The sluggish kinetics of the anodic oxygen evolution reaction (OER) and the valueless product O₂ are tricky issues for water splitting. Replacing the OER with a more thermodynamically favorable selective methanol oxidation reaction (SMOR) to combine with the hydrogen evolution reaction can not only lower the applied voltage but also simultaneously produce value-added formate in the anode and hydrogen energy in the cathode. Herein, a mirror-like heterostructure of NiCoSe₄@NiCo-LDH supported on cobalt foam (NCS/CF) was synthesized by partial selenidation of NiCo-LDH to facilitate the SMOR. Experimental tests and theoretical calculations revealed the “shuttle-like” role of Se in NCS/CF, by which electrons of Ni were first transferred to Se and then to Co. Moreover, the superiority of the bimetallic compound was also proved by comparing the activity of NCS/CF to that of the counterparts NiSe₂@Ni(OH)₂/CF (NS/CF) and CoSe₂@Ni(OH)₂/CF (CS/CF). Owing to the unique electronic effect of the strongly coupled hetero-interface and the bimetallic synergism, more accessible active sites, fast charge transfer ability, facilitated catalytic kinetics, and modulated electron redistribution were achieved. Therefore, improved SMOR performance was obtained with ∼100% faradaic efficiency of methanol-to-formate. The potential at 10 and 100 mA cm⁻² was only 1.274 and 1.432 V vs. RHE, respectively, outperforming most existing catalysts. In addition, the two-electrode electrolyzer of methanol-assisted water electrolysis with NCS/CF as both the anode and cathode only required an applied cell voltage of 1.380 V to reach 10 mA cm⁻², 253 mV less than that of pure water splitting. Meanwhile, outstanding catalytic stability was achieved by continuously delivering a current density of 100 mA cm⁻² for 100 hours without obvious attenuation. The inference of the “shuttle-like” role of Se will provide new insight into the electronic redistribution in the NiCo-LDH derivative that is incorporated with foreign atoms. The integration of methanol upgradation and hydrogen generation exploits an energy-saving way to simultaneously obtain value-added organic substances and green hydrogen.

中文翻译：

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一种高效的 NiCoSe4/NiCo-LDH/CF 催化剂，用于通过选择性甲醇电氧化联产增值甲酸盐和氢气


阳极析氧反应（OER）的缓慢动力学和无价值的产物O ₂是水分解的棘手问题。用热力学上更有利的选择性甲醇氧化反应（SMOR）代替OER，与析氢反应结合，不仅可以降低外加电压，还可以同时在阳极产生增值的甲酸盐，在阴极产生氢能。在此，通过NiCo-LDH的部分硒化以促进SMOR，合成了负载在泡沫钴（NCS/CF）上的NiCoSe ₄ @NiCo-LDH的镜状异质结构。实验测试和理论计算揭示了Se在NCS/CF中的“穿梭”作用，Ni的电子首先转移到Se，然后转移到Co。此外，通过活性比较也证明了双金属化合物的优越性。 NCS/CF 与对应物 NiSe ₂ @Ni(OH) ₂ /CF (NS/CF) 和 CoSe ₂ @Ni(OH) ₂ /CF (CS/CF) 的关系。由于强耦合异质界面的独特电子效应和双金属协同作用，实现了更容易的活性位点、快速的电荷转移能力、促进的催化动力学和调制的电子重新分布。因此，获得了改进的 SMOR 性能，甲醇转化为甲酸盐的法拉第效率约为 100%。相对于RHE，在10和100 mA cm ^-2下的电势分别仅为1.274和1.432 V，优于大多数现有催化剂。 此外，以NCS/CF为阳极和阴极的甲醇辅助水电解双电极电解槽只需施加1.380 V的槽电压即可达到10 mA cm ^-2 ，比纯水分解低253 mV 。同时，通过连续提供100 mA cm ^-2的电流密度100小时而没有明显衰减，实现了出色的催化稳定性。 Se 的“类航天飞机”作用的推论将为与外来原子结合的 NiCo-LDH 衍生物中的电子重新分布提供新的见解。甲醇提质与制氢一体化，探索一种节能的方式，同时获得高附加值的有机物质和绿色氢气。