molecule due to the high C═O bonding energy (750 kJ/mol) [50]. Consequently, a substantial negative reduction potential of −1.9 V (vs. NHE) is required for the one-electron reduction of CO2 to generate CO2•− [57]. Additionally, the kinetic inertness of CO2, originating from its poor solubility in solvents and the multi-step process involving electron and proton transfer (Table 1 and Fig. 4), presents a bottleneck for CO2RR. Moreover, the presence of side reactions, such as H2 evolution reaction, can hinder the efficient utilization of photons for the desired product. To address these issues, one potential solution is to create CO2 activation sites on photocatalysts.

    Table 1

    Table 1.  Photocatalytic multielectron processes of CO2RR [61,62].
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    Figure 4

    Figure 4.  Proposed reaction paths for PPs photocatalytic CO2RR.
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    PPs have been recognized as ideal CO2 adsorbents that can adsorb CO2 and then activate it. Increasing the BET specific surface area and microporosity of PPs is one of commonly used approach to enhance CO2 adsorption capacity [58]. Modifying the surface structure of photocatalyst also proves to be an effective means to provide the active sites for CO2 adsorption. Three primary strategies have been developed in this regard, i.e., heteroatoms doping, defect engineering, and introducing CO2-philic groups to enhance the adsorption [59,60].

    2.2 Tunable band structures

    Upon the absorption of a photon with energy equal to or higher than the band gap, an electron is excited from the valence band maximum (VBM) to the conduction band minimum (CBM), leaving behind a hole as a quasiparticle [61-66]. Once spatially separated, these carriers can migrate to the surface for redox reactions [59]. To maximize light utilization, a smaller band gap will be highly desirable. Additionally, the band structure should straddle the potentials associated with CO2RR and oxygen evolution reaction (OER), when using water as the hole scavenger [67-74]. Screening photocatalysts with suitable band structures can be a time-consuming work. However, PPs provide a promising solution to this challenge as the band structure can be easily adjusted by varying the starting materials.

    2.3 Designable metal supporter

    Cocatalysts play a crucial role in photocatalysis as they facilitate charge separation/transport and catalyze surface redox reactions [75-77]. Furthermore, the complicate reaction process (Table 1) often leads to low product selectivity, which can be alleviated by the presence of a highly selective active center. Different metals lead to various kinetic and thermodynamic properties, thereby influencing the reaction pathway and the types of products. PPs, with their well-defined coordination environment and enhanced metal-support interactions, demonstrate remarkable catalytic performance in heterogeneous reactions [78-81]. Recent advancements in the implementation of molecular-based design for CO2 reduction have proven highlighted the importance of microenvironments and electronic properties of single-metal sites active centers in determining catalytic activity and selectivity [82-85]. PPs containing catalytically active metal centers enable precise control over atomic configuration. These designed PP materials allow fine-tuning of chelating abilities and steric effects of ligands, thereby facilitating accurate modulation of the local coordination environment and electronic properties of active centers. In addition, such metal cocatalyst possess unfilled d orbitals, making them highly receptive to CO2 adsorption and capable of forming intermediates with anchor effects at active sites.

    2.4 High stability in photocatalytic CO2RR

    The stability of catalyst is a critical parameter in photocatalytic CO2RR, as it determines the practical applicability of the catalyst [86]. The stability of PPs catalytic systems can be divided into two aspects: the stability of active sites and the stability of the PPs skeleton. During the catalytic reaction, active sites may aggregate or become poisoned, resulting in inactivity, and the skeleton may undergo collapse or breakage, resulting in reduced catalytic efficiency of the overall system [87]. To address these challenges, robust PPs skeletons, such as CTFs and olefin-linked COFs, have been developed and explored the inactivation mechanism [88].

    3. Application of porous polymer based catalysts in photocatalytic CO2 reduction reaction

    3.1 Photocatalytic CO2RR by COF based catalysis

    In 2005, Yaghi et al. discovered COFs, which provided hope for effective photocatalysts [89]. COFs are composed of various organic molecular building blocks that are ordered periodically through covalent bonds. These bonds include imine, triazine, β-ketoenamine, hydrazone, olefin, azine, and others [90]. The structural features of COF offer numerous advantages, such as suitable energy band structures, designability of periodic structures, high surface area, reactant accessibility, and low density. Given these inherent advantages and the potential impact on the global energy crisis [91-96], two main methods are used to develop a well-designed plan to further developing efficient system (Fig. 5).

    Figure 5

    Figure 5.  The effect of COF based catalysis for photocatalytic CO2RR. (a) Anchor effect on metalated-COF. (b) Support effect on COF based heterostructure.
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    Compared to other photocatalysts, COFs can combine porosity with crystallinity to stabilize intermediates for photocatalytic CO2RR. For example, an azine-based COF, N3COF, was shown to exhibit gas phase photocatalytic CO2 reduction ability [97]. However, several challenges remain, including limited visible-light harvesting ability, poor selectivity, and difficulty in separating photogenerated electron–hole pairs [98-103]. In this regard, particular attention is warranted in regulating the coordination spheres in single COF catalysts and fabricating COF heterojunctions to address these pressing challenges in CO2RR.

    COFs represent a wide class of materials that can alter the chemical environment through anchoring different types of metals and ligands for CO2RR catalysis. The photosensitive metal sites in COFs can transport photogenerated electrons, which typically act as active sites for initiating photocatalysis. This feature ensures high electron−hole separation and promotes high activity in photocatalysis. In a recent study by Huang et al., they reported a newly designed 2D COF incorporating a Re complex, which exhibited intrinsic light absorption and charge separation properties (Fig. 6a) [103]. This hybrid catalyst efficiently reduced CO2 to CO under visible light illumination with higher selectivity (98%) and activity than its homogeneous Re counterpart. More importantly, through advanced transient optical and X-ray absorption spectroscopy, as well as in situ diffuse reflectance spectroscopy, they unraveled three key intermediates (Re-COF−, TEOA+-Re-COF−, Re-COF-CO2 adduct) that are responsible for charge separation, the induction period, and rate limiting step in catalysis. This work not only demonstrates the potential of COFs as next generation photocatalysts for solar fuel conversion, but also provides unprecedented insight into the mechanistic origins of high product selectivity in light-driven CO2 reduction.

    Figure 6

    Figure 6.  Photosensitive metal Re site in COFs for PCO2RR. (a) The structure of 2D Re-COF Copied with permission [103]. Copyright 2018, American Chemical Society. (b) The structure of 2D bipyridine-containing COF with Re site. Copied with permission [104]. Copyright 2020, the Royal Society of Chemistry.
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    In addition, Cooper's group demonstrated that tethering a rhenium complex, [Re(bpy)(CO)3Cl], into a COF structure, results in a heterogeneous photocatalyst with a strong visible light absorption, high CO2 binding affinity, and improved catalytic performance compared to its homogeneous counterpart (Fig. 6b) [104]. This COF incorporates bipyridine sites, which allow for the ligation of the Re complex, into a π-conjugated backbone that is chemically robust and promotes light-harvesting.

    Another promising approach involves incorporating molecular catalytic components into the intrinsic pores of COFs, enabling the resultant composites to possess advantages of both homogeneous and heterogeneous catalysts. However, the binding ability of bipyridyl unit in COFs is not strong enough to stabilize active metal centers, leading to unavoidable metal leaching during CO2 reduction, even in the presence of excess bipyridyl units [105,106]. Porphyrin units, with stronger chelating coordination ability towards metal ions, offer a promising alternatives [107,108]. Consequently, metalloporphyrin-based COFs have been developed by introducing porphyrin units into the host frameworks. Ultrathin Co-porphyrin-based COF nanosheets and corresponding bulk materials show high durability and cyclability in visible-light-driven CO2-to-CO conversion [109]. Lan et al. demonstrated that crystalline porphyrin-tetrathiafulvalene COFs can serve as photocatalysts for reducing CO2 with H2O (Fig. 7a) [110]. Effective transfer of photogenerated electrons from tetrathiafulvalene to porphyrin via covalent bonding allows for separated electrons and holes for CO2 reduction and H2O oxidation, respectively. Tuning the metal ion of COF, these TTCOFs exhibited a broad visible-light absorption range, and the corresponding band gaps (Eg) were determined to be 1.15, 1.49, 1.33, and 1.39 eV for TTCOF-2H/Zn/Ni/Cu by Tauc plots, respectively. By adjusting the band structures of TTCOFs, TTCOF-Zn achieved higher CO evolution of 12.33 µmol under visible light illumination after 60 h than that of TTCOF-Cu (8.65 µmol) and TTCOF-Ni (0.462 µmol) with almost 100% selectivity, accompanied by H2O oxidation to O2 (Figs. 7b and c). In Jiang's work, by fine-tuning the inter-layer spacing of porphyrin-based 2D COFs (Fig. 8a) [111], MPor-DPPCOFs, showed excellent photocatalytic activity for CO2RR, with a CO generation rate of 10,200 µmol g–1 h–1 and a CO selectivity up to 82% (Figs. 8b and c).

    Figure 7

    Figure 7.  (a) The synthesis of TTCOF-M and (b, c) photocatalyst CO2RR performance. Copied with permission [110]. Copyright 2019, Wiley-VCH.
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    Figure 8

    Figure 8.  (a) The synthesis of MPor-DPP-COF and (b, c) photocatalyst CO2RR performance. Copied with permission [111]. Copyright 2022, American Chemical Society.
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    Considering the unambiguous structures, high density of catalytic sites, and strong conjugation ability of metalloporphyrin-based COFs [112,113], exploiting isostructural platforms based on them can offer valuable insights into the chemical interactions between metal active sites and the reagents/reactive intermediates during CO2 photoreduction. However, the activities of pristine COFs are still unsatisfactory partly due to photogenerated carriers easily recombination. To enhance the solar-to-fuel conversion efficiency, COF-based heterostructures combining COFs with metal-sulfides [114-119], metal-oxides [120-122], carbon materials [123,124], or MOFs [125,126], have gained increasing attention. These heterostructures facilitate interfacial photo-generated carrier separation and promote surface redox reactions. In Lan's work, “all solid states direct Z-Scheme heterostructure” has been proposed for photocatalytic CO2RR, COF-semiconductor Z-scheme photocatalysts combining COFs (COF-316/318) with water-oxidation semiconductors (TiO2, Bi2WO6, and α-Fe2O3) were synthesized, exhibiting high CO2-to-CO conversion efficiencies (up to 69.67 µmol g–1 h–1) using H2O as the only electron donor, without the need for additional photosensitizers or sacrificial agents (Fig. 9a) [113]. This marks the first report of covalently bonded COF/inorganic-semiconductor systems utilizing the Z-scheme for artificial photosynthesis. The key to achieving successful integration lies in the effective transfer of charge carriers between the semiconductor and the COF (Fig. 9b). Furthermore, specific active sites for CO2 reduction in the COF, such as pyridine (site-N) and cyano group (site-CN), were considered [113,127]. The pyridine group facilitates the first step of CO2 activation, then the cyano group promotes the proton-coupled electron-transfer process (*COO-*CO). The combination of pyridine and cyano groups leads to higher CO2 reduction activity.

    Figure 9

    Figure 9.  (a) COF-semiconductor Z-scheme system for artificial photosynthesis. (b) The charge-transfer process under light irradiation with the Z-scheme model. Copied with permission [113]. Copyright 2020, Wiley-VCH.
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    As discussed above, the interactions between the photocatalyst and CO2 play a crucial role in subsequent photocatalytic reduction. Herein, Liu et al. reported the 1D/2D heterojunction (COF-5/CoAl-LDH) by direct in-situ synthesis of the COF-5 colloid on the surface of CoAl layered double hydroxide (LDH) was used as the prospective photocatalyst for CO2 reduction (Fig. 10a) [128]. The CoAl-LDH is rich in metal atoms coordinated by six-fold hydroxyl groups, providing favorable adsorption of CO2 and stabilization of the intermediate COOH*. The band structure of COF and LDH contributes to a type II heterostructure, inhibiting the recombination of carriers generated by photon absorption of COF (Fig. 10b). Through the synergistic effect of promoted CO2 adsorption and enhanced charge separation, the optimal COF-5/CoAL-LDH heterostructure achieved a CO generation selectivity of 96.4% and a CO generation rate of 53 µmol g–1 h–1.

    Figure 10

    Figure 10.  (a) The synthesis of COF-5/CoAl-LDH nanocomposite and (b) proposed mechanism. Copied with permission [128]. Copyright 2022, Wiley-VCH.
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    The introduction of molecular catalytic components into the internal cavities of COFs is a promising method that combines the advantages of homogeneous and heterogeneous catalysts [129-133]. In the work of Wang et al., carbon quantum dots were prepared from the pyrolysis of metalloporphyrin (M-PCD) and immobilized in the pores of as-synthesized TD COF via sonication and thermal treatment under N2 (Fig. 11a) [134]. This configuration enables the adsorption of CO2 and prevents the leaching of the carbon quantum dots. The resulting M-PCD@TD-COF heterostructure exhibits a CO evolution rate of 578 µmol h–1 g–1 with 98% selectivity towards CO under visible light irradiation, further enhanced by [Ru(bpy)3]2+(Figs. 11b and c). The corresponding energy level diagram is shown in Fig. 11d. The conduction band of Ni-PCD@TD-COF is lower than the LUMO of [Ru(bpy)3]Cl2, so that the photoexcited electrons in the LUMO of photosensitizers could transfer to the CBM of Ni-PCD@TD-COF, enabling the reduction of adsorbed CO2 to generate CO. Another COF-based heterostructure was fabricated by Do et al., where they synthesized TpPa-1 COF on graphene oxide (GO) and then reduced GO to reduced graphene oxide (rGO) in situ (Fig. 12a) [135]. The inclusion of rGO promotes the effective utilization of photo-generated carriers and increases the absorption of visible light (Fig. 12b). This optimized COF/rGO photocatalyst achieved a CO evolution rate of 200 µmol h–1 g–1 with 89% selectivity towards CO under visible light irradiation. Defective g-C3N4 can also form a heterostructure with COF for photocatalytic CO2RR, as discovered by Ye et al. (Fig. 13a) [136]. In this work, N-vacancies in g-C3N4 increase the Fermi level difference between the TP-TTA COF and g-C3N4 facilitating charge transfer (Fig. 13b). This leads to a CO production rate of 576 µmol h–1 g–1 with 90.4% selectivity towards CO under visible light irradiation.

    Figure 11

    Figure 11.  (a) The structure of TD-COF and Ni-PCD@TD-COF. (b, c) The CO2RR performance of Ni-TPAP. (d) The energy-level diagram showing the electron transfer from [Ru(bpy)3]Cl2 to Ni-PCD@TD-COF. Copied with permission [134]. Copyright 2020, Wiley-VCH.
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    Figure 12

    Figure 12.  (a) The in situ process for the synthesis of covalently bonded rGOx@TpPa-1 composites. (b) The energy level diagram of TpPa-1 and rGOx@TpPa-1. Copied with permission [135]. Copyright 2021, American Chemical Society.
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    Figure 13

    Figure 13.  (a) The preparation of g-C3N4/COF heterojunction. (b) The relative band energy positions and S-scheme charge transfer mechanism between Tp-Tta COF and g-C3N4. Copied with permission [136]. Copyright 2022, Elsevier B.V.
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    More recently, Zhou et al. studied a series of COF-organic molecular heterostructures as effective photocatalysts for CO2RR [137]. Anthracene, pyrene, and perylene were assembled on TMBen COF (olefin-linked COFs named as TMBen) via an end-capping strategy. The formation of covalent bond facilitates charge separation through a Type II pathway and minimized charge recombination. Among them, the TMBen-Perylene heterostructure showed the highest CO2RR activity with a rate of 93.0 µmol h–1 g–1 under visible light irradiation, using TEOA as the hole sacrificial agent. The brief summary of the photocatalytic performances of the COF-based photocatalysts in CO2RR are listed in Table 2 [103-106,108,109,113,114,138-141].

    Table 2

    Table 2.  Summary of photocatalytic CO2 reduction using COF based photocatalysts.
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    3.2 Photocatalytic CO2RR by CTF based catalysis

    Two dimensional crystalline CTFs consist of covalently bonded aromatic triazines and exhibit unique structural characteristics, such as strong conjugated structure, delocalized electrons, and abundant active centers. These characteristics make CTFs highly promising in energy storage and conversion applications. In particular, CTFs are considered ideal photocatalysts for CO2 reduction because of the strong interaction between N atoms in triazine cores and CO2 [142,143]. This interaction, known as dipole or quadrupole interactions, dramatically reduces the energy barrier for CO2 reduction, facilitating electron acceptance and subsequent reduction. One of the advantages of CTFs as photocatalytic systems is the synergic coordination between triazine units and nanoparticles or metal ions, as well as the confinement effect of the frameworks. This makes CTFs an attractive platform for immobilization metal nanoparticles [144-147]. To enhance photocatalytic efficiency and selectivity, co-catalysts (metal complexes), have been widely incorporated into CTFs frameworks to reduce overpotential, promote transfer kinetics, and enhance interfacial interactions during catalytic processes, leading to higher selectivity and efficiency in specific products formation [148]. Therefore, CTFs can serve as carriers for anchoring metal single atoms and assembling molecular-based complex for photocatalytic CO2 reduction (Fig. 14) [148-157].

    Figure 14

    Figure 14.  CTFs via synthesis methods that use varying aromatic and cyanuric halides as monomers.
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    Maximizing atom-utilization efficiency on CTFs is crucial for facilitating charge separation and CO2 activation in photocatalytic CO2 reduction. Using suitable supports with strong interactions with the single atoms can help maintain the single-atom state of metal atoms. Moreover, the metal-support interaction can modify the electronic structure of the confined single atoms, influencing CO2 capture and activation in metal centers. Recently, Wu's group reported a well-defined positioned synthesis of Pt single atoms in ethylene glycol (EG)-modified CTF (Pt-SA/CTF-1) using a photo-deposition method for efficient photoreduction CO2 to CH4 under visible light irradiation [158]. The well-defined coordination structure of Pt–N(C) sites in the Pt-SA/CTF-1 catalyst demonstrates that Pt single atoms confined in CTF-1 not only improve CO2 adsorption and activation but also accelerate the separation and transfer of photogenerated carriers in CTF-1 (Fig. 15a). When exposed to visible light, Pt-SA/CTF-1 is excited, generating electron and hole pairs. The photogenerated electrons are then transferred to the single Pt atoms, while the holes are quenched by TEA. With a continuous supply of electrons, the adsorbed CO2 are activated to formed carbonate (–CO32−); which are subsequently reduced to intermediates such as HCOOH and HCHO, and finally transformed into CH4, as the main reduction product (Figs. 15b and c). The high affinity of Pt-SA/CTF-1 for CO2 also played a crucial role in promoting the formation of Pt-CO2 adduct and consequently boosts the performance of photocatalytic CO2 reduction (Fig. 15d).

    Figure 15

    Figure 15.  (a) The structure of Pt-SAC/CTF-1. (b) Photocatalytic CO2 conversion rates of CTF-1, CTF-EG, Pt-NP/CTF-1, Pt-SA/CTF-1 and Pt/C3N4-EG. (c) In-situ FTIR spectra of the adsorbed species for Pt-SA/CTF-1. (d) The mechanization of photocatalytic CO2 reduction for Pt-SA/CTF-1. Copied with permission [158]. Copyright 2022, Elsevier B.V.
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    Similarly, Zhang's group has successfully designed and synthesized photocatalysts using CTFs anchored with copper single atoms (Cu-SA/CTF) to enhance the conversion of CO2 (Fig. 16a) [159]. These Cu-SA/CTF photocatalysts exhibit superior performance with a high selectivity of 98% in the photocatalytic CO2 conversion to CH4 (Fig. 16b). The introduction of Cu single atoms enhances CO2 adsorption capacity, visible light absorption ability, and separation efficiency of photogenerated carriers, ultimately improving the photocatalytic activity. The photocatalytic pathway of Cu-SA/CTF involves the adsorption of *CO, and *HO intermediates. Subsequently, the adsorbed *CO can react with protons and electrons to produce COOH*. Then, COOH* species could be further protonated into CHOH or CH4. The desorption of CO was obtained via the dissociation of OH from COOH* (Figs. 16c and d). In brief, the photocatalytic conversation process is described as CO2 to CH4. It demonstrated that constructing excellent molecular-based CTFs endows their high selective for photocatalysis CO2RR.

    Figure 16

    Figure 16.  (a) The structure of Cu-SA/CTF. (b) Photocatalytic CO2 reduction performance of CTF-1, Cu-NP/CTF, and Cux-SA/CTF. (c) In-situ FTIR spectra of the adsorbed species for Cu0.10-SA/CTF. (d) The conversion of photocatalytic CO2 reduction for Cux-SA/CTF. Copied with permission [159]. Copyright 2022, Springer.
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    In Cao's work, a pyridine-based CTF (CTF-py) derived from 2,6-dicyanopyridine is employed as a porous platform to anchor the Re carbonyl complex Re(CO)3Cl (Re-CTF-py). The resulting Re-CTF-py photocatalyst demonstrates high efficiency in photocatalytic CO2 reduction to CO, achieving a turnover number (TON) of 4.8. The CO evolution rate reached 353.05 µmol g–1 h–1 within 10 h under full light irradiation in a solid-gas system. Moreover, the single-site Re-CTF-py catalyst prevents the dimerization and leaching of active Re species, ensuring sustained activity [160]. Single-site catalysts with metal atoms have shown remarkable activity and selectivity in this field, achieving the maximized atomic efficiency and diverse chemical activities of CTFs with possess large surface areas and tunable pore sizes.

    Surface functionalization is another strategy to achieve high CO2RR activity and product selectivity. Baeg et al. designed a photocatalyst/biocatalyst system utilizing perylene-based CTFs prepared through polycondensation between cyanuric chloride and perylene diimide that may provide an excellent platform to unify light harvesting capabilities of perylene with the desirable properties of CTFs for artificial photosynthesis (Fig. 17a) [161]. Upon irradiation, this system exclusively generates 9.3 µmol of HCOOH, with a formation rate of ~881.3 µmol h–1 g–1 in an elaborated buffer solution containing CTF, a coenzyme, a rhodium complex, a formate dehydrogenase enzyme, and ascorbic acid (Fig. 17b). The photograph of the flexible CTF film and the chemical structure is shown in Fig. 17c. Photoexcited electrons migrated to the photocatalyst/metal complex substrate, while photoexcited holes are captured by ascorbic acid to prevent rapid recombination. The metal complex undergoes reduction by excite electrons, coenzyme NADH, and formate dehydrogenase, ultimately resulting in the two-electron reduction of CO2 to HCOOH. The polymeric structure, suitable band gap, and highly ordered π electron channel systems of the CTF film photocatalyst greatly facilitate charge carrier transport contribute to the excellent selectivity observed.

    Figure 17

    Figure 17.  (a) Schematic illustration of the CTF film photocatalyst-enzyme coupled system involved in the exclusive production of formic acid from CO2. (b) Photocatalytic activities of the CTF and monomer for selective enzymatic production of formic acid from CO2. (c) Photograph of the flexible film photocatalyst along with the detailed chemical structure of the CTF. Copied with permission [161]. Copyright 2016, the Royal Society of Chemistry.
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    The positions of CBM and VBM of photocatalysts significantly influence the redox abilities of photo-generated electrons and holes during photocatalytic reactions. Zhu's work introduces aheterostructure of CTF and g-C3N4 in CO2 photoreduction for the first time (Fig. 18a) [162]. The combined g-C3N4/CTF enhanced photocatalytic activity, achieving transform rates of CO2 to CO reaching 151.1 µmol h–1 g–1 within 30 h. The optimal g-C3N4/CTF heterostructure efficiently separates charges and suppresses recombination under visible light irradiation, resulting in CO2 photoreduction efficiency is 25.5 and 2.5 times higher than that of CTF and g-C3N4, respectively. The CBM potential of this heterostructure enables effective interfacial electrons transfer from g-C3N4 to CTF for thermodynamically favorable CO2 reduction to CO. The VBM potentials of g-C3N4 and CTF, which are more positive than that of H2O oxidization, allow the holes to oxidize H2O to O2 and H+ (Fig. 18b). The stability of the g-C3N4/CTF heterostructure in photocatalytic systems is attributed to the crystal structure stability. Additionally, in the photocatalytic CO2 reduction process, [Co(bpy)3]2+ acts as an electron harvesting agent from the semiconductor, activating CO2 and breaking the C═O bond to selectively produce CO in synergy with g-C3N4/CTF. These outstanding features are expected to provide a new method for the fabrication of superior heterostructure photocatalysts by combining CTF with C3N4 to optimize the band structure and achieve higher product selectivity in this field.

    Figure 18

    Figure 18.  (a) The synthesis and photocatalytic procedure of CN/CTF heterostructure. (b) Energy band structure of the as-synthesized CN/CTF heterostructure. Copied with permission [162]. Copyright 2018, the Royal Society of Chemistry.
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    Based on the above, several strategies can be employed to optimize CTFs for selective photocatalytic CO2RR. These include the anchoring effect of single active sites, improvement of charge separation, fine-tuning of band structures, and enhancement of transfer efficiency through molecular-level structural design. Additionally, it is crucial to select an appropriate synthesis method to preserve the semiconductive property of the CTFs while also controlling the morphology and porosity for efficient photocatalytic applications. However, the synthesis of ordered and well-defined CTFs remains a significant challenge. The brief summary of the photocatalytic performances of the CTF-based photocatalysts in CO2RR are listed in Table 3 [158-160,163-168].

    Table 3

    Table 3.  Summary of photocatalytic CO2 reduction using CTF based photocatalysts.
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    3.3 Photocatalytic CO2RR by cmp based catalysis

    CMPs have attracted significant interest due to their porous structures and organic functionalities, which allow for various synthetic diversification. Since their first synthesis in 2007 by Cooper's group, a variety of CMPs, including thiophene-containing CMPs, light-emitting CMPs, soluble CMPs, core-shell CMPs, CMP films, comonomer-doped CMPs, and tetraphenylethylene-interweaving CMPs, have been developed for applications in gas adsorption, molecular separation, electronics, and catalysis. The photocatalytic performance of CMPs relies on factors such as surface area, linkage geometry, conjugation degree, and band gap. In recent years, various strategies have been proposed to improve photocatalytic performance of CMPs (Fig. 19).

    Figure 19

    Figure 19.  Molecular based strategies to improve the photocatalytic performances of CMPs.
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    One of the main strategies is to regulate the molecular structure of CMPs by adjusting synthesis methods, reaction conditions, and monomer types. This approach has been proven effective in enhancing their photocatalytic performance. Another strategy is to consider different donors and electron acceptor units, which can lead to the development of D–π–A CMP photocatalysts with expanded light absorption range [169]. Additionally, the morphology of CMP materials can also influence their photocatalytic performances. Surface modification with polar groups such as –NO2 [170], arylamines [171], –OH [172], –COOH [173], –SO3H [174], and heterocyclic nitrogen atoms [175] can significantly increase the binding energy of CO2 so as to improve CO2 absorption ability.

    By appropriate designing and constructing molecular building blocks, molecular-level precise control over chemical transformations catalyzed by CMPs can be achieved [176,177]. This has generated extensive interest in CMPs for CO2 conversion. However, as far as we know, few examples have been reported on the use of CMPs as photocatalysts for CO2 photoreduction in Table 4.

    Table 4

    Table 4.  Summary of photocatalytic CO2 reduction using CMPs.
    DownLoad: CSV

    As discussed in the previous sections of this review, both COFs and CTFs exhibit intriguing optoelectronic properties, which can be further enhanced by utilizing different organic precursors and tuning their structures. One effective approach to achieve this is through molecular-based modification, where the optical characteristics of polymers can be easily adjusted by incorporating different organic moieties. For instance, Wang et al. explored the use of CMPs for CO2 reduction and investigated the influence of their structure on catalytic efficiency [178]. By incorporating electron-withdrawing BT units into the triazine poly-network, the photocatalytic CO2 reduction to CO was significantly enhanced, achieving CO formation rates of up to 18.2 µmol/h with a selectivity of 81.6%. The introduction of organic electron-withdrawing and electron-donating units in the polymer backbone, particularly based on triazine, promoted charge separation surface redox reactions, enabling stable photoconversion of CO2 to CO under visible-light irradiation.

    Furthermore, Xu's group designed a new 2D CMPs based on metalloporphyrin as the main structural and functional unit, with thiophene as the link moiety for CO2 reduction [179]. They successfully modified the electronic properties of metalloporphyrin units by incorporating various metal atoms (Fe, Mg, Mn, and Cu) into CMP networks. Calculation results indicated that these CMPs possessed catalytic properties, high stability, and adjustable electronic structures, with Fe-modified thiophene-linked metalloporphyrin (Fe-TMP) exhibiting the highest catalytic activity for CO2 reduction. The pathway for the H3COH intermediate to CH4 was also confirmed (Fig. 20a), with the adsorbed H3COH* being reduced to CH3* assisted by the adsorbed H atom. Finally, the formed CH3* species was further transferred to CH4* by another H atom. The thermodynamically preferred reduction process was the carboxyl pathway, resulting in methane as the final reduction product and formic acid as a side product.

    Figure 20

    Figure 20.  The mechanism of CO2RR of metalloporphyrin based CMPs. (a) The optimized structures of various intermediate species adsorbed on the Fe-TMP substrate and the overall pathway of CO2 reduction and each elemental step's activation barriers. Copied with permission [179]. Copyright 2018, the Royal Society of Chemistry. (b) The energy-level diagram and proposed mechanism for photocatalytic CO2RR of POPn-Fe. Copied with permission [180]. Copyright 2021, American Chemical Society.
    DownLoad: Full-Size Img PowerPoint

    To control the selectivity of photocatalysts, CO2-philic monomers can be utilized in the construction of CMP networks to facilitate the efficient capture and highly selective conversion of CO2. Recently, He's group reported the synthesis of two ferric porphyrin-based porous organic polymers semiconductors for visible light-driven CO2RR to produce syngas with tunable CO/H2 ratio (Fig. 20b) [180]. They found that the ferric porphyrin site was responsible for CO evolution, while the uncoordinated porphyrin unit played a role in H2 formation, thus achieving selectivity control. The extended π-conjugation with a biphenyl linker in the polymer resulted in a lower conduction band potential, enabling the ferric porphyrin sites to capture electrons from the photosensitizer and produce more CO. By changing the linker from benzene to biphenyl, the ratio of CO/H2 could be adjusted from 1:1 to 1:1.5, and under irradiation with 450 nm wavelengths, the ratio could reach 1:2. This demonstrated that modifying surface active sites was beneficial for improving product selectivity.

    Another strategy involves providing multi-active sites to enhance catalytic efficiency and directly identify the activity of metal centers. Zang's group designed and prepared a series of CMPs containing well-defined M–N4 and M–N2O2 single-atom sites (Fig. 21a) [181]. The introduction of salphen unit with Ni–N2O2 catalytic centers into a phthalocyanine-based Ni–N4 framework achieved remarkable CO generation ability (1942.5 µmol g–1 h–1) with a high selectivity of 96% over H2 in CO2 photoreduction. Through control experiments and theoretical studies, the Ni–N2O2 moiety was found to be a more active site for CO2RR compared to the traditional Ni–N4 moiety. This can be attributed to the reduction of energy barriers, enhanced adsorption of reaction radicals *COOH by the M-N2O2 active sites, and improvement of the charge transportation (Figs. 21b and c). This study confirmed that molecular-based structural modification can easily tune the photoactivity and selectivity for photocatalytic CO2RR.

    Figure 21

    Figure 21.  (a) The structure of NiPc–MPOP and the high CO2 reduction activity of Ni–N2O2 species compared to that of Ni–N4. (b, c) The high CO2 reduction activity of Ni–N2O2 species compared to that of Ni–N4. Copied with permission [181]. Copyright 2021, Wiley-VCH.
    DownLoad: Full-Size Img PowerPoint

    Additionally, the presence of permanent porosity in these materials allows for facile diffusion of substrate, while π-conjugation throughout the CMP network facilitates charge migration to reaction sites [182,183]. Inspired by the intermolecular π–π stacking structure of Co (II) bipyridine complex cocatalyst, Ye and co-workers constructed a series of novel CMPs (Fig. 22a) through Sonogashira and Suzuki coupling methods, with or without alkynyl bridges and pyrene comonomers possessing two or four functional end groups, resulting in linear or crosslinked polymers [184]. Combined with simulation and experimental results, they found that the presence of alkyne facilitated intramolecular electron transfer, leading to lower local electron density and thus poor intermolecular electron transfer between photocatalysts and cocatalysts (Fig. 22b). CO2 photoreduction experiments supported their findings, demonstrating higher CO production rates (11.37 and 4.03 µmol/h) for samples without alkynyl bridges. Alkynyl-containing photocatalysts only generated a moderate amount of CO (0.5 µmol/h).

    Figure 22

    Figure 22.  (a) Illustration of synthesis and the strategy of eliminating the charge-transfer bridge. (b) Proposed process of electron transfer over the CP-A series and CP-D series for the CO2 photoreduction reaction. Copied with permission [184]. Copyright 2020, Springer Nature.
    DownLoad: Full-Size Img PowerPoint

    4. Summary and perspective

    In this review, we provide a comprehensive summary of recent advancements in molecular-based design of PPs for photocatalytic CO2 reduction. Molecular design plays a pivotal role in achieving desired properties of polymers. For instance, tethering an antenna molecule can improve visible light absorption, constructing Z-scheme photocatalyst system can decrease the recombination of charge carriers, and deposition of highly dispersed single active site can provide more active sites. The influence of atom manufacturing on heterogeneous photocatalysts is explored, highlighting the importance of active sites, light absorption capabilities, and the transportation of photogenerated carriers. Various molecular manufacturing approaches, such as single active site, anchoring metal molecular complexes, and metal-semiconductor systems, are discussed for their potential to improve performance and product selectivity in photocatalytic CO2RR. Molecular engineering of PPs enables favorable electronic structure regulation of active sites, affecting CO2 adsorption and activation behaviors, thereby enhancing CO2 conversion efficiency and product selectivity.

    While these PPs have proven to be promising photocatalysts, further efforts are required to compete with traditional photocatalysts and address some key challenges in the future. While catalyst design represents a crucial step and has made significant progress, the understanding of the reaction mechanism and pathways involved in photocatalytic CO2 reduction remains in its nascent stages. To achieving high activity and product selectivity in CO2 reduction photocatalysts, further exploration and optimization of various factors are necessary. These factors include band structure, charge carrier separation, reactant adsorption/activation, surface reaction sites, and intermediate adsorption/desorption processes. Challenges and obstacles persist in the design, fabrication, and application of modified photocatalysts. It is imperative to focus on developing highly efficient methods for scalable production of controllable molecular-based porous polymers. Additionally, a deeper comprehension of the structure-activity relationship between molecular-based photocatalysts and their performance is crucial. Exploring the effects of surface or interface-engineered atoms, rather than bulk atoms, on CO2 reduction may offer valuable insights.

    Regarding the PPs we mentioned in this review, many issues need to be resolved. For COF-based PPs, research can focus on developing core-shell structures to enhance charge separation at intimate interfaces between the COF and supports. The design of COFs with donor–acceptor (D–A) structures can also facilitate intramolecular charge transfer to achieve efficient photocatalytic CO2 reduction. Compared to COFs, CTFs have a limited number of structures that are well-defined and crystalline, which has posed challenges to conducting in-depth studies on structure-activity relationships. Therefore, there is a pressing need for advanced development in CTF synthesis to address this limitation. Despite their potential, CMPs still face challenges in competing with other photocatalysts. It is crucial to develop suitable synthetic strategies to incorporate photocatalytically active components into CMP networks for more complex reactions. Moreover, efforts should be made to enhance the crystallinity of CMPs or design novel structures that facilitate efficient charge transfer and minimize photoexcited carriers recombination.

    In conclusion, the molecular-based strategy shows promising potential for creating highly efficient photocatalysts for CO2RR. Anticipated breakthroughs in molecular-based photocatalysts are expected in the near future, and are poised to greatly improve the selective photocatalytic conversion of CO2.

    Declaration of competing interest

    The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

    Acknowledgment

    We appreciate the National Natural Science Foundation of China (No. 22005154) for financial support.


    1. [1]

      M. Meinshausen, N. Meinshausen, W. Hare, et al., Nature 458 (2009) 1158–1162. doi: 10.1038/nature08017

    2. [2]

      T.R. Karl, K.E. Trenberth, Science 302 (2003) 1719–1723. doi: 10.1126/science.1090228

    3. [3]

      C. Zhou, J. Shi, W. Zhou, et al., ACS Catal. 10 (2020) 302–310. doi: 10.1021/acscatal.9b04309

    4. [4]

      Q. Guo, S.G. Xia, X.B. Li, et al., Chem. Commun. 56 (2020) 7849. doi: 10.1039/D0CC01091J

    5. [5]

      W. Zhou, K. Cheng, J. Kang, et al., Chem. Soc. Rev. 48 (2019) 3193–3228. doi: 10.1039/C8CS00502H

    6. [6]

      L. Lu, X.F. Sun, J. Ma, et al., Angew. Chem. Int. Ed. 57 (2018) 14149–14153. doi: 10.1002/anie.201808964

    7. [7]

      X. He, Y. Cao, X.D. Lang, et al., ChemSusChem 11 (2018) 3382–3387. doi: 10.1002/cssc.201801621

    8. [8]

      J. Artz, T.E. Müller, K. Thenert, et al., Chem. Rev. 118 (2018) 434–504. doi: 10.1021/acs.chemrev.7b00435

    9. [9]

      K. Chen, J. Xiao, T. Hisatomi, et al., Chem. Sci. 14 (2023) 9248–9257. doi: 10.1039/D3SC03198E

    10. [10]

      G. Wang, C.T. He, R. Huang, et al., J. Am. Chem. Soc. 142 (2020) 19339–19345. doi: 10.1021/jacs.0c09599

    11. [11]

      Y.N. Gong, J.H. Mei, W.J. Shi, et al., Angew. Chem. Int. Ed. 63 (2024) e202318735.

    12. [12]

      J.H. Zhang, Y.N. Gong, H.J. Wang, et al., Proc. Natl. Acad. Sci. U. S. A. 119 (2022) e2118278119.

    13. [13]

      Q. Zhang, S. Gao, Y. Guo, et al., Nat. Commun. 14 (2023) 1147. doi: 10.1038/s41467-023-36779-4

    14. [14]

      J. Zhang, Y. Wang, H. Wang, D. Zhong, T. Lu, Chin. Chem. Lett. 33 (2022) 2065–2068. doi: 10.1016/j.cclet.2021.09.035

    15. [15]

      M.T. Ming, Y.C. Wang, W.X. Tao, et al., Green Chem. 25 (2023) 6207–6211. doi: 10.1039/D3GC01461D

    16. [16]

      H. Lv, P. Li, X. Li, et al., Chem. Eng. J. 451 (2023) 138745. doi: 10.1016/j.cej.2022.138745

    17. [17]

      J.W. Liu, C.Y. Chen, K. Zhang, L. Zhang, Chin. Chem. Lett. 32 (2021) 649–659. doi: 10.1016/j.cclet.2020.07.040

    18. [18]

      N. Elgrishi, M.B. Chambers, X. Wang, M. Fontecave, Chem. Soc. Rev. 46 (2017) 761–796. doi: 10.1039/C5CS00391A

    19. [19]

      M. Ding, R.W. Flaig, H.L. Jiang, O.M. Yaghi, Chem. Soc. Rev. 48 (2019) 2783–2828. doi: 10.1039/C8CS00829A

    20. [20]

      H. Rao, C. Lim, J. Bonin, G.M. Miyake, M. Robert, J. Am. Chem. Soc. 140 (2018) 17830–17834. doi: 10.1021/jacs.8b09740

    21. [21]

      A. Savateev, M. Antonietti, ACS Catal. 8 (2018) 9790–9808. doi: 10.1021/acscatal.8b02595

    22. [22]

      X.B. Li, C.H. Tung, L.Z. Wu, Nat. Rev. Chem. 2 (2018) 160–173. doi: 10.1038/s41570-018-0024-8

    23. [23]

      A.G. Slater, A.I. Cooper, Science 348 (2015) aaa8075. doi: 10.1126/science.aaa8075

    24. [24]

      C. Cometto, R. Kuriki, L. Chen, et al., J. Am. Chem. Soc. 140 (2018) 7437–7440. doi: 10.1021/jacs.8b04007

    25. [25]

      Y. Li, S. Zhang, W. Cheng, et al., Adv. Mater. 34 (2022) 2105204. doi: 10.1002/adma.202105204

    26. [26]

      H. Kim, D. Shin, W. Yang, et al., J. Am. Chem. Soc. 143 (2021) 925–933. doi: 10.1021/jacs.0c11008

    27. [27]

      A. Savateev, I. Ghosh, B. König, M. Antonietti, Angew. Chem. Int. Ed. 57 (2018) 15936–15947. doi: 10.1002/anie.201802472

    28. [28]

      W.J. Wang, K.H. Chen, Z.W. Yang, B.W. Peng, L.N. He, J. Mater. Chem. A 9 (2021) 16699–16705. doi: 10.1039/D1TA04418D

    29. [29]

      X. Wang, Y. Pan, H. Ning, et al., Appl. Catal. B 266 (2020) 118630. doi: 10.1016/j.apcatb.2020.118630

    30. [30]

      Y. Li, S. Wang, X.S. Wang, et al., J. Am. Chem. Soc. 142 (2020) 19259–19267. doi: 10.1021/jacs.0c09060

    31. [31]

      Y.N. Gong, L. Jiao, Y. Qian, et al., Angew. Chem. Int. Ed. 59 (2020) 2705–2709. doi: 10.1002/anie.201914977

    32. [32]

      A. Guan, Z. Chen, Y. Quan, et al., ACS Energy Lett. 5 (2020) 1044–1053. doi: 10.1021/acsenergylett.0c00018

    33. [33]

      Y. Cai, J. Fu, Y. Zhou, et al., Nat. Commun. 12 (2021) 586. doi: 10.1038/s41467-020-20769-x

    34. [34]

      D. Gao, T. Liu, G. Wang, X. Bao, ACS Energy Lett. 6 (2021) 713–727. doi: 10.1021/acsenergylett.0c02665

    35. [35]

      X. Cui, W. Li, P. Ryabchuk, K. Junge, M. Beller, Nat. Catal. 1 (2018) 385–397. doi: 10.1038/s41929-018-0090-9

    36. [36]

      R. Lang, T. Li, D. Matsumura, et al., Angew. Chem. Int. Ed. 55 (2016) 16054–16058. doi: 10.1002/anie.201607885

    37. [37]

      S. Lin, C.S. Diercks, Y.B. Zhang, et al., Science 349 (2015) 1208–1213. doi: 10.1126/science.aac8343

    38. [38]

      G. Huang, Q. Niu, J. Zhang, et al., Chem. Eng. J. 427 (2022) 131018. doi: 10.1016/j.cej.2021.131018

    39. [39]

      J.H. Kou, C.H. Lu, J. Wang, et al., Chem. Rev. 117 (2017) 1445–1514. doi: 10.1021/acs.chemrev.6b00396

    40. [40]

      L. Rademacher, T. Beglau, B. Ali, et al., J. Mater. Chem. A 12 (2024) 2093–2109. doi: 10.1039/D3TA05597C

    41. [41]

      Y. Liang, X. Wu, X. Liu, C. Li, S. Liu, Appl. Catal. B 304 (2022) 120978. doi: 10.1016/j.apcatb.2021.120978

    42. [42]

      J. Ran, M. Jaroniec, S.Z. Qiao, Adv. Mater. 30 (2018) 1704649. doi: 10.1002/adma.201704649

    43. [43]

      K. Li, B. Peng, T. Peng, ACS Catal. 6 (2016) 7485–7527. doi: 10.1021/acscatal.6b02089

    44. [44]

      H.L. Wu, X.B. Li, C.H. Tung, L.Z. Wu, Adv. Mater. 31 (2019) 1900709. doi: 10.1002/adma.201900709

    45. [45]

      S. Kramer, N.R. Bennedsen, S. Kegnæs, ACS Catal. 8 (2018) 6961–6982. doi: 10.1021/acscatal.8b01167

    46. [46]

      P. Kaur, J.T. Hupp, S.T. Nguyen, ACS Catal. 1 (2011) 819–835. doi: 10.1021/cs200131g

    47. [47]

      C. Qian, W. Zhou, J. Qiao, et al., J. Am. Chem. Soc. 142 (2020) 18138–18149. doi: 10.1021/jacs.0c08436

    48. [48]

      J.Q. Dong, X. Han, Y. Liu, H.Y. Li, Y. Cui, Angew. Chem. Int. Ed. 59 (2020) 13722–13733. doi: 10.1002/anie.202004796

    49. [49]

      B. Han, X. Ou, Z. Zhong, et al., Small 16 (2020) 2002985. doi: 10.1002/smll.202002985

    50. [50]

      C. Dai, B. Liu, Energy Environ. Sci. 13 (2020) 24–52. doi: 10.1039/C9EE01935A

    51. [51]

      X. Chen, S. Shen, L. Guo, S.S. Mao, Chem. Rev. 110 (2010) 6503–6570. doi: 10.1021/cr1001645

    52. [52]

      X. Liu, S. Inagaki, J. Gong, Angew. Chem. Int. Ed. 55 (2016) 14924–14950. doi: 10.1002/anie.201600395

    53. [53]

      C. Wang, Z. Sun, Y. Zheng, Y.H. Hu, J. Mater. Chem. A 7 (2019) 865–887. doi: 10.1039/C8TA09865D

    54. [54]

      X. Wang, S. Blechert, M. Antonietti, ACS Catal. 2 (2012) 1596–1606. doi: 10.1021/cs300240x

    55. [55]

      Y. Zheng, L. Lin, B. Wang, X. Wang, Angew. Chem. Int. Ed. 54 (2015) 12868–12884. doi: 10.1002/anie.201501788

    56. [56]

      C. Chen, W. Ma, J. Zhao, Chem. Soc. Rev. 39 (2010) 4206–4219. doi: 10.1039/b921692h

    57. [57]

      D.D. Zhu, J.L. Liu, S.Z. Qiao, Adv. Mater. 28 (2016) 3423. doi: 10.1002/adma.201504766

    58. [58]

      S. Zhang, S. Wang, L. Guo, et al., J. Mater. Chem. C 8 (2020) 192–200. doi: 10.1039/C9TC05297F

    59. [59]

      H.P. Liang, A. Acharjya, D.A. Anito, et al., ACS Catal. 9 (2019) 3959–3968. doi: 10.1021/acscatal.8b04032

    60. [60]

      Y. Chen, G. Ji, S. Guo, et al., Green Chem. 19 (2017) 5777–5781. doi: 10.1039/C7GC02346D

    61. [61]

      L. Zhang, Z.J. Zhao, J. Gong, Angew. Chem. Int. Ed. 56 (2017) 11326–11353. doi: 10.1002/anie.201612214

    62. [62]

      X.F. Yang, A. Wang, B. Qiao, et al., Acc. Chem. Res. 46 (2013) 1740–1748. doi: 10.1021/ar300361m

    63. [63]

      J.L. White, M.F. Baruch, J.E. Pander Ⅲ, et al., Chem. Rev. 115 (2015) 12888–12935. doi: 10.1021/acs.chemrev.5b00370

    64. [64]

      M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Chem. Rev. 95 (1995) 69–96. doi: 10.1021/cr00033a004

    65. [65]

      A.L. Linsebigler, G. Lu, J.T. Yates, Chem. Rev. 95 (1995) 735–758. doi: 10.1021/cr00035a013

    66. [66]

      S. Sorcar, Y. Hwang, C.A. Grimes, Mater. Today 20 (2017) 507–515. doi: 10.1016/j.mattod.2017.09.005

    67. [67]

      P.V. Kamat, J. Phys. Chem. Lett. 3 (2012) 663–672. doi: 10.1021/jz201629p

    68. [68]

      M.A. Henderson, Surf. Sci. Rep. 66 (2011) 185–297. doi: 10.1016/j.surfrep.2011.01.001

    69. [69]

      A. Fujishima, X. Zhang, D.A. Tryk, Surf. Sci. Rep. 63 (2008) 515–582. doi: 10.1016/j.surfrep.2008.10.001

    70. [70]

      S.H. Szczepankiewicz, A.J. Colussi, M.R. Hoffmann, J. Phys. Chem. B 104 (2000) 9842–9850. doi: 10.1021/jp0007890

    71. [71]

      D.M. Adams, L. Brus, C.E.D. Chidsey, et al., J. Phys. Chem. B 107 (2003) 6668–6697.

    72. [72]

      M. Jakob, H. Levanon, P.V. Kamat, Nano Lett. 3 (2003) 353–358. doi: 10.1021/nl0340071

    73. [73]

      S. Kim, S.J. Hwang, W. Choi, J. Phys. Chem. B 109 (2005) 24260–24267. doi: 10.1021/jp055278y

    74. [74]

      J.T. DuBose, P.V. Kamat, Chem. Rev. 122 (2022) 12475–12494. doi: 10.1021/acs.chemrev.2c00172

    75. [75]

      X. Chang, T. Wang, J. Gong, Energy Environ. Sci. 9 (2016) 2177–2196. doi: 10.1039/C6EE00383D

    76. [76]

      A. Behera, A.K. Kar, R. Srivastava, Mater. Horiz. 9 (2022) 607–639. doi: 10.1039/D1MH01490K

    77. [77]

      T. Oshima, T. Ichibha, K. Qin, et al., Angew. Chem. Int. Ed. 57 (2018) 8154–8158. doi: 10.1002/anie.201803931

    78. [78]

      S.N. Habisreutinger, L. Schmidt-Mende, J.K. Stolarczyk, Angew. Chem. Int. Ed. 52 (2013) 7372–7408. doi: 10.1002/anie.201207199

    79. [79]

      A. Wang, J. Li, T. Zhang, Nat. Rev. Chem. 2 (2018) 65–81. doi: 10.1038/s41570-018-0010-1

    80. [80]

      B. Qiao, A. Wang, X. Yang, et al., Nat. Chem. 3 (2011) 634–641. doi: 10.1038/nchem.1095

    81. [81]

      L.H. Shao, A.X. Huang, X.C. Yan, et al., J. Colloid Interface Sci. 633 (2023) 233–242. doi: 10.1016/j.jcis.2022.11.094

    82. [82]

      J. Fu, B. Zhu, C. Jiang, et al., Small 13 (2017) 1603938. doi: 10.1002/smll.201603938

    83. [83]

      B.H. Lee, S. Park, M. Kim, et al., Nat. Mater. 18 (2019) 620–626. doi: 10.1038/s41563-019-0344-1

    84. [84]

      C. Gao, J. Low, R. Long, et al., Chem. Rev. 120 (2020) 12175–12216. doi: 10.1021/acs.chemrev.9b00840

    85. [85]

      J.C. Liu, Y. Tang, Y.G. Wang, T. Zhang, J. Li, Natl. Sci. Rev. 5 (2018) 638–641. doi: 10.1093/nsr/nwy094

    86. [86]

      J. Li, Q. Guan, H. Wu, et al., J. Am. Chem. Soc. 141 (2019) 14515–14519. doi: 10.1021/jacs.9b06482

    87. [87]

      Y. Zhang, B. Xia, J. Ran, K. Davey, S.Z. Qiao, Adv. Energy Mater. 10 (2020) 1903879. doi: 10.1002/aenm.201903879

    88. [88]

      A.P. Côté, A.I. Benin, N.W. Ockwig, et al., Science 310 (2005) 1166–1170. doi: 10.1126/science.1120411

    89. [89]

      H. Wang, H. Wang, Z. Wang, et al., Chem. Soc. Rev. 49 (2020) 4135–4165. doi: 10.1039/D0CS00278J

    90. [90]

      K.K. Niu, T.X. Luan, J. Cui, et al., ACS Catal. 14 (2024) 2631–2641. doi: 10.1021/acscatal.3c05454

    91. [91]

      C.Y. Lin, D.T. Zhang, Z.H. Zhao, Z.H. Xia, Adv. Mater. 30 (2018) 1703646. doi: 10.1002/adma.201703646

    92. [92]

      P. Pachfule, A. Acharjya, J. Roeser, et al., J. Am. Chem. Soc. 140 (2018) 1423–1427. doi: 10.1021/jacs.7b11255

    93. [93]

      T. Sick, A.G. Hufnagel, J. Kampmann, et al., J. Am. Chem. Soc. 140 (2018) 2085–2092. doi: 10.1021/jacs.7b06081

    94. [94]

      J.D. Xiao, H.L. Jiang, Acc. Chem. Res. 52 (2019) 356–366. doi: 10.1021/acs.accounts.8b00521

    95. [95]

      X. Liu, X. Ding, T. Zheng, et al., ACS Appl. Mater. Interfaces 16 (2024) 4741–4750. doi: 10.1021/acsami.3c16319

    96. [96]

      Y. Fu, X. Zhu, L. Huang, et al., Appl. Catal. B 239 (2018) 46. doi: 10.1016/j.apcatb.2018.08.004

    97. [97]

      F. Chen, H. Huang, L. Guo, Y. Zhang, T. Ma, Angew. Chem. Int. Ed. 58 (2019) 10061–10073. doi: 10.1002/anie.201901361

    98. [98]

      J. Fu, K. Jiang, X. Qiu, J. Yu, M. Liu, Mater. Today 32 (2020) 222–243. doi: 10.1016/j.mattod.2019.06.009

    99. [99]

      S. Xu, E.A. Carter, Chem. Rev. 119 (2019) 6631–6669. doi: 10.1021/acs.chemrev.8b00481

    100. [100]

      Y. Fang, X. Wang, Chem. Commun. 54 (2018) 5674–5687. doi: 10.1039/C8CC02046A

    101. [101]

      E. Jin, M. Asada, Q. Xu, et al., Science 357 (2017) 673–676. doi: 10.1126/science.aan0202

    102. [102]

      R. Chen, J.L. Shi, Y. Ma, et al., Angew. Chem. Int. Ed. 58 (2019) 6430–6434. doi: 10.1002/anie.201902543

    103. [103]

      S. Yang, W. Hu, X. Zhang, et al., J. Am. Chem. Soc. 140 (2018) 14614–14618. doi: 10.1021/jacs.8b09705

    104. [104]

      Z. Fu, X. Wang, A.M. Gardner, et al., Chem. Sci. 11 (2020) 543–550. doi: 10.1039/C9SC03800K

    105. [105]

      W. Zhong, R. Sa, L. Li, et al., J. Am. Chem. Soc. 141 (2019) 7615–7621. doi: 10.1021/jacs.9b02997

    106. [106]

      D.L. Meng, M.D. Zhang, D.H. Si, et al., Angew. Chem. Int. Ed. 60 (2021) 25485–25492. doi: 10.1002/anie.202111136

    107. [107]

      H.B. Huang, Z.B. Fang, R. Wang, et al., Small 18 (2022) e2200407.

    108. [108]

      P.X. Li, X.Y. Yan, X.M. Song, et al., ACS Sustain. Chem. Eng. 9 (2021) 2319–2325. doi: 10.1021/acssuschemeng.0c08559

    109. [109]

      H. Zhao, X. Yang, R. Xu, et al., J. Mater. Chem. A 6 (2018) 20152–20160. doi: 10.1039/C8TA05970E

    110. [110]

      M. Lu, J. Liu, Q. Li, et al., Angew. Chem. Int. Ed. 58 (2019) 12392–12397. doi: 10.1002/anie.201906890

    111. [111]

      X. Wang, X. Ding, T. Wang, et al., ACS Appl. Mater. Interfaces 14 (2022) 41122–41130. doi: 10.1021/acsami.2c12542

    112. [112]

      J. Tang, Z. Liang, H. Qin, et al., Angew. Chem. Int. Ed. 62 (2023) e202214449.

    113. [113]

      M. Zhang, M. Lu, Z.L. Lang, et al., Angew. Chem. Int. Ed. 59 (2020) 6500–6506. doi: 10.1002/anie.202000929

    114. [114]

      D. Wang, X. Li, L.L. Zheng, et al., Nanoscale 10 (2018) 19509–19516. doi: 10.1039/C8NR06691D

    115. [115]

      D. Wang, H. Zeng, X. Xiong, et al., Sci. Bull. 65 (2020) 113–122. doi: 10.1016/j.scib.2019.10.015

    116. [116]

      R. Gao, J. Bai, R. Shen, et al., J. Mater. Sci. Technol. 137 (2023) 223–231. doi: 10.1016/j.jmst.2022.09.001

    117. [117]

      Y. Chen, D. Yang, Y. Gao, et al., Research 2021 (2021) 9798564.

    118. [118]

      Y. Wang, Z. Hu, W. Wang, et al., Chem. Sci. 12 (2021) 16065–16073. doi: 10.1039/D1SC05893B

    119. [119]

      Y. Feng, J. Li, S. Ye, S. Gao, R. Cao, Sustain. Energy Fuels 6 (2022) 5089–5099. doi: 10.1039/D2SE01159J

    120. [120]

      C.C. Li, M.Y. Gao, X.J. Sun, et al., Appl. Catal. B 266 (2020) 118586. doi: 10.1016/j.apcatb.2020.118586

    121. [121]

      L. Liu, J. Zhang, X. Tan, et al., Nano Res. 13 (2020) 983–988. doi: 10.1007/s12274-020-2728-6

    122. [122]

      M. Zhang, J.N. Chang, Y.F. Chen, et al., Adv. Mater. 23 (2021) 2105002.

    123. [123]

      P. Dong, A. Zhang, T. Cheng, et al., Chin. J. Catal. 43 (2022) 2592–2605. doi: 10.1016/S1872-2067(22)64094-4

    124. [124]

      C. Lin, C. Han, L. Gong, et al., Catal. Sci. Technol. 11 (2021) 2616–2621. doi: 10.1039/D0CY02330B

    125. [125]

      W. Han, L.H. Shao, X.J. Sun, et al., Appl. Catal. B 317 (2022) 121710. doi: 10.1016/j.apcatb.2022.121710

    126. [126]

      G. Yuan, L. Tan, P. Wang, et al., Mater. Lett. 325 (2022) 132863. doi: 10.1016/j.matlet.2022.132863

    127. [127]

      Z. Han, R. Kortlever, H.Y. Chen, J.C. Peters, T. Agapie, ACS Cent. Sci. 3 (2017) 853–859. doi: 10.1021/acscentsci.7b00180

    128. [128]

      S. Ou, M. Zhou, W. Chen, Y. Zhang, Y. Liu, ChemSusChem 15 (2022) e202200184.

    129. [129]

      Q. Sun, B. Aguila, J. Perman, N. Nguyen, S. Ma, J. Am. Chem. Soc. 138 (2016) 15790–15796. doi: 10.1021/jacs.6b10629

    130. [130]

      J. Thote, H.B. Aiyappa, A. Deshpande, et al., Chem. Eur. J. 20 (2014) 15961–15965. doi: 10.1002/chem.201403800

    131. [131]

      B.P. Biswal, H.A. Vignolo-González, T. Banerjee, et al., J. Am. Chem. Soc. 141 (2019) 11082–11092. doi: 10.1021/jacs.9b03243

    132. [132]

      T. Banerjee, F. Haase, G. Savasci, et al., J. Am. Chem. Soc. 139 (2017) 16228–16234. doi: 10.1021/jacs.7b07489

    133. [133]

      Y. Liu, Y. He, Anal. Chem. 95 (2023) 14440–14446. doi: 10.1021/acs.analchem.3c02936

    134. [134]

      H. Zhong, R. Sa, H. Lv, et al., Adv. Funct. Mater. 30 (2020) 2002654. doi: 10.1002/adfm.202002654

    135. [135]

      V.N. Gopalakrishnan, D.T. Nguyen, J. Becerra, et al., ACS Appl. Energy Mater. 4 (2021) 6005–6014.

    136. [136]

      J. Wang, Y. Yu, J. Cui, et al., Appl Catal. B 301 (2022) 120814. doi: 10.1016/j.apcatb.2021.120814

    137. [137]

      H. Lin, Y. Liu, Z. Wang, et al., Angew. Chem. Int. Ed. 61 (2022) e202214142.

    138. [138]

      W. Shi, X. Guo, C. Cui, et al., Appl. Catal. B 243 (2019) 236. doi: 10.1016/j.apcatb.2018.09.076

    139. [139]

      Y. Fu, D. Sun, Y. Chen, et al., Angew. Chem. Int. Ed. 51 (2012) 3364–3367. doi: 10.1002/anie.201108357

    140. [140]

      D. Sun, Y. Fu, W. Liu, et al., Chem. Eur. J. 19 (2013) 14279–14285. doi: 10.1002/chem.201301728

    141. [141]

      D. Sun, W. Liu, Y. Fu, et al., Chem. Eur. J. 20 (2014) 4780–4788. doi: 10.1002/chem.201304067

    142. [142]

      S. Zhang, S. Wang, L. Guo, et al., J. Mater. Chem. C 8 (2020) 192–200. doi: 10.1039/C9TC05297F

    143. [143]

      B. Zhu, L. Zhang, D. Xu, B. Cheng, J. Yu, J. CO2 Util. 21 (2017) 327–335. doi: 10.1016/j.jcou.2017.07.021

    144. [144]

      Z.J. Li, D.H. Wang, Y.E. Wu, Y.D. Li, Natl. Sci. Rev. 5 (2018) 673–689. doi: 10.1093/nsr/nwy056

    145. [145]

      M.Z. Ma, Z.A. Huang, D.E. Doronkin, et al., Appl. Catal. B 300 (2022) 120695. doi: 10.1016/j.apcatb.2021.120695

    146. [146]

      K. Qi, M. Chhowalla, D. Voiry, Mater. Today 40 (2020) 173. doi: 10.1016/j.mattod.2020.07.002

    147. [147]

      J. Liang, Q. Song, J. Wu, et al., ACS Nano 16 (2022) 4152–4161. doi: 10.1021/acsnano.1c10003

    148. [148]

      Q. Jiang, L. Sun, J. Bi, et al., ChemSusChem 11 (2018) 1108–1113. doi: 10.1002/cssc.201702220

    149. [149]

      T. Jadhav, Y. Fang, W. Patterson, et al., Angew. Chem. Int. Ed. 58 (2019) 13753–13757. doi: 10.1002/anie.201906976

    150. [150]

      P. Puthiaraj, Y.R. Lee, S. Zhang, W.S. Ahn, J. Mater. Chem. A 4 (2016) 16288–16311. doi: 10.1039/C6TA06089G

    151. [151]

      J.S.M. Lee, A.I. Cooper, Chem. Rev. 120 (2020) 2171–2214. doi: 10.1021/acs.chemrev.9b00399

    152. [152]

      P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem. Int. Ed. 47 (2008) 3450–3453. doi: 10.1002/anie.200705710

    153. [153]

      H.B. Yang, S.F. Hung, S. Liu, et al., Nat. Energy 3 (2018) 140–147. doi: 10.1038/s41560-017-0078-8

    154. [154]

      X.M. Hu, H.H. Hval, E.T. Bjerglund, et al., ACS Catal. 8 (2018) 6255–6264. doi: 10.1021/acscatal.8b01022

    155. [155]

      C. Costentin, S. Drouet, M. Robert, J.M. Savéant, Science 338 (2012) 90–94. doi: 10.1126/science.1224581

    156. [156]

      J. Shen, R. Kortlever, R. Kas, et al., Nat. Commun. 6 (2015) 8177. doi: 10.1038/ncomms9177

    157. [157]

      X. Zhu, C. Tian, G.M. Veith, et al., J. Am. Chem. Soc. 138 (2016) 11497–11500. doi: 10.1021/jacs.6b07644

    158. [158]

      G. Huang, Q. Niu, J. Zhang, et al., Chem. Eng. J. 427 (2022) 131018. doi: 10.1016/j.cej.2021.131018

    159. [159]

      G. Huang, Q. Niu, Y. He, et al., Nano Res. 15 (2022) 8001–8009. doi: 10.1007/s12274-022-4629-3

    160. [160]

      R. Xu, X.S. Wang, H. Zhao, et al., Catal. Sci. Technol. 8 (2018) 2224–2230. doi: 10.1039/C8CY00176F

    161. [161]

      R.K. Yadav, A. Kumar, N.J. Park, K.J. Kong, J.O.A. Baeg, J. Mater. Chem. A 4 (2016) 9413–9418. doi: 10.1039/C6TA01625A

    162. [162]

      J. He, X. Wang, S. Jin, Z.Q. Liu, M. Zhu, Chin. J. Catal. 43 (2022) 1306–1315. doi: 10.1016/S1872-2067(21)63936-0

    163. [163]

      R. Luo, M. Chen, F. Zhou, et al., J. Mater. Chem. A 9 (2021) 25731–25749. doi: 10.1039/D1TA08146B

    164. [164]

      J. Bi, B. Xu, L. Sun, et al., ChemSusChem 12 (2019) 4493–4499. doi: 10.1002/cssc.201901997

    165. [165]

      S. Guo, P. Yang, Y. Zhao, et al., ChemSusChem 13 (2020) 6278–6283. doi: 10.1002/cssc.202000712

    166. [166]

      Y.L. Yan, Q.J. Fang, J.k. Pan, et al., Chem. Eng. J. 408 (2021) 127358. doi: 10.1016/j.cej.2020.127358

    167. [167]

      P. Gotico, B. Boitrel, R. Guillot, et al., Angew. Chem. Int. Ed. 58 (2019) 4504–4509. doi: 10.1002/anie.201814339

    168. [168]

      Q. Wang, J. Wang, J.C. Wang, et al., ChemSusChem 14 (2021) 1131–1139. doi: 10.1002/cssc.202002847

    169. [169]

      R.S. Sprick, J.X. Jiang, B. Bonillo, et al., J. Am. Chem. Soc. 137 (2015) 3265–3270. doi: 10.1021/ja511552k

    170. [170]

      R. Banerjee, H. Furukawa, D. Britt, et al., J. Am. Chem. Soc. 131 (2009) 3875-3270. doi: 10.1021/ja809459e

    171. [171]

      R. Vaidhyanathan, S.S. Iremonger, G.K.H. Shimizu, et al., Science 330 (2010) 650–653. doi: 10.1126/science.1194237

    172. [172]

      W. Lu, D. Yuan, J. Sculley, et al., J. Am. Chem. Soc. 133 (2011) 18126–18129. doi: 10.1021/ja2087773

    173. [173]

      L.H. Xie, M.P. Suh, Chem. Eur. J. 19 (2013) 11590–11597. doi: 10.1002/chem.201301822

    174. [174]

      L. Qin, G.J. Xu, C. Yao, Y.H. Xu, Chem. Commun. 52 (2016) 12602–12605. doi: 10.1039/C6CC05097B

    175. [175]

      A. Yassin, M. Trunk, F. Czerny, et al., Adv. Funct. Mater. 27 (2017) 1700233. doi: 10.1002/adfm.201700233

    176. [176]

      D.S. Amaraseela, N.M. Sarih, S. Habibu, Energy Adv. 2 (2023) 1127–1133. doi: 10.1039/D2YA00346E

    177. [177]

      J. Weber, A. Thomas, J. Am. Chem. Soc. 130 (2008) 6334–6335. doi: 10.1021/ja801691x

    178. [178]

      C.A. Trickett, A. Helal, B.A. Almaythalony, et al., Nat. Rev. Mater. 2 (2017) 201745.

    179. [179]

      C. Chen, C. Tang, W. Xu, Y. Li, L. Xu, Phys. Chem. Chem. Phys. 20 (2018) 9536–9542. doi: 10.1039/C8CP00974K

    180. [180]

      X. Yao, K. Chen, L.Q. Qiu, Z.W. Yang, L.N. He, Chem. Mater. 33 (2021) 8863–8872. doi: 10.1021/acs.chemmater.1c03136

    181. [181]

      X.Y. Dong, Y.N. Si, Q.Y. Wang, S. Wang, S.Q. Zang, Adv. Mater. 33 (2021) 2101568. doi: 10.1002/adma.202101568

    182. [182]

      Y. Xie, T.T. Wang, X.H. Liu, K. Zou, W.Q. Deng, Nat. Commun. 4 (2013) 1960. doi: 10.1038/ncomms2960

    183. [183]

      X. Yu, Z. Yang, B. Qiu, et al., Angew. Chem. Int. Ed. 58 (2019) 632–636. doi: 10.1002/anie.201812790

    184. [184]

      S. Wang, X. Hai, X. Ding, et al., Nat. Commun. 11 (2020) 1149. doi: 10.1038/s41467-020-14851-7

  • Figure 1  CO2RR to product solar fuel molecules and the reaction mechanism from semiconductor catalysts.

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    Figure 2  Main factors influencing the product selectivity of photocatalytic CO2 reduction reactions.

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    Figure 3  Classification of precise active sites effects of PPs in photocatalytic CO2RR for improving reaction reactivity.

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    Figure 4  Proposed reaction paths for PPs photocatalytic CO2RR.

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    Figure 5  The effect of COF based catalysis for photocatalytic CO2RR. (a) Anchor effect on metalated-COF. (b) Support effect on COF based heterostructure.

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    Figure 6  Photosensitive metal Re site in COFs for PCO2RR. (a) The structure of 2D Re-COF Copied with permission [103]. Copyright 2018, American Chemical Society. (b) The structure of 2D bipyridine-containing COF with Re site. Copied with permission [104]. Copyright 2020, the Royal Society of Chemistry.

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    Figure 7  (a) The synthesis of TTCOF-M and (b, c) photocatalyst CO2RR performance. Copied with permission [110]. Copyright 2019, Wiley-VCH.

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    Figure 8  (a) The synthesis of MPor-DPP-COF and (b, c) photocatalyst CO2RR performance. Copied with permission [111]. Copyright 2022, American Chemical Society.

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    Figure 9  (a) COF-semiconductor Z-scheme system for artificial photosynthesis. (b) The charge-transfer process under light irradiation with the Z-scheme model. Copied with permission [113]. Copyright 2020, Wiley-VCH.

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    Figure 10  (a) The synthesis of COF-5/CoAl-LDH nanocomposite and (b) proposed mechanism. Copied with permission [128]. Copyright 2022, Wiley-VCH.

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    Figure 11  (a) The structure of TD-COF and Ni-PCD@TD-COF. (b, c) The CO2RR performance of Ni-TPAP. (d) The energy-level diagram showing the electron transfer from [Ru(bpy)3]Cl2 to Ni-PCD@TD-COF. Copied with permission [134]. Copyright 2020, Wiley-VCH.

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    Figure 12  (a) The in situ process for the synthesis of covalently bonded rGOx@TpPa-1 composites. (b) The energy level diagram of TpPa-1 and rGOx@TpPa-1. Copied with permission [135]. Copyright 2021, American Chemical Society.

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    Figure 13  (a) The preparation of g-C3N4/COF heterojunction. (b) The relative band energy positions and S-scheme charge transfer mechanism between Tp-Tta COF and g-C3N4. Copied with permission [136]. Copyright 2022, Elsevier B.V.

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    Figure 14  CTFs via synthesis methods that use varying aromatic and cyanuric halides as monomers.

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    Figure 15  (a) The structure of Pt-SAC/CTF-1. (b) Photocatalytic CO2 conversion rates of CTF-1, CTF-EG, Pt-NP/CTF-1, Pt-SA/CTF-1 and Pt/C3N4-EG. (c) In-situ FTIR spectra of the adsorbed species for Pt-SA/CTF-1. (d) The mechanization of photocatalytic CO2 reduction for Pt-SA/CTF-1. Copied with permission [158]. Copyright 2022, Elsevier B.V.

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    Figure 16  (a) The structure of Cu-SA/CTF. (b) Photocatalytic CO2 reduction performance of CTF-1, Cu-NP/CTF, and Cux-SA/CTF. (c) In-situ FTIR spectra of the adsorbed species for Cu0.10-SA/CTF. (d) The conversion of photocatalytic CO2 reduction for Cux-SA/CTF. Copied with permission [159]. Copyright 2022, Springer.

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    Figure 17  (a) Schematic illustration of the CTF film photocatalyst-enzyme coupled system involved in the exclusive production of formic acid from CO2. (b) Photocatalytic activities of the CTF and monomer for selective enzymatic production of formic acid from CO2. (c) Photograph of the flexible film photocatalyst along with the detailed chemical structure of the CTF. Copied with permission [161]. Copyright 2016, the Royal Society of Chemistry.

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    Figure 18  (a) The synthesis and photocatalytic procedure of CN/CTF heterostructure. (b) Energy band structure of the as-synthesized CN/CTF heterostructure. Copied with permission [162]. Copyright 2018, the Royal Society of Chemistry.

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    Figure 19  Molecular based strategies to improve the photocatalytic performances of CMPs.

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    Figure 20  The mechanism of CO2RR of metalloporphyrin based CMPs. (a) The optimized structures of various intermediate species adsorbed on the Fe-TMP substrate and the overall pathway of CO2 reduction and each elemental step's activation barriers. Copied with permission [179]. Copyright 2018, the Royal Society of Chemistry. (b) The energy-level diagram and proposed mechanism for photocatalytic CO2RR of POPn-Fe. Copied with permission [180]. Copyright 2021, American Chemical Society.

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    Figure 21  (a) The structure of NiPc–MPOP and the high CO2 reduction activity of Ni–N2O2 species compared to that of Ni–N4. (b, c) The high CO2 reduction activity of Ni–N2O2 species compared to that of Ni–N4. Copied with permission [181]. Copyright 2021, Wiley-VCH.

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    Figure 22  (a) Illustration of synthesis and the strategy of eliminating the charge-transfer bridge. (b) Proposed process of electron transfer over the CP-A series and CP-D series for the CO2 photoreduction reaction. Copied with permission [184]. Copyright 2020, Springer Nature.

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    Table 1.  Photocatalytic multielectron processes of CO2RR [61,62].
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    Table 2.  Summary of photocatalytic CO2 reduction using COF based photocatalysts.
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    Table 3.  Summary of photocatalytic CO2 reduction using CTF based photocatalysts.
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    Table 4.  Summary of photocatalytic CO2 reduction using CMPs.
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  • 发布日期:  2025-01-15
  • 收稿日期:  2024-02-21
  • 接受日期:  2024-05-10
  • 修回日期:  2024-03-13
  • 网络出版日期:  2024-05-11
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