Utilizing sunlight to convert CO2 into chemical fuels could simultaneously address the greenhouse effect and fossil fuel crisis. ZnSe nanocrystals are promising candidates for photocatalysis because of their low toxicity and excellent photoelectric properties. However, pristine ZnSe generally has low catalytic activities due to serious charge recombination and the lack of efficient catalytic sites for CO2 reduction. Herein, a ZnSe nanorods-CsSnCl3 perovskite (ZnSe-CsSnCl3) type II heterojunction composite is designed and prepared for photocatalytic CO2 reduction. The ZnSe-CsSnCl3 type II heterojunction composite exhibits enhanced photocatalytic activity for CO2 reduction with respect to pristine ZnSe nanorods. The experimental characterizations and theoretical calculations reveal that the efficient charge separation and lowered free energy of CO2 reduction facilitate the CO2 conversion on the ZnSe-CsSnCl3 heterojunction composite. This work presents a type II heterojunction composite photocatalyst based on ecofriendly metal chalcogenides and metal halide perovskites. Our study has also promoted the understanding of the CO2 reduction mechanisms on perovskite nanocrystals, which could be valuable for the development of metal halide perovskite photocatalysts.

ZnSe Nanorods-CsSnCl3 Perovskite Heterojunction Composite for Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction is an appealing approach to convert solar energy into high value-added chemicals All-inorganic CsPbBr3 quantum dots (QDs) have emerged as a promising photocatalyst for reducing CO2 However, pristine CsPbBr3 has a low catalytic performance, mainly due to severe charge recombination Herein, a 0D/2D heterojunction of CsPbBr3 QDs/Bi2WO6 nanosheet (CPB/BWO) photocatalysts is fabricated for photocatalytic CO2 reduction The CPB/BWO photocatalyst achieves excellent photocatalytic performance: the total yield of CH4/CO is 503 μmol g-1, nearly 95 times higher than the pristine CsPbBr3 The CPB/BWO heterojunction also exhibits much-improved stability during photocatalytic reactions On the basis of various characterization techniques, our investigations verified a direct Z-scheme charge migration mechanism between CsPbBr3 QDs and Bi2WO6 nanosheets The improved photocatalytic performance is originated from the high spatial separation of photoexcited charge carriers in CPB/BWO, which can also preserve strong individual redox abilities of two components This work reports an efficient direct Z-scheme heterojunction photocatalytic system based on metal halide perovskites The novel strategy we proposed may bring up new opportunities for the development of metal halide perovskite photocatalysts with greatly enhanced activities

Direct Z-Scheme 0D/2D Heterojunction of CsPbBr3 Quantum Dots/Bi2WO6 Nanosheets for Efficient Photocatalytic CO2 Reduction

Covalent Organic Frameworks as Emerging Platforms for CO2 Photoreduction

Porphyrin-based covalent organic frameworks (Por-COF) nanosheets were vertically anchored on carbon nanotubes (CNT) with covalent connection for efficient electrocatalytic CO2 reduction reaction (CO2RR). The CNT not only acts as ideal carriers for the dispersion of Pro-COF but also facilitates electron transfer along porphyrin planes to immobilized metal active sites. As a result, covalently linked MWCNT-Por-COF-M (M: Co, Ni, Fe) display improved electrocatalytic CO2-to-CO activity and selectivity compared to pure Por-COF-M and MWCNT@Por-COF-M without covalent connection between two components. In particular, MWCNT-Por-COF-Co exhibits superior activity (FECO: 99.3%), higher partial current density and good durability in 0.5 M KHCO3 by H-type cell, while MWCNT-Por-COF-Cu exhibits the highest CH4 faradaic efficiency of 71.2% in 1.0 M KOH by flow cell. The results of HRTEM and Auger spectrum revealed that the high performance of MWCNT-Por-COF-Cu could be attributed to the generated Copper-based nanoclusters during the electrocatalytic CO2RR process.

Covalently anchoring covalent organic framework on carbon nanotubes for highly efficient electrocatalytic CO2 reduction

Recent advances in metal halide perovskite photocatalysts: Properties, synthesis and applications

Photocatalytic reduction of CO2 into value-added chemical fuels is an appealing approach to address energy crisis and global warming. CsPbBr3 quantum dots (QDs) are good candidates for CO2 reduction because of their excellent photoelectric properties, including high molar extinction coefficient, low exciton binding energy, and defect tolerance. However, the pristine CsPbBr3 QDs generally have low photocatalytic performance mainly due to dominant charge recombination and lack of efficient catalytic sites for CO2 adsorption/activation. Herein, we report a new photocatalytic system, in which CsPbBr3 QDs are coupled with covalent triazine frameworks (CTFs) for visible-light-driven CO2 reduction. In this hybrid photocatalytic system, the robust triazine rings and periodical pore structures of CTFs promote the charge separation in CsPbBr3 and endow them with strong CO2 adsorption/activation capacity. The resulting photocatalytic system exhibits excellent photocatalytic activity towards CO2 reduction. This work presents a new photocatalytic system based on CTFs and perovskite QDs for visible-light-driven CO2 reduction, which highlights the potential of perovskite-based photocatalysts for solar fuel applications.

Coupling CsPbBr 3 Quantum Dots with Covalent Triazine Frameworks for Visible‐Light‐Driven CO 2 Reduction

Harvesting solar energy to convert carbon dioxide (CO2) into fossil fuels shows great promise to solve the current global problems of energy crisis and climate change. To achieve this goal, it is desirable to develop efficient catalysts with visible light response to cater for the solar spectrum. CdTe QDs are ideal candidates for absorbing visible light, but it is difficult to directly perform CO2 reduction due to the lack of effective catalytic sites. Herein, we report a strategy for the activation of mercaptopropionic acid (MPA)-capped CdTe QDs for visible-light-driven CO2 reduction, in which iron ions (Fe2+) are immobilized onto CdTe QDs using L-cysteine as a bridging ligand (CdTe-b-Fe). This ligand bridging strategy can immobilize Fe2+ ions on the surface of CdTe QDs as catalytic sites, and these catalytic sites can be conveniently adjusted by directly adding different types or numbers of metal ions. In addition to effectively immobilizing catalytic sites, the bridging ligands can also provide a pathway for electron transport between CdTe QDs and the catalytic sites. The CdTe-b-Fe QD system based on the ligand bridging strategy exhibits excellent catalytic properties: the yield of CH4/CO (two products together) is 126 μmol g−1 h−1, and the selectivity for carbon-based products approaches 98%. This work presents a facile strategy for immobilizing catalytic sites on QDs and provides a platform for designing efficient visible-light driven catalysts for CO2 reduction.

Immobilization of catalytic sites on quantum dots by ligand bridging for photocatalytic CO2 reduction.

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Coupling CsPbBr 3 Quantum Dots with Covalent Triazine Frameworks for Visible‐Light‐Driven CO 2 Reduction

Immobilization of catalytic sites on quantum dots by ligand bridging for photocatalytic CO2 reduction.