Abstract When it comes to using solar energy to promote catalytic reactions, photocatalysis technology is the first choice. However, sunlight can not only be directly converted into chemical energy through a photocatalytic process, it can also be converted through different energy‐transfer pathways. Using sunlight as the energy source, photocatalytic reactions can proceed independently, and can also be coupled with other catalytic technologies to enhance the overall catalytic efficiency. Therefore, sunlight‐driven catalytic reactions are diverse, and need to be given a specific definition. We propose a timely perspective for catalytic reactions driven by sunlight and give them a specific definition, namely “solar energy catalysis”. The concept of different types of solar energy catalysis, such as photocatalysis, photothermal catalysis, solar cell powered electrocatalysis, and pyroelectric catalysis, are highlighted. Finally, their limitations and future research directions are discussed.

Solar Energy Catalysis

The photocatalytic transformation of carbon dioxide (CO2) into carbon‐based fuels or chemicals using sustainable solar energy is considered an ideal strategy for simultaneously alleviating the energy shortage and environmental crises. However, owing to the low energy utilization of sunlight and inferior catalytic activity, the conversion efficiency of CO2 photoreduction is far from satisfactory. In this study, a MOF‐derived hollow bimetallic oxide nanomaterial is prepared for the efficient photoreduction of CO2. First, a unique ZIF‐67‐on‐InOF‐1 heterostructure is successfully obtained by growing a secondary Co‐based ZIF‐67 onto the initial InOF‐1 nanorods. The corresponding hollow counterpart has a larger specific surface area after acid etching, and the oxidized bimetallic H‐Co3O4/In2O3 material exhibits abundant heterogeneous interfaces that expose more active sites. The energy band structure of H‐Co3O4/In2O3 corresponds well with the photosensitizer of [Ru(bpy)3]Cl2, which results in a high CO yield of 4828 ± 570 µmol h−1 g−1 and stable activity over a consecutive of six runs, demonstrating adequate photocatalytic performance. This study demonstrates that the rational design of MOF‐on‐MOF heterostructures can completely exploit the synergistic effects between different components, which may be extended to other MOF‐derived nanomaterials as promising catalysts for practical energy conversion and storage.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/advs.202300797

MOF‐on‐MOF‐Derived Hollow Co3O4/In2O3 Nanostructure for Efficient Photocatalytic CO2 Reduction

We report an oxygen vacancy (Vo)-rich metallic MoO2-x nano-sea-urchin with partially occupied band, which exhibits super CO2 (even directly from the air) photoreduction performance under UV, visible and near-infrared (NIR) light illumination. The Vo-rich MoO2-x nano-sea-urchin displays a CH4 evolution rate of 12.2 and 5.8 μmol gcatalyst-1 h-1 under full spectrum and NIR light illumination in concentrated CO2, which is ca. 7- and 10-fold higher than the Vo-poor MoO2-x, respectively. More interestingly, the as-developed Vo-rich MoO2-x nano-sea-urchin can even reduce CO2 directly from the air with a CO evolution rate of 6.5 μmol gcatalyst-1 h-1 under NIR light illumination. Experiments together with theoretical calculations demonstrate that the oxygen vacancy in MoO2-x can facilitate CO2 adsorption/activation to generate *COOH as well as the subsequent protonation of *CO towards the formation of CH4 because of the formation of a highly stable Mo-C-O-Mo intermediate.

Identification of the Active Sites on Metallic MoO2-x Nano-Sea-Urchin for Atmospheric CO2 Photoreduction Under UV, Visible and Near-Infrared Light Illumination.

Photocatalytic technology to convert CO2 into chemical fuel is one of the most promising ways to alleviate the greenhouse effect. However, due to the low photocatalytic efficiency and poor product...

Photothermal-coupled solar photocatalytic CO2 reduction with high efficiency and selectivity on MoO3−x@ZnIn2S4 core-shell S-scheme heterojunction

Utilizing localized surface plasmon resonance (LSPR) effect of catalysts to facilitate photothermal catalysis of CO2 to CH4 is an attractive strategy for mitigating CO2 emissions. Herein, we demonstrate that Ru/HxMoO3-y synthesized via H-spillover exhibits plasmonic absorption in the visible-near-infrared (Vis-NIR) region, achieving a CH4 yield of 20.8 mmol/gcat/h (520 mmol/gRu/h) with 100 % selectivity in the CO2 methanation under Vis-NIR light irradiation at 140 °C. Irradiation with Vis-NIR light substantialy increases the CH4 yield (~ 4.7 fold) compared with that under dark conditions. The abundant surface oxygen vacancies provide active sites for CO2 adsorption and activation. In situ infrared spectroscopic analysis reveals that photothermal catalytic CO2 methanation follows *CO pathway. This work represents a simple strategy for developing a plasmonic catalyst for efficient photothermal catalytic CO2 methanation. 

Ru/H MoO3- with Plasmonic Effect for Boosting Photothermal Catalytic CO2 Methanation

Infrared (IR) light serves as an attractive renewable source of solar energy for photothermal CO2 methanation. Herein, we report the synthesis of Ni nanoparticles (NPs) supported on TiO2 (Ni/TiO2) derived from MIL-125(Ti) (MOFs), which achieves a CH4 production rate of 271.9 mmol gNi-1 h-1 with nearly 100% selectivity and good durability at least 48 h under IR irradiation. The results indicate the catalytic performance is predominantly driven by thermal energy from efficient IR light conversion. IR light acts as the most effective light source and induces highest activity and CH4 selectivity over 8Ni/TiO2 compared with UV–vis and full spectrum light. Highly-dispersed small-size Ni NPs, rich oxygen vacancies (OVs), strong adsorption capacity and enhanced CO2 activation ability contribute to the high catalytic performance. OVs over Ni/TiO2 play a crucial role in the CH4 formation. This work demonstrates a feasible strategy towards the synthesis of MOF-derived catalysts for efficient photothermal CO2 methanation.

Efficient infrared-light-driven photothermal CO2 reduction over MOF-derived defective Ni/TiO2

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Efficient infrared-light-driven photothermal CO2 reduction over MOF-derived defective Ni/TiO2