Highly selective electrosynthesis of 3,4-dihydroisoquinoline accompanied with hydrogen production over three-dimensional hollow CoNi-based microarray electrocatalysts  

作　　者：Yu Xin Liyu Chen Yingwei Li Kui Shen 

机构地区：[1]Guangdong Provincial Key Lab for Green Chemical Product Technology,School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510640,China [2]State Key Laboratory of Pulp and Paper Engineering,School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510640,China

出　　处：《Nano Research》2024年第4期2509-2519,共11页纳米研究（英文版）

基　　金：support from the Natural Science Foundation of Guangdong Province(No.2023B1515040005);the National Natural Science Foundation of China(Nos.22378135,21825802,and 22138003);the State Key Laboratory of Pulp and Paper Engineering(No.2022PY05).

摘　　要：Electrocatalytic oxidation reaction of biomass-based derivatives is an excellent candidate to replace water oxidation for obtaining both value-added products and hydrogen(H_(2)),but the exploration of competent electrocatalysts is still highly challenging.Herein,two new types of three-dimensional self-supported hollow microarrays containing CoNi layered double hydroxide(CoNi-LDH)and N-doped carbon nanosheets decorated with CoNi alloyed nanoparticles(CoNi-NC)on carbon cloth(CC)are prepared,which are further used as efficient electrocatalysts for tetrahydroisoquinoline(THIQ)electrooxidation and hydrogen evolution reaction(HER),respectively.We demonstrate that the Co-modulated electronic environment for Ni(II)/Ni(Ⅲ)redox-looping in CoNi-LDH is the main factor to boost the selectivity of 3,4-dihydroisoquinoline(DHIQ)for the indirect electrooxidation process of THIQ.Density functional theory(DFT)calculations reveal that the Ni(Ⅲ)/Co(Ⅲ)dual sites of CoNi-LDH exhibit enhanced adsorption for THIQ but poorer adsorption for DHIQ compared to pure Co(Ⅲ)or Ni(Ⅲ).Therefore,the Ni(Ⅲ)/Co(Ⅲ)dual sites can effectively inhibit the peroxidation of DHIQ to isoquinoline(IQ)over CoNi-LDH,thus improving the selectivity of DHIQ to nearly 100%,much higher than that of its pure Ni counterpart.Moreover,CC@CoNi-NC can deliver high HER activity with low overpotential(40 mV@10 mA·cm^(-2))and high exchange current density(3.08 mA·cm^(-2)).Impressively,the assembled flow-cell device with CC@CoNi-LDH anode and CC@CoNi-NC cathode only requires low cell voltage and electricity consumption of 1.6 V and 3.50 kWh per cubic meter of H_(2)(@25 mA·cm^(-2)).

关 键 词：highly selective electrosynthesis dihydroisoquinolines hydrogen evolution reaction metal-organic frameworks hollow microarrays 

分 类 号：O64[理学—物理化学]