Extraordinary d–d hybridization in Co(Cu)0.5OxHy microcubes facilitates PhCH2O* –Co(Ⅳ) coupling for benzyl alcohol electrooxidation

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL Applied Catalysis B: Environmental Pub Date : 2024-01-15 DOI:10.1016/j.apcatb.2024.123739

Lei Huang , Xiongchao Lin , Ke Zhang , Jun Zhang , Caihong Wang , Sijian Qu , Yonggang Wang

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Abstract

A series of bimetallic hydroxides Co(M)_0.5O_xH_y (M = Cu, Ni, Mn, Zn) were fabricated for the benzyl alcohol oxidation reaction (BAOR). The active origin and synergistic effect of bimetallic electrocatalysts were adequately deciphered. The reaction was found be principally initiated from the sequential oxidation of Co²⁺ (i.e., Co²⁺ to Co³⁺ to Co⁴⁺), followed by the spontaneous proton–coupled electron transfer (PCET) process between Co⁴⁺ and benzyl alcohol (BA) molecules. Besides, the adsorption free energy of BA molecules on Co(Cu)_0.5O_xH_y was successfully optimized by Cu doping owing to the extraordinary d–d orbital hybridization between Co and Cu atom. As a result, an extra high conversion rate (95.3%) of BA and selectivity (98.2%) of benzoic acid were achieved under 0.5 V vs. Hg/HgO. These insights are essential for a comprehensive understanding of the BAOR mechanism and the design of Co–based catalysts.

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Co(Cu)0.5OxHy 微立方体中的非凡 d-d 杂化促进了 PhCH2O*-Co(Ⅳ) 偶联用于苯甲醇电氧化反应

为苯甲醇氧化反应（BAOR）制备了一系列双金属氢氧化物 Co(M)0.5OxHy（M = 铜、镍、锰、锌）。研究充分揭示了双金属电催化剂的活性来源和协同效应。研究发现，该反应主要是由 Co2+ 的顺序氧化（即 Co2+ 到 Co3+ 再到 Co4+）引发的，随后是 Co4+ 与苯甲醇（BA）分子之间自发的质子耦合电子转移（PCET）过程。此外，由于 Co 原子和 Cu 原子间非凡的 d-d 轨道杂化作用，Cu 掺杂成功地优化了 BA 分子在 Co(Cu)0.5OxHy 上的吸附自由能。因此，在 0.5 V vs. Hg/HgO 条件下，苯甲酸的转化率（95.3%）和选择性（98.2%）都达到了极高的水平。这些见解对于全面了解 BAOR 机理和设计 Co 基催化剂至关重要。

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来源期刊

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

期刊介绍： Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.