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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

王克, 汤飞, 姚孝璋, HitanshuKumar, 干林. 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. 新型炭材料(中英文), 2022, 37(6): 1183-1192. doi: 10.1016/S1872-5805(21)60078-1
引用本文: 王克, 汤飞, 姚孝璋, HitanshuKumar, 干林. 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. 新型炭材料(中英文), 2022, 37(6): 1183-1192. doi: 10.1016/S1872-5805(21)60078-1
WANG Ke, TANG Fei, YAO Xiao-zhang, Hitanshu Kumar, GAN Lin. Chemical vapor deposition of two-dimensional transition metal sulfides on carbon paper for electrocatalytic hydrogen evolution. New Carbon Mater., 2022, 37(6): 1183-1192. doi: 10.1016/S1872-5805(21)60078-1
Citation: WANG Ke, TANG Fei, YAO Xiao-zhang, Hitanshu Kumar, GAN Lin. Chemical vapor deposition of two-dimensional transition metal sulfides on carbon paper for electrocatalytic hydrogen evolution. New Carbon Mater., 2022, 37(6): 1183-1192. 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
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

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

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
  • 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。
  • FIG. 1966.  FIG. 1966.

    FIG. 1966..  FIG. 1966.

    图  1  TMDs(MoS2、NbS2、WS2)的合成示意图

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

    图  2  在12 L/h的气体流速下,生长在碳纸上的MoSx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MoSx的XRD谱图

    Figure  2.  SEM images of synthesized MoSx 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 MoSx on carbon paper with a flow of 12 L/h under 750 °C or 850 °C

    图  3  在800 °C下,生长在碳纸上的NbSx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

    图  4  三种合成的WSx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 WSx 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

    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

    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

    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)

    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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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

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