The development of catalysts with high activity, selectivity, and stability is critical for biomass upgrading coupled with hydrogen evolution. In this study, we present a simple method for fabricating crystalline-amorphous phase heterostructures using the etching effect of the acidic medium generated during cobalt salt hydrolysis, resulting in the formation of NiCo(OH)_x-modified Ni/NiMoO₄ nanosheets electrode (NiCo(OH)_x/Ni/NiMoO₄/NF). The nanosheets array formed during the synthesis process enlarges the surface area of the prepared catalyst, which facilitates the exposure of electrochemically active sites and improves mass transfer. Unexpectedly, the strong coupling interactions between the amorphous-crystalline heterointerface optimize the adsorption of reaction molecules and the corresponding charge transfer process, consequently boosting the catalytic activity for the 5-hydroxymethylfurfural oxidation reaction (HMFOR) and hydrogen evolution reaction (HER). Specifically, NiCo(OH)_x/Ni/NiMoO₄/NF catalyst requires only 1.34 V to obtain a current density of 10 mA cm⁻² for HMFOR-coupled H₂ evolution, and operates stably for 13 consecutive cycles with good product selectivity. This work thus provides insights into the design of efficient and robust catalysts for HMFOR-assisted H₂ evolution.

开发具有高活性、选择性和稳定性的催化剂对于生物质升级和析氢至关重要。在这项研究中，我们提出了一种简单的方法，利用钴盐水解过程中产生的酸性介质的蚀刻作用来制造晶体-非晶相异质结构，从而形成NiCo(OH) _x修饰的Ni/NiMoO ₄纳米片电极（NiCo (OH) _x /Ni/NiMoO ₄ /NF)。合成过程中形成的纳米片阵列扩大了所制备催化剂的表面积，有利于电化学活性位点的暴露并改善传质。出乎意料的是，非晶-结晶异质界面之间的强耦合相互作用优化了反应分子的吸附和相应的电荷转移过程，从而提高了5-羟甲基糠醛氧化反应（HMFOR）和析氢反应（HER）的催化活性。具体而言，NiCo(OH) _x /Ni/NiMoO ₄ /NF催化剂仅需要1.34 V即可获得10 mA cm ^-2的电流密度以用于HMFOR耦合H ₂析出，并且连续13个循环稳定运行且具有良好的产物选择性。因此，这项工作为 HMFOR 辅助 H ₂演化的高效且稳健的催化剂设计提供了见解。