Pd - Ni(OH)2催化剂上工业电流密度下聚对苯二甲酸乙酯衍生醇协同和选择性电氧化制乙醇酸的研究

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Angewandte Chemie International Edition Pub Date : 2023-01-19 DOI:10.1002/anie.202300094
Fulai Liu, Xutao Gao, Rui Shi, Prof.?Dr. Zhengxiao Guo, Prof.?Dr. Edmund C. M. Tse, Prof.?Dr. Yong Chen
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引用次数: 10

摘要

电重整聚对苯二甲酸乙酯(pet)衍生的乙二醇(EG)为精细化学品和氢气是解决严重塑料污染的理想方案。在这里,我们报道了在Pd - Ni(OH)2催化剂上,即使在工业级电流密度(600 mA cm - 2, 1.15 V vs. RHE)下,EG电氧化成乙醇酸(GA)也具有很高的法拉第效率和选择性(> 85%)。值得注意的是,可以实现超过200小时的稳定电解,优于所有现有的钯基催化剂。实验与理论相结合的结果表明:1)Ni(OH)2促进OH*生成在促进eg - ga氧化和去除有毒羰基物质中起着关键作用,从而获得高活性和稳定性;2) d带中心下移的Pd与亲氧Ni可协同促进GA从活性Pd位点快速解吸转移到非活性Ni位点,避免过度氧化,从而实现高选择性。
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Concerted and Selective Electrooxidation of Polyethylene-Terephthalate-Derived Alcohol to Glycolic Acid at an Industry-Level Current Density over a Pd−Ni(OH)2 Catalyst

Electro-reforming of Polyethylene-terephthalate-derived (PET-derived) ethylene glycol (EG) into fine chemicals and H2 is an ideal solution to address severe plastic pollution. Here, we report the electrooxidation of EG to glycolic acid (GA) with a high Faraday efficiency and selectivity (>85 %) even at an industry-level current density (600 mA cm−2 at 1.15 V vs. RHE) over a Pd−Ni(OH)2 catalyst. Notably, stable electrolysis over 200 h can be achieved, outperforming all available Pd-based catalysts. Combined experimental and theoretical results reveal that 1) the OH* generation promoted by Ni(OH)2 plays a critical role in facilitating EG-to-GA oxidation and removing poisonous carbonyl species, thereby achieving high activity and stability; 2) Pd with a downshifted d-band center and the oxophilic Ni can synergistically facilitate the rapid desorption and transfer of GA from the active Pd sites to the inactive Ni sites, avoiding over-oxidation and thus achieving high selectivity.

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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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