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强化 NiOOH 相在 5-羟甲基糠醛氧化中的稳定性。

Strengthening the Stability of the Reconstructed NiOOH Phase for 5-Hydroxymethylfurfural Oxidation.

机构信息

School of Chemistry and Chemical Engineering, Jiangsu Univers ity, Zhenjiang 212013, P. R. China.

Baotou Research Institute of Rare Earths, Baotou 014030, P. R. China.

出版信息

Inorg Chem. 2023 Apr 24;62(16):6499-6509. doi: 10.1021/acs.inorgchem.3c00562. Epub 2023 Apr 10.

Abstract

Electrochemical oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) is a promising approach to produce high-value chemicals such as 2,5-furandicarboxylic acid (FDCA). However, the undesirable stability of catalysts commonly limits its potential application value. In this work, NiOOH derived from Ni(OH) was determined as the main catalytic site for HMF oxidation, but the collapse of Ni(OH) caused severe instability during the electrocatalytic process because of the crystal structure mismatch between NiOOH and Ni(OH). The implantation of Ce in Ni(OH) (Ce-Ni(OH)) was successfully realized to address the stability issue of bare Ni(OH), since the larger ion radius of Ce could increase the Ni-O bond length and -spacing. As a result, the activity of 14%Ce-Ni(OH) has not obviously decayed after the 50 cyclic voltammetry (CV)-cycle test. HMF conversion is close to 100%, and the Faraday efficiency (FE) reaches 86.6% at the potential of 0.45 V vs Ag/AgCl. This study provides a new strategy to design stable catalysts for the conversion of biomass derivatives.

摘要

电化学氧化生物质衍生的 5-羟甲基糠醛(HMF)是生产 2,5-呋喃二甲酸(FDCA)等高价值化学品的一种很有前途的方法。然而,催化剂的不稳定性通常限制了其潜在的应用价值。在这项工作中,确定 Ni(OH) 衍生的 NiOOH 是 HMF 氧化的主要催化位点,但由于 NiOOH 和 Ni(OH)之间的晶体结构不匹配,Ni(OH)的塌陷导致电催化过程中出现严重的不稳定性。通过在 Ni(OH)中植入 Ce(Ce-Ni(OH))成功地解决了裸 Ni(OH)的稳定性问题,因为 Ce 的较大离子半径可以增加 Ni-O 键长和间距。结果,在 50 个循环伏安(CV)-循环测试后,14%Ce-Ni(OH)的活性没有明显下降。在 0.45 V 对 Ag/AgCl 的电位下,HMF 的转化率接近 100%,法拉第效率(FE)达到 86.6%。这项研究为设计生物质衍生物转化的稳定催化剂提供了一种新策略。

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