炭纸衬底上化学气相沉积直立型二维过渡金属硫化物及其电催化产氢性能

王克; 汤飞; 姚孝璋; HitanshuKumar; 干林

doi:10.1016/S1872-5805(21)60078-1

炭纸衬底上化学气相沉积直立型二维过渡金属硫化物及其电催化产氢性能

doi: 10.1016/S1872-5805(21)60078-1

王克^1,,
汤飞¹,
姚孝璋¹,
HitanshuKumar^{1, 2},
干林^1, ,

1.
清华大学深圳国际研究生院，材料研究院，广东深圳 518055
2.
深圳大学，材料学院，广东深圳 518055

基金项目: 国家自然科学基金（No. 52173222）；广东珠江人才计划地方创新研究团队项目（No. 2017BT01N111）；广东省自然科学基金杰出青年基金（No. 2016A030306035）。

详细信息

作者简介:
王克：王　克，硕士. E-mail：wang-k16@mails.tsinghua.edu.cn

通讯作者:
干　林，博士，副教授. E-mail：lgan@sz.tsinghua.edu.cn

中图分类号: TB33
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- 被引次数: 0
出版历程
- 收稿日期: 2019-05-24
- 修回日期: 2019-07-23
- 网络出版日期: 2022-10-24
- 刊出日期: 2022-12-01

Chemical vapor deposition of two-dimensional transition metal sulfides on carbon paper for electrocatalytic hydrogen evolution

WANG Ke^1
,,
TANG Fei¹,
YAO Xiao-zhang¹,
Hitanshu Kumar^{1, 2},
GAN Lin^{1
, ,}

1.
Institute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, Guangdong, China
2.
College of Materials Science, Shenzhen University, Shenzhen 518055, Guangdong, China

Funds: National Natural Science Foundation of China (52173222), Guangdong Pearl River Talent Plan Local Innovation Research Team (2017BT01N111), Outstanding Youth Fund of Guangdong Natural Science Foundation (2016A030306035).

More Information

Corresponding author: GAN Lin, Ph.D, Associate Professor. E-mail: lgan@sz.tsinghua.edu.cn

摘要

摘要: 以MoS₂为代表的二维过渡金属硫化物近年来在电催化水分解产氢反应中表现出良好的电催化活性而受到广泛关注。但二维过渡金属硫化物的导电性一般较差、且催化活性位常在有限的边缘位置，成为限制其催化性能的重要因素。本文通过化学气相沉积方法研究了在炭纸基底上直接生长3种过渡金属硫化物（MoS₂、NbS₂和WS₂）构筑一体化催化电极，以提高整个电极的导电性。通过优化生长工艺，实现了炭纸表面3种过渡金属硫化物的直立型生长并对电催化产氢反应表现出良好的催化性能，尤其是WS₂表现出新颖的纳米片/纳米纤维层次结构，其对产氢反应表现出最佳的催化性能。在此基础上，对炭纸上生长的过渡金属硫化物通过阴极电化学活化处理的方式引入硫缺陷，从而提高其HER活性。结合透射电子显微镜和原位电化学拉曼光谱仪研究了二维过渡金属硫化物在电化学活化前后的结构变化尤其是所产生的硫缺陷的微观结构，为其产氢性能的提升提供合理的解释。
- 化学气相沉积 /
- 炭纸 /
- 过渡金属二硫化物 /
- 阴极电化学活化 /
- 电催化析氢
Abstract: Hydrogen is considered the most likely alternative clean energy fuel to traditional fossil fuels. One of the most attractive hydrogen production strategies is water splitting, but the need for expensive Pt precious metal catalysts to catalyze the hydrogen evolution reaction (HER) is a problem. Recently, two-dimensional transition metal dichalcogenides (TMDs), especially MoS₂, have attracted intense interest as a non-precious metal HER catalyst due to their low cost and relatively high catalytic activity. However, their poor electron conductivity and the limited number of active sites at their edges have greatly limited their overall catalytic performance. We report the direct growth of three representative TMDs (MoS₂, NbS₂ and WS₂) on a conductive carbon paper substrate using chemical vapor deposition and have studied the effects of temperature and gas flow rate on their morphology and structure. All the as-grown TMDs have a 2D nanosheet morphology and were aligned perpendicular to the carbon paper. The WS₂ nanosheets had the smallest sheet size with a diameter of ca. 100-200 nm and, more interestingly, were assembled into a one-dimensional nanofiber, leading to the highest HER activity. Additional electrochemical cathodic activation further improved the HER activity of the TMDs, and the structural changes after the activation were investigated by TEM combined with in-situ electrochemical Raman spectroscopy. The activated NbS₂ contained large triangular or truncated triangular S vacancy areas, which is distinctly different from the individual S vacancies in MoS₂.
- Chemical vapor deposition /
- Carbon paper /
- Transition metal dichalcogenides /
- Cathodic electrochemical activation /
- Electrocatalytic hydrogen evolution

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图 1 TMDs（MoS₂、NbS₂、WS₂）的合成示意图

Figure 1. Schematic of synthesis of TMDs (MoS₂, NbS₂, WS₂)

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图 2 在12 L/h的气体流速下，生长在碳纸上的MoS_x的SEM照片：750 °C的（a）低倍和（b）高倍照片，850 °C的（c）低倍和（d）高倍照片；12 L/h的气体流速下850 °C生长的MoS₂的（e）TEM照片和（f）HRTEM照片，内嵌图为其FFT以及（g）尺寸分布图；（h）12 L/h的气体流速下，750 °C和850 °C生长在碳纸上的MoS_x的XRD谱图

Figure 2. SEM images of synthesized MoS_x on carbon paper with a flow of 12 L/h. (a-b) 750 °C, (c-d) 850 °C, (e) TEM image, (f) HRTEM image with FFT and (g) size distribution of MoS₂ on carbon paper with a flow of 12 L/h under 850 °C and (h) XRD patterns of synthesized MoS_x on carbon paper with a flow of 12 L/h under 750 °C or 850 °C

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图 3 在800 °C下，生长在碳纸上的NbS_x的SEM照片：12 L/h的气体流速的（a）低倍和（b）高倍照片，40 L/h的气体流速的（c）低倍和（d）高倍照片；在800 °C，12 L/h的气体流速下生长的NbS₂的（e）TEM照片和（f）HRTEM照片，内嵌图为其FFT以及（g）尺寸分布图；（h）在800 °C，12 L/h和40 L/h的气体流速下，生长在碳纸上的NbS₂的XRD图谱

Figure 3. SEM images of synthesized NbS₂ on carbon paper under 750 °C with a flow of (a-b) 12 L/h, (c-d) 40 L/h, (e) TEM image, (f) HRTEM image with FFT and (g) size distribution of NbS₂ on carbon paper under 800 °C with a flow of 40 L/h and (h) XRD patterns of synthesized NbS₂ on carbon paper under 800 °C with a flow of 12 L/h or 40 L/h

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图 4 三种合成的WS_x的SEM图：（a-b）850 °C及4 L/h的气体流速，（c-d）850 °C及12 L/h的气体流速，（e-f）750 °C及12 L/h的气体流速；在750 °C，12 L/h的气体流速下生长的WS₂的（g）TEM照片和（h）HRTEM照片，内嵌图为其FFT以及（i）尺寸分布图；（j）在750 °C，12 L/h的气体流速下，生长在碳纸上的WS₂的XRD图谱

Figure 4. SEM images of three types of synthesized WS_x on carbon paper (a-b) under 850 °C with a flow of 4 L/h, (c-d) under 850 °C with a flow of 12 L/h, (e-f) under 750 °C with a flow of 12 L/h. (g) TEM image, (h) HRTEM image with FFT, (i) size distribution and (j) XRD patterns of WS₂ on carbon paper under 750 °C with a flow of 12 L/h

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图 5 三种TMDs在0.05 mol L⁻¹ H₂SO₄中的HER电催化性能：（a）碳纸及MoS₂ (850 °C, 12 L/h)、NbS₂ (800 °C, 40 L/h)、WS₂ (750 °C, 12 L/h)的HER极化曲线，（b）MoS₂、NbS₂、WS₂的Tafel斜率图

Figure 5. (a) HER plots and (b) Tafel slopes of MoS₂, NbS₂ and WS₂

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图 6 MoS₂、NbS₂和WS₂在0.05 mol L⁻¹ H₂SO₄中阴极电化学活化（-1.0 V, 3 min）前后的HER极化曲线

Figure 6. HER plots of MoS₂, NbS₂ and WS₂ before and after electrochemical cathodic activation

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图 7 （a）活化后的MoS₂的HRTEM照片及该区域的FFT，（b）活化后的NbS₂的TEM照片以及（b）中两个区域（c）I和（d）II的EDX谱图

Figure 7. (a) HRTEM image of activated MoS₂ with FFT, (b) TEM image of activated NbS₂, EDX patterns of two regions (c) I and (d) II from Fig. 7(a)

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图 8 三种TMDs在0~ –0.6 V（vs. RHE）电位下的原位电化学拉曼光谱图：（a-b）MoS₂、（c）NbS₂、（d）WS₂

Figure 8. In-situ electrochemical Raman spectra of (a, b) MoS₂, (c) NbS₂ and (d) WS₂ under steady state chronoamperometry by holding at each potential (from 0 to -0.6 V/RHE) for 2 min

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