Xin Yu, Fu Hongchuan, Chen Liyu, Ji Yongfei, Li Yingwei, Shen Kui
Guangdong Provincial Key Lab of Green Chemical Product Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China.
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China.
ACS Cent Sci. 2024 Oct 3;10(10):1920-1932. doi: 10.1021/acscentsci.4c01085. eCollection 2024 Oct 23.
The electricity-driven 5-hydroxymethylfurfural (HMF) oxidation reaction has exhibited increasing potential to produce high-value-added 2,5-furandicarboxylic acid (FDCA). Unfortunately, the competitive oxygen evolution reaction (OER) can decrease the yield and Faradaic efficiency (FE) of FDCA under high potentials. Here, we report a general MOF-templated strategy to construct a new class of hollow high-entropy layered hydroxide array (HE-LHA) electrocatalysts including quinary, senary, and septenary phases composed of CoNiMnCuZn with Cd and Mg on carbon cloth (CC) for boosting the HMF oxidation reaction (HMFOR) by suppressing the OER. Impressively, the septenary CC@CoNiMnCuZnCdMg-LHA exhibits a low potential of 1.42 V for the HMFOR but a high potential of 1.68 V for the OER to achieve 100 mA cm, ranking it among one of the best electrocatalysts for the HMFOR. Finite element simulations show its hollow array morphology can induce a strong local electric field over all of the shell, thus favoring the electrocatalytic process. electrochemical impedance spectroscopy and theoretical calculations further reveal that the Co, Ni, Cu, Zn, Mn, Cd, and Mg metals in high-entropy LHAs can accelerate the HMFOR but suppress the OER by optimizing the adsorption energy of the HMF* and OH*. This work sheds light on the rational design and construction of high-entropy nanoarchitectures for advanced electrocatalysis.
电驱动的5-羟甲基糠醛（HMF）氧化反应在生产高附加值的2,5-呋喃二甲酸（FDCA）方面展现出越来越大的潜力。不幸的是，竞争性析氧反应（OER）会在高电位下降低FDCA的产率和法拉第效率（FE）。在此，我们报道了一种通用的金属有机框架模板策略，用于构建一类新型的中空高熵层状氢氧化物阵列（HE-LHA）电催化剂，该催化剂包括由CoNiMnCuZn以及Cd和Mg组成的五元、六元和七元相，负载于碳布（CC）上，通过抑制OER来促进HMF氧化反应（HMFOR）。令人印象深刻的是，七元相CC@CoNiMnCuZnCdMg-LHA在HMFOR时的低电位为1.42 V，但在析氧反应达到100 mA cm时的高电位为1.68 V，使其跻身HMFOR最佳电催化剂之列。有限元模拟表明，其空心阵列形态可在整个壳层上诱导出强烈的局部电场，从而有利于电催化过程。电化学阻抗谱和理论计算进一步揭示，高熵层状氢氧化物中的Co、Ni、Cu、Zn、Mn、Cd和Mg金属可以通过优化HMF和OH的吸附能来加速HMFOR，但抑制OER。这项工作为先进电催化的高熵纳米结构的合理设计和构建提供了思路。
