Designing efficient and durable bifunctional catalysts for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is desirable for the co-production of biomass-upgraded chemicals and sustainable hydrogen, which is limited by the competitive adsorption of hydroxyl species (OH_ads) and HMF molecules. Here, we report a class of Rh–O₅/Ni(Fe) atomic site on nanoporous mesh-type layered double hydroxides with atomic-scale cooperative adsorption centers for highly active and stable alkaline HMFOR and HER catalysis. A low cell voltage of 1.48 V is required to achieve 100 mA cm^–2 in an integrated electrolysis system along with excellent stability (>100 h). Operando infrared and X-ray absorption spectroscopic probes unveil that HMF molecules are selectively adsorbed and activated over the single-atom Rh sites and oxidized by in situ-formed electrophilic OH_ads species on neighboring Ni sites. Theoretical studies further demonstrate that the strong d–d orbital coupling interactions between atomic-level Rh and surrounding Ni atoms in the special Rh–O₅/Ni(Fe) structure can greatly facilitate surface electronic exchange-and-transfer capabilities with the adsorbates (OH_ads and HMF molecules) and intermediates for efficient HMFOR and HER. We also reveal that the Fe sites in Rh–O₅/Ni(Fe) structure can promote the electrocatalytic stability of the catalyst. Our findings provide new insights into catalyst design for complex reactions involving competitive adsorptions of multiple intermediates.

中文翻译：

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Rh-O5/Ni(Fe) 合作站点用于高效生物质升级以及氢气生产

设计用于 5-羟甲基糠醛 (HMF) 氧化反应 (HMFOR) 和析氢反应 (HER) 的高效耐用的双功能催化剂对于生物质升级化学品和可持续氢气的联产来说是可取的，但受到羟基竞争吸附的限制物种（OH _ads）和 HMF 分子。在这里，我们报道了纳米孔网状层状双氢氧化物上的一类Rh– O _{5 /Ni(Fe)原子位点，具有原子级协同吸附中心，用于高活性和稳定的碱性HMFOR和HER催化。}在集成电解系统中需要 1.48 V 的低电池电压才能实现 100 mA cm ^–2以及出色的稳定性（>100 小时）。Operando红外和 X 射线吸收光谱探针揭示了 HMF 分子在单原子 Rh 位点上选择性吸附和激活，并被邻近 Ni 位点上原位形成的亲电子 OH _ad物质氧化。_{理论研究进一步表明，特殊的Rh-O 5} /Ni(Fe)结构中原子级Rh与周围Ni原子之间强的d-d轨道耦合相互作用可以极大地促进与吸附物的表面电子交换和转移能力。 OH _ads和 HMF 分子）以及高效 HMFOR 和 HER 的中间体。_{我们还发现Rh–O 5} /Ni(Fe)结构中的Fe位点可以提高催化剂的电催化稳定性。我们的研究结果为涉及多种中间体竞争吸附的复杂反应的催化剂设计提供了新的见解。