Converting CO2 into CO, CH4, and other hydrocarbons using solar energy presents a viable approach for addressing energy shortages. In this study, photocatalysts with S-deficient WO3/Zn3In2S6 (WO3/VS-ZIS) S-scheme heterojunctions have been successfully synthesized. Under UV-vis light irradiation, 20 %WO3/VS-ZIS demonstrated significantly improved CO2 reduction activity and CH4 selectivity. Detailed characterization and density functional theory (DFT) calculations reveal that the enhanced performance is due to the synergistic optimization of the S-scheme heterojunction and sulfur vacancies (VS) for CO2 reduction. The presence of VS aids in the adsorption and activation of CO2 and enhances the separation of charge carriers. The 2D/2D S-scheme heterostructure assembled with WO3 nanosheets not only accelerates the migration and separation of photoexcited charge carriers but also improves the adsorption of H2O and the formation of VS, thereby increasing the adsorption and activation of CO2 and facilitating the protonation of CO* to produce CH4. This study clarifies the synergistic effect of VS and S-scheme heterostructures in improving photocatalytic performance, offering valuable insights into the photoactivation process of CO2 at VS in S-scheme heterojunctions.

The photocatalytic CO2 reduction reaction is severely limited by sluggish charge kinetics. To address this issue, a strategy utilizing non-metal-doped layered double hydroxide (LDH) has been developed to control the electronic structure of spindle-shaped nanoflowers, resulting in efficient photocatalytic CO2 reduction. The results demonstrate that the designed catalyst yields 263.16 μmol g-1 h-1 for the photoreduction of CO2 to CO. Furthermore, the in situ Fourier transform infrared spectrum (FT-IR) analysis demonstrate that the specific S-ligand (S-bridge) facilitates CO2 activation, ensuring the continuous production of *COOH. The hydrothermal-assisted ionic liquid method proposed in this study offers guidance for modifying catalysts.

To enhance the economic viability of photocatalytic materials for carbon capture and conversion, the challenge of employing expensive photosensitizer must be overcome. This study aims to improve the visible light utilization with zirconium-based metal-organic frameworks (Zr-MOFs) by employing a multi-component post-synthetic modification (PSM) strategy. An economical photosensitiser and copper ions are introduced into MOF 808 to enhance its photoreduction properties. Notably, the PSM of MOF 808 shows the highest CO yield up to 236.5 μmol g-1 h-1 with aHCOOH production of 993.6 μmol g-1 h-1 under non-noble metal, and its mechanistic insight for CO2 reaction is discussed in detail. The research results have important reference value for the potential application of photocatalytic metal-organic frameworks.

Global warming is the biggest threat to the entire world owing to the continuous release of greenhouse gases such as CO2 from various sources. Herein, we have utilized renewable energy for the conversion of CO2 to valuable feedstocks through a semiconductor-mediated photocatalytic system. The cadmium sulfide nanoflowers (CS-NFs) decorated graphitic carbon nitride (CN) through a solvothermal route to form a Z-scheme CSCN heterojunction. The as-synthesized material has been characterized by various spectroscopic and microscopic tools. The optimal CSCN-0.5 (1:0.5) photocatalyst achieves a CO production rate of 130.9 μmol g-1 under visible light irradiation of 4h (λ > 420 nm), doubling that of pristine CS-NFs and CN. CO, along with CH4 (3.4 μmol g-1) and C2H6 (2.9 μmol g-1), is the sole product detected. Experimental results indicate that the CSCN-0.5 photocatalyst spatially separates electron-hole pairs, suppresses charge carrier recombination, and maintains robust redox ability, enhancing CO2 photoreduction. The CO2 reduction mechanism over CSCN heterojunction was also studied through in-situ DRIFTS and electron spin resonance (ESR) measurements. Therefore, CSCN proves that it could be used as a robust photocatalyst for the CO2 reduction reactions towards C1 and C2 feedstocks.

Solar-energy-powered CO2 reduction into valuable chemical fuels represents a highly promising strategy to address the currently energy and environmental issues. Owing to the nontoxicity and robust reduction capability, lead-free Cs3Bi2Br9 perovskite quantum dots (PQDs) are regarded as an attractive material for CO2 photoreduction. Nevertheless, the potential of their applications in this field has been restricted by the severe charge recombination, resulting in unsatisfactory photocatalytic performance. Herein, a step-scheme-based Cs3Bi2Br9@Nb2O5 (CBB@Nb2O5) nanocomposite was fabricated by embedding the CBB PQDs into mesoporous Nb2O5. Experimental studies, along with theoretical calculations, revealed that the charge migration route in the CBB@Nb2O5 nanocomposite conformed to the step-scheme (S-scheme) mode, enabling effective charge separation and strong redox ability preservation. Profiting from the promoted charge separation, as well as the improved CO2 adsorption contributed by mesoporous Nb2O5, the CBB@Nb2O5 nanocomposite unveiled superior CO2 photoreduction performance, with CO evolution rate reaching 143.63 μmol g-1h-1. The present study provides a potential strategy to manufacture highly-efficient perovskite-based photocatalysts for achieving carbon neutrality.

This study assessed the photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction. The TNA photocatalysts were fabricated by titanium anodization and submitted to an annealing treatment for crystallization and/or cathodic reduction to introduce Ti3+ and oxygen vacancies into the TiO2 structure. The cathodic reduction demonstrated a significant effect on the generated photocurrent. The photoactivity of the four TNA catalysts in CO2 reduction with water vapor was evaluated under UV irradiation for 3 h, where CH4 and H2 were detected as products. The annealed sample exhibited the best performance towards methane with a production rate of 78 μmol gcat-1 h-1, followed by the amorphous film, which also exhibited an impressive formation rate of 64 μmol gcat-1 h-1. The amorphous and reduced-amorphous films exhibited outstanding photoactivity regarding H2 production (142 and 144 μmol gcat-1 h-1, respectively). The annealed catalyst also revealed a good performance for H2 production (132 μmol gcat-1 h-1) and high stability up to five reaction cycles. Molecular dynamic simulations demonstrated the changes in the band structure by introducing oxygen vacancies. The topics covered in this study contribute to the Sustainable Development Goals (SDG), involving affordable and clean energy (SDG#7) and industry, innovation, and infrastructure (SDG#9).

Photocatalytic CO2 reduction to valuable fuels has proved to be a favourable process to produce renewable energy and reduce CO2 emissions, which mostly depends on designing effective photocatalysts with the rapid separation rate of charge carriers. In this contribution, mesoporous n-n heterojunction Li2MnO3/WO3 nanocomposites were designed via a simplistic sol-gel process for CO2 reduction utilizing visible illumination (λ > 420 nm). XRD and TEM measurements confirmed the synthesized Li2MnO3/WO3 nanocomposite is a monoclinic structure, and its particle size is 25 ± 5 nm. The obtained Li2MnO3/WO3 exhibited narrower bandgap energy (1.74 eV), larger surface area (212 m2g-1), exceedingly visible absorbing, and lower recombination of electron and hole. The yield of CH3OH was determined about 198, 871, 1140, 1550 and 1570 mmolg-1 for bare WO3 and 5%, 10%, 15% and 20% Li2MnO3/WO3 nanocomposites, respectively. These results evidenced that the 15% Li2MnO3/WO3 photocatalyst exhibited the best reduction ability compared to other nanocomposites. The CO2 reduction over 15% Li2MnO3/WO3 photocatalyst achieved a maximal CO2 conversion with the substantially boosted CH3OH, i.e., 1550 mmolg-1 after 9 h, which was enhanced 7.8 folds great than of WO3 NPs. Mesoporous Li2MnO3/WO3 nanocomposites, in comparison with bare WO3 NPs, created more active sites for facilitating CO2 and had a specific electric field to more effectively separate charge carriers. The Li2MnO3/WO3 photocatalyst has superior photostability during the continuous reduction of CO2 for 45 h with no remarkable decrease. The possible direct S-scheme mechanism for electron transfer over Li2MnO3/WO3 photocatalyst with the enhanced CO2 reduction ability was discussed. The present work demonstrates an avenue for building highly effective heterostructure photocatalysts in solar-energy-induced potential applications.

The major challenge in the photocatalytic reduction of CO2 is to achieve high conversion efficiency while maintaining selectivity for a single product. Photocatalysts containing single-metal Cu2+ with 3d9 and Zn2+ with 3d10 on g-C3N4 were prepared using a high-energy ball mill. Single-atom Zn inner electron configuration is stable (3d10) and the peripheral empty orbitals act as electron traps to trap photo-generated electrons and improve the efficiency of charge separation; Zn is an active site to enhance the adsorption and activation of CO2. The stable electron configuration can reduce the energy required for the overall reaction and increase the activity while changing the reaction pathway to form CO. As a result, the 0.5 mol% Zn/g-C3N4 (Zn-CN-0.5) photocatalyst achieves ∼100 % selectivity for the photocatalytic reduction of CO2 to CO at a rate of ∼21.1 μmol·g-1·h-1. In contrast, the 0.5 mol% Cu/g-C3N4 (Cu-CN-0.5) photocatalyst with an unstable electronic structure does not exhibit high selectivity.

Photocatalytic conversion of carbon dioxide (CO2) into high value-added chemicals is an attractive yet challenging process, primarily due to the readily recombination of hole-electron pairs in photocatalysts. Herein, dual-oxygen-vacancy mediated Z-scheme Bi2Sn2O7/Sn/NiAl-layered double hydroxide (VO,O-20BSL) heterojunctions were hydrothermally synthesized and subsequently modified with Sn monomers to enhance photocatalytic activity toward CO2 reduction. The abundance of oxygen vacancies endowed the VO,O-20BSL with extended optical adsorption, enhanced charges separation, and superior CO2 adsorption and activation. The interfacial charges transfer of the VO,O-20BSL was demonstrated to follow a Z-scheme mechanism via photochemical deposition of metal/metal oxide. Under visible light irradiation, the VO,O-20BSL exhibited the highest yields of carbon monoxide (CO) and methane (CH4), with values of 72.03 and 0.85 umol·g-1·h-1, respectively, which were 2.66 and 1.57 times higher than that of the VO-NiAl-layered double hydroxide (VO-1LDH). In situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) revealed that carboxylic acid groups (COOH*) and aldehyde groups (CHO*) were the predominant intermediates during CO2 reduction, and accordingly, possible CO2 reduction pathways and mechanism were proposed. This study presents a feasible approach to incorporate dual vacancies into Z-scheme heterojunctions for CO2 reduction.

Hollow structure hybrids have gained considerable attention for their ability to reduce CO2 owing to their rich active sites, high gas adsorption ability, and excellent light utilization capacity. Herein, a template-engaged strategy was provided to fabricate copper sulphide@cerium dioxide (CuS@CeO2) p-n heterojunction hollow cube photocatalysts using Cu2O cubes as a sacrificial template. The sequential steps of loading of CeO2 nanolayer, sulfidation, and etching reaction facilitate the formation of CuS@CeO2 p-n heterojunction hollow cubes. Compared with the single CuS, CeO2, and their physical mixture, the CuS@CeO2 p-n heterojunction hollow cube photocatalyst expresses a higher performance toward photocatalytic CO2 reduction under solid-gas reaction conditions due to the faster separation of photogenerated charges. The further enhanced performance of CuS@CeO2 p-n heterojunction hollow cubes was achieved by decorating pt nanoparticles due to the fact that Pt nanoparticles had a high electron affinity and CO2 adsorption capacity, and the highest CO and CH4 yields of the optimized hybrid reached 195.8 μmol g-1 h-1 and 19.96 μmol g-1 h-1, respectively. This work might provide a strategy for designing and synthesizing efficient hollow heterostructured photocatalysts for solar energy conversion and utilization.