Nasir Muhammad Salman, Sheng Bowen, Zhao Ying, Ye Haotian, Song Jun, Li Jinglin, Wang Ping, Wang Tao, Wang Xinqiang, Huang Zhen, Zhou Baowen
Key Laboratory for Power Machinery and Engineering of Ministry of Education, Research Center for Renewable Synthetic Fuel, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
State Key Laboratory of Artificial Microstructure and Mesoscopic Physics, School of Physics, Nano-Optoelectronics Frontier Center of Ministry of Education (NFC-MOE), Peking University, Beijing 100871, China.
Sci Bull (Beijing). 2025 Feb 15;70(3):373-382. doi: 10.1016/j.scib.2024.11.021. Epub 2024 Nov 19.
Solar-driven overall conversion of CO and HO into fuels and chemicals shows an ultimate strategy for carbon neutrality yet remains a huge challenge. Herein, an integrated photocatalytic redox architecture of Zn NPs/GaN Nanowires (NWs)/Si is explored for light-driven overall conversion of CO and HO into CH and HO simultaneously without any external sacrificial agents and additives. The as-designed architecture affords a benchmark CH activity of 189 mmol g h with a high selectivity of 93.6%, in the synchronized formation of HO at a considerable rate of 25 m g h. Moreover, a considerable turnover number of 27,280 mol CH per mol Zn was achieved over a long-term operation of 80 h. By operando spectroscopic characterizations, isotope experiments, and density functional theory calculations, it is unraveled that Zn sites are synergetic with GaN to drive CO-to-CH conversion with a lowered energy barrier of 0.27 eV while inhibiting hydrogen evolution reaction with a relatively high energy barrier of 0.93 eV. Notably, owing to the unique surface properties of GaN, water is split into *OH and *H, followed by the formation of HO because of the alleviated adsorption strength of *OH by Zn NPs. Together, the hierarchical architecture enables the achievement of high activity and high selectivity of CH from CO reduction in distilled water along with the generation of HO. This work provides an integrated photocatalytic redox architecture for the synchronized production of CH and HO with the only inputs of CO, distilled water, and light.
太阳能驱动将CO和H₂O整体转化为燃料和化学品是实现碳中和的终极策略，但仍然是一个巨大的挑战。在此，探索了一种Zn NPs/GaN纳米线（NWs）/Si的集成光催化氧化还原结构，用于在无任何外部牺牲剂和添加剂的情况下，将CO和H₂O光驱动整体同时转化为CH₄和H₂O₂。所设计的结构实现了189 mmol g⁻¹ h⁻¹的基准CH₄活性，选择性高达93.6%，同时以25 μmol g⁻¹ h⁻¹的可观速率同步生成H₂O₂。此外，在80小时的长期运行中，每摩尔Zn实现了相当可观的27280摩尔CH₄的周转数。通过原位光谱表征、同位素实验和密度泛函理论计算，揭示了Zn位点与GaN协同作用，以降低0.27 eV的能垒驱动CO到CH₄的转化，同时以0.93 eV的相对高能垒抑制析氢反应。值得注意的是，由于GaN独特的表面性质，水被分解为OH和H，随后由于Zn NPs对*OH吸附强度的缓解而形成H₂O₂。总之，这种分层结构能够在蒸馏水中从CO还原中实现CH₄的高活性和高选择性以及H₂O₂的生成。这项工作提供了一种集成光催化氧化还原结构，用于以CO、蒸馏水和光作为唯一输入同步生产CH₄和H₂O₂。
