A robust sandwich structural catalyst of (Cu/CuCo-MOF)2/MXene double heterojunction with outstanding activity toward hydrogen generation

Wenjing Xu, Mei Liu, Shuling Liu, Shuyan Guan, Huanhuan Zhang, Ruofan Shen, Yongfeng Wang, Baojun Li
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Abstract

Non-noble metal catalysts have exhibited promising prospects in ammonia borane (NHBH) hydrolysis, but their activity and stability still need to be further improved. Herein, a 2D sandwich heterostructural catalyst with Cu/CuCo-MOF and MXene-MOF double heterojunction has been prepared by coupling TiCT MXene with bimetal organic framework nanosheets using a facile in situ growth strategy. The optimized CuCo-MOF/MX exhibits unprecedented activity with a turnover frequency (TOF) of 82.3 min and excellent cycle stability, comparable to precious metal catalysts. Spectroscopic characterization and density functional theory (DFT) calculations reveal that Cu/CuCo-MOF heterojunction provides CuCo dual active sites for catalysis, and MXene-MOF heterojunction modulates the electronic structure and valence states of Cu sites via the TiCT interlayer with 2D electron promoter effect to improve the synergistic effect of CuCo dual active sites. These modulation optimize the adsorption and dissociation of reactants, leading to a lower reaction barrier. This work provides insight into the 2D electron promoter effect, proposes a novel strategy for improving the performance of non-precious metal catalysts through constructing double heterojunction with 2D electron promoter effect.
具有优异制氢活性的(Cu/CuCo-MOF)2/MXene 双异质结坚固夹层结构催化剂
非贵金属催化剂在氨硼烷(NHBH)水解中表现出了广阔的前景,但其活性和稳定性仍有待进一步提高。本文采用简便的原位生长策略,将 TiCT MXene 与双金属有机框架纳米片耦合,制备了一种具有 Cu/CuCo-MOF 和 MXene-MOF 双异质结的二维夹层异质结构催化剂。优化后的 CuCo-MOF/MX 表现出前所未有的活性,翻转频率 (TOF) 高达 82.3 分钟,循环稳定性极佳,可与贵金属催化剂媲美。光谱表征和密度泛函理论(DFT)计算表明,Cu/CuCo-MOF 异质结提供了用于催化的 CuCo 双活性位点,而 MXene-MOF 异质结通过具有二维电子促进效应的 TiCT 夹层调节了 Cu 位点的电子结构和价态,从而提高了 CuCo 双活性位点的协同效应。这些调制优化了反应物的吸附和解离,从而降低了反应势垒。这项研究深入探讨了二维电子促进效应,提出了一种通过构建具有二维电子促进效应的双异质结来提高非贵金属催化剂性能的新策略。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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