Page 171 - 《精细化工》2022年第2期

第 39 卷第 2 期 精 细 化 工 Vol.39, No.2
2022 年 2 月 FINE CHEMICALS Feb. 2022

有机电化学与工业
氧化石墨烯生长钨基氧化物酸环境电催化析氢

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张 凯 ，蒋平平 ，曹圣平 ，蒋国强 ，张萍波 ，冷 炎
（1. 江南大学 化学与材料工程学院 合成与生物胶体教育部重点实验室，江苏 无锡 214122；2. 宁夏百
川新材料有限公司，宁夏 银川 750002；3. 江苏百川高科新材料股份有限公司，江苏 江阴 214422）
摘要：以磷钨酸为钨源，单层氧化石墨烯（GO）为载体，引入碳纳米管（CNTs），通过一步水热法和在空气中
煅烧制备了纳米异质结（WO 3 -rGO-CNTs）。通过 FTIR、XRD、XPS、TG、SEM、EDS、TEM 和 BET 对其进行
了表征，利用线性伏安法和循环伏安法对其进行了电催化析氢（HER）反应测试。结果表明，WO 3 晶体粒子均
匀、有序地分布在单层 GO 和 CNTs 的表面上。WO 3 -rGO-CNTs 在酸性电解质中表现出优异的 HER 催化活性。
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当电流密度为 10 mA/cm 时，其过电势为 218 mV，Tafel 斜率为 130.5 mV/dec。当过电势为–0.5 V vs.可逆氢电
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极（RHE）时，其阻抗为 8.2 Ω。同时，WO 3 -rGO-CNTs 可以在 218 mV（电流密度为 10 mA/cm ）过电势下，
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保持 50 h 的稳定性和耐久性，其双层电容为 1.20 mF/cm 。WO 3 晶体与 GO 和 CNTs 间异质结结构的存在产生了
协同效应：GO 为 WO 3 晶体提供了广阔的金属反应活性位点，而 CNTs 则提供了利于电子传输的活性轨道。
关键词：电催化产氢；单层 GO；纳米异质结；电催化活性；协同效应；有机电化学与工业
中图分类号：TQ116.2；TQ426 文献标识码：A 文章编号：1003-5214 (2022) 02-0375-07

Hydrogen evolution reaction for tungsten-based oxides grown on
graphene oxide in acidic environment

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ZHANG Kai , JIANG Pingping , CAO Shengping , JIANG Guoqiang ,
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ZHANG Pingbo , LENG Yan
（1. Key Laboratory of Synthetic and Biological Colloids of Ministry of Education, School of Chemical and Material
Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China; 2. Ningxia Baichuan New Materials Co., Ltd.,
Yinchuan 750002, Ningxia, China; 3. Jiangsu Baichuan High-Tech New Materials Co., Ltd., Jiangyin 214422, Jiangsu,
China）
Abstract: Nano heterojunction (WO 3-rGO-CNTs) was synthesized using phosphotungstic acid and
single-layer graphene oxide (GO) as tungsten source and carrier and introducing carbon nanotubes (CNTs)
by one-step hydrothermal method and calcination in air. The sample was characterized by FTIR, XRD, XPS,
TG, SEM, EDS, TEM and BET. The performance of WO 3-rGO-CNTs for hydrogen evolution reaction
(HER) was tested by linear sweep voltammetry and cyclic voltammetry. The results showed that WO 3
crystals were uniformly and orderly distributed on the surface of single-layer GO and CNTs. After
introduction of CNTs, prepared WO 3-rGO-CNTs exhibited excellent HER catalytic activities in an acidic
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electrolyte. At 10 mA/cm , the overpotential was 218 mV and the Tafel slope was 130.5 mV/dec. At an
overpotential of –0.5 V vs. reversible hydrogen electrode (RHE), the impedance was 8.2 Ω. Meanwhile,
WO 3-rGO-CNTs could maintain long-term stability and durability for up to 50 h at an overpotential of 218
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mV (current density of 10 mA/cm ), while its double-layer capacitance was 1.20 mF/cm . WO 3 crystals, GO
and CNTs had synergistic effect due to the existence of heterogeneous structure. GO provided wide metal
reaction active sites for WO 3 crystals, while CNTs provided active orbitals conducive to electron transport.
Key words: electrocatalytic hydrogen production; single-layer graphene oxide; nano heterojunction;
electrocatalytic activity; synergistic effect; electro-organic chemistry and industry

收稿日期：2021-08-04; 定用日期：2021-10-09; DOI: 10.13550/j.jxhg.20210785
基金项目：国际交流合作项目（BX 2019018）；2018 年度江苏省研究生培养创新工程项目（KYCX18_1810）
作者简介：张 凯（1992—），男，博士生，E-mail：zhangkaikd@163.com。联系人：蒋平平（1957—），男，教授，博士生导师，E-mail：
ppjiang@jiangnan.edu.cn。