Room-temperature fabrication of defective CoOxHy nanosheets with abundant oxygen vacancies and high porosity as efficient 5-hydroxymethylfurfural oxidation electrocatalysts

Zhong，Ruyi1; Wu，Puwei1; Wang，Qi2; Zhang，Xiting1; Du，Lei1; Liu，Yunhua1; Yang，Huakang1; Gu，Meng2; Zhang，Z. Conrad3; Huang，Limin4; Ye，Siyu1

2023

10.1039/d3gc00588g

Green Chemistry   影响因子和分区

1463-9262

1463-9270

Recently, cobalt oxides/hydroxides have attracted increasing attention in the electrocatalytic oxidation reaction of 5-hydroxymethylfurfural (HMFOR) under ambient conditions for 2,5-furandicarboxylic acid (FDCA) production, but understanding of the interplay of defective sites (i.e., oxygen vacancies and porosity) remains lacking. Herein, a series of defective cobalt oxide hydrate (CoOH) nanosheets were fabricated via room-temperature reductive treatments with methylamine (MA) and/or NaBH (BH). These defective CoOH nanosheets possessed abundant oxygen vacancies in relation to high Co/Co ratios and high porosity, with a largely maintained ultrathin lamellar framework, and thus exhibited markedly improved catalytic activity and selectivity for HMFOR. DFT calculations also verified the beneficial role of oxygen vacancies towards HMF adsorption and activation, preferentially via the aldehyde group of HMF. In the optimal CoOH-MA, 98% FDCA yield and a faradaic efficiency of 83% were achieved within 200 min at a constant potential of 1.52 V vs. RHE. The mesoporosity mainly induced by MA improved the mass transportation of reactants and products, leading to a higher rate of HMFOR. Meanwhile, with the additional in-sheet micropores mainly induced by BH, the selectivity towards the oxidation intermediate 5-formyl-2-furancarboxylic acid (FFCA) significantly increased, probably due to the accelerated penetration of FFCA instead of further oxidation to FDCA. This work highlights the simultaneous regulation of the oxygen vacancies and porosity of metal oxide/hydroxide catalysts by facile reductive treatments for efficient electrochemical biomass conversion.

SCI ; EI

英语

通讯

Shenzhen Science and Technology Innovation Commission[JCYJ20220818100212027] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Guangdong Provincial Department of Education Innovation Project[2022KQNCX056] ; Guangdong Basic and Applied Basic Research Foundation[2022B1515120079] ; Shenzhen Science and Technology Innovation Committee Foundation[JCYJ20190809142019365] ; Outstanding Youth Project of the Guangdong Provincial Natural Science Foundation[2022B1515020020] ; National Natural Science Foundation of China[22250710133] ; null[2022A1515110354]

Chemistry ; Science & Technology - Other Topics

Chemistry, Multidisciplinary ; Green & Sustainable Science & Technology

WOS:000980250500001

ROYAL SOC CHEMISTRY

20231914077718

Catalyst activity ; Cobalt compounds ; Electrocatalysis ; Electrocatalysts ; Fabrication ; Hydrogen production ; Oxidation ; Oxygen vacancies ; Porosity ; Reaction intermediates ; Redox reactions

Gas Fuels:522 ; Nanotechnology:761 ; Electrochemistry:801.4.1 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Physical Properties of Gases, Liquids and Solids:931.2 ; Solid State Physics:933 ; Crystalline Solids:933.1

CHEMISTRY

2-s2.0-85158014263

Scopus

1.Huangpu Hydrogen Energy Innovation Center/Guangzhou Key Laboratory for Clean Energy and Materials,School of Chemistry and Chemical Engineering,Guangzhou University,Guangzhou,510006,China
2.Department of Materials Science and Engineering,Southern University of Science and Technology,Shenzhen,518055,China
3.Dalian National Laboratory for Clean Energy,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,116023,China
4.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China

Zhong，Ruyi,Wu，Puwei,Wang，Qi,et al. Room-temperature fabrication of defective CoOxHy nanosheets with abundant oxygen vacancies and high porosity as efficient 5-hydroxymethylfurfural oxidation electrocatalysts[J]. Green Chemistry,2023,25(12):4674-4684.

Zhong，Ruyi.,Wu，Puwei.,Wang，Qi.,Zhang，Xiting.,Du，Lei.,...&Ye，Siyu.(2023).Room-temperature fabrication of defective CoOxHy nanosheets with abundant oxygen vacancies and high porosity as efficient 5-hydroxymethylfurfural oxidation electrocatalysts.Green Chemistry,25(12),4674-4684.

Zhong，Ruyi,et al."Room-temperature fabrication of defective CoOxHy nanosheets with abundant oxygen vacancies and high porosity as efficient 5-hydroxymethylfurfural oxidation electrocatalysts".Green Chemistry 25.12(2023):4674-4684.