School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang, Henan 453007, PR China.
Key Laboratory of Yellow River and Huai River Water Environment and Pollution Control, Ministry of Education, Henan Key Laboratory for Environment Pollution Control, International Joint Laboratory on Key Techniques in Water Treatment, Henan Province, School of Environment, Henan Normal University, Xinxiang, Henan 453007, PR China.
J Colloid Interface Sci. 2023 Oct 15;648:259-269. doi: 10.1016/j.jcis.2023.05.173. Epub 2023 Jun 2.
Efficient catalytic electrodes for cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER) are pivotal for massive production of green hydrogen from water electrolysis, and the further replacement of kinetically sluggish OER by tailored elecrooxidation of certain organics is a promising way to co-produce hydrogen and value-added chemicals via a more energy-saving and safer manner. Herein, amorphous Ni-Co-Fe ternary phosphides (NiCoFe-Ps) with different Ni:Co:Fe ratios electrodeposited onto Ni foam (NF) substrate were served as self-supported catalytic electrodes for alkaline HER and OER. The NiCoFe-P electrode deposited in solution at Ni:Co:Fe ratio of 4:4:1 displayed low overpotential (61 mV at -20 mA cm) and acceptable durability for HER, while the NiCoFe-P electrode fabricated in deposition solution at Ni:Co:Fe ratio of 2:2:1 showed good OER efficiency (overpotential of 275 mV at 20 mA cm) and robust durability, the further replacement of OER by anodic methanol oxidation reaction (MOR) enabled selective production of formate with 110 mV lower anodic potential at 20 mA cm. The HER-MOR co-electrolysis system based on NiCoFe-P cathode and NiCoFe-P anode could save 1.4 kWh of electric energy per cubic meter of H relative to mere water electrolysis. The current work offers a feasible approach to co-produce H and value-upgraded formate via an energy-saving manner by rational design of catalytic electrodes and construction of co-electrolysis system, and paves the way for cost-effective co-preparation of more value-added organics and green hydrogen via electrolysis.
用于阴极析氢反应 (HER) 和阳极析氧反应 (OER) 的高效催化电极对于通过水电解大规模生产绿色氢气至关重要，而通过定制电氧化某些有机物来进一步替代动力学缓慢的 OER 是通过更节能和更安全的方式共生产氢气和增值化学品的有前途的方法。在此，沉积在 Ni 泡沫 (NF) 基底上的不同 Ni:Co:Fe 比例的非晶态 Ni-Co-Fe 三元磷化物 (NiCoFe-Ps) 被用作碱性 HER 和 OER 的自支撑催化电极。在 Ni:Co:Fe 比为 4:4:1 的溶液中沉积的 NiCoFe-P 电极显示出低过电位 (在-20 mA cm 时为 61 mV) 和对 HER 的可接受的耐久性，而在 Ni:Co:Fe 比为 2:2:1 的沉积溶液中制备的 NiCoFe-P 电极显示出良好的 OER 效率 (在 20 mA cm 时为 275 mV 的过电位) 和稳健的耐久性，通过阳极甲醇氧化反应 (MOR) 进一步替代 OER ，可以在 20 mA cm 时以 110 mV 更低的阳极电势选择性地生产甲酸盐。基于 NiCoFe-P 阴极和 NiCoFe-P 阳极的 HER-MOR 共电解系统可以相对于单纯的水电解每立方米氢气节省 1.4 kWh 的电能。这项工作通过合理设计催化电极和构建共电解系统，提供了一种通过节能方式共生产 H 和增值甲酸盐的可行方法，并为通过电解更经济有效地共制备更多增值有机物和绿色氢气铺平了道路。
