通过诱导局域电场和电子局域化协同碱性析氢

doi:10.1016/S1872-2067(23)64532-2

催化学报 ›› 2023, Vol. 54: 229-237.DOI: 10.1016/S1872-2067(23)64532-2

通过诱导局域电场和电子局域化协同碱性析氢

王其忧^a^,^b^,¹, 龚钰杰^a^,¹, 谭耀^b, 资鑫^b, Reza Abazari^c, 李红梅^b, 蔡超^b, 刘康^b, 傅俊伟^b, 陈善勇^d, 罗涛^b, 张世国^e, 李文章^d, 盛义发^a, 刘俊^a^,^*(), 刘敏^b^,^*()

^a南华大学电气工程学院, 湖南衡阳421001, 中国
^b中南大学物理学院, 粉末冶金国家重点实验室, 湖南省二氧化碳绿色资源化利用国际联合研究中心, 湖南长沙410083, 中国
^c马拉赫大学化学系, 马拉赫, 伊朗
^d中南大学化学化工学院, 湖南长沙410083, 中国
^e湖南大学材料科学与工程学院, 湖南长沙410082, 中国

收稿日期:2023-08-17 接受日期:2023-10-10 出版日期:2023-11-18 发布日期:2023-11-15
通讯作者: *电子信箱: 2021000103@usc.edu.cn (刘俊), minliu@csu.edu.cn (刘敏).
作者简介:¹共同第一作者.
基金资助:
湖南省自然科学基金(2023JJ30499);广东省自然科学基金(2022A1515010198);国家自然科学基金(22002189);国家自然科学基金(52202125);国家自然科学基金(22376222);中南大学高级交叉学科研究计划项目(2023QYJC012);中南大学创新驱动研究计划(2023CXQD042)

Cooperative alkaline hydrogen evolution via inducing local electric field and electron localization

Qiyou Wang^a^,^b^,¹, Yujie Gong^a^,¹, Yao Tan^b, Xin Zi^b, Reza Abazari^c, Hongmei Li^b, Chao Cai^b, Kang Liu^b, Junwei Fu^b, Shanyong Chen^d, Tao Luo^b, Shiguo Zhang^e, Wenzhang Li^d, Yifa Sheng^a, Jun Liu^a^,^*(), Min Liu^b^,^*()

^aSchool of Electrical Engineering, University of South China, Hengyang 421001, Hunan, China
^bHunan Joint International Research Center for Carbon Dioxide Resource Utilization, State Key Laboratory of Powder Metallurgy, School of Physics, Central South University, Changsha 410083, Hunan, China
^cDepartment of Chemistry, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
^dCollege of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, China
^eCollege of Materials Science and Engineering, Hunan University, Changsha 410082, Hunan, China

Received:2023-08-17 Accepted:2023-10-10 Online:2023-11-18 Published:2023-11-15
Contact: *E-mail: 2021000103@usc.edu.cn (J. Liu), minliu@csu.edu.cn (M. Liu).
About author:¹Contributed equally to this work.
Supported by:
Hunan Provincial Natural Science Foundation of China(2023JJ30499);Guangdong Provincial Natural Science Foundation of China(2022A1515010198);Natural Science Foundation of China(22002189);Natural Science Foundation of China(52202125);Natural Science Foundation of China(22376222);Central South University Research Programme of Advanced Interdisciplinary Studies(2023QYJC012);Central South University Innovation-Driven Re-search Programme(2023CXQD042)

摘要/Abstract

摘要：

碱性析氢反应(HER)可将间歇性可再生能源转化为可存储的清洁能源, 因而备受关注. 然而, 水解离速度缓慢以及H中间体(*H)吸附和解吸困难限制了碱性HER的进一步发展. 目前, 针对碱性电解水解离缓慢问题, 通常采用调整电催化剂结构降低水分解热动力学能垒, 以及改变三相界面微环境加速中间产物的扩散等方法来促进水分解进行. 此外, 可以通过调控活性位点电子结构来优化*H的吸脱附. 但是采用单一的策略很难同时促进H₂O的解离和*H的吸脱附, 难以获得令人满意的碱性HER性能. 因此, 探索一种能同时促进H₂O的解离和*H的吸脱附协同策略对提升碱性HER的性能至关重要.

本文提出了一种协同策略, 通过构建高曲率二硫化钴纳米针(CoS₂ NNs)和原子级铜(Cu)的掺杂分别实现诱导纳米尺度的局域电场和原子尺度的电子局域化, 从而促进碱性HER的H₂O解离和*H吸脱附. 首先, 采用有限元法模拟和密度泛函理论计算, 从理论上分别证实了纳米尺度局域电场可以加速H₂O解离以及原子尺度电子局域化可以促进*H吸附. 受理论计算结果启发, 通过一步水热法和原位硫化相结合的方法制备了高曲率的Cu掺杂CoS₂纳米针(Cu-CoS₂ NNs). 采用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)和四探针测试等技术进行表征, 研究了Cu-CoS₂ NNs的形貌、物相结构、化学组成和导电性. 结果表明, 在Cu原子引入后, Cu-CoS₂ NNs依然保持着高曲率的纳米针结构, 证明了Cu在CoS₂ NNs中的原子分散状态. 相较于低曲率的Cu掺杂CoS₂纳米线(Cu-CoS₂ NWs), Cu-CoS₂ NNs只存在形貌上的区别, 二者的化学组成和比例均非常接近. 同时, 上述材料都具有很强的导电性, 且电导率基本相同, 这与有限元模拟结果一致. 原位衰减全反射红外光谱和电响应测试结果表明, Cu-CoS₂ NNs具有较好的解离H₂O和吸附*H的能力. 在1 mol L^-1 KOH溶液和10 mA cm^-2电流密度下, 该催化剂的析氢过电位仅为64 mV, 展现出较好的电化学析氢性能. 催化剂还表现出非常好的碱性析氢稳定性, 在标准氢电势(RHE)-0.18 V下, 可在100 mA cm^-2电流密度下稳定工作达100 h.

综上所述, 本文通过诱导局域电场和电子局域化构建了一种协同策略, 所制备的Cu-CoS₂ NNs表现出很好的催化碱性HER性能和应用前景, 为碱性HER电催化剂的理性设计提供了一定的参考.

关键词: 碱性析氢, 局域电场, 电子局域化, 铜掺杂, 二硫化钴纳米针尖

Abstract:

Alkaline hydrogen evolution reaction (HER) represents a promising means to store intermittent renewable energy into clean energy. Unfortunately, the sluggish H₂O dissociation and difficult *H adsorption-desorption are prominent obstacles to the development of alkaline HER. Herein, we developed a cooperative strategy via nanoneedle inducing local electric field and atomic doping causing electron localization for alkaline HER based on the preparation of Cu doped CoS₂ nanoneedles (Cu-CoS₂ NNs). Finite element method simulations and density functional theorycalculations demonstrate the local electric field accelerates H₂O dissociation and electron localization facilitates *H adsorption, respectively. In situ attenuated total reflection infrared spectroscopy and electro-response measurement experimentally reveal the superior ability to H₂O dissociation and *H adsorption for Cu-CoS₂ NNs. As a result, the Cu-CoS₂ NNs exhibit an ultralow overpotential of 64 mV at -10 mA cm^-2 and long-term stability over 100 h at -100 mA cm^-2 during alkaline HER, which outperforms most electrocatalysts in recently published works.

Key words: Alkaline hydrogen evolution, Local electric field, Electron localization, Cu doping, CoS₂ nanoneedles

王其忧, 龚钰杰, 谭耀, 资鑫, Reza Abazari, 李红梅, 蔡超, 刘康, 傅俊伟, 陈善勇, 罗涛, 张世国, 李文章, 盛义发, 刘俊, 刘敏. 通过诱导局域电场和电子局域化协同碱性析氢[J]. 催化学报, 2023, 54: 229-237.

Qiyou Wang, Yujie Gong, Yao Tan, Xin Zi, Reza Abazari, Hongmei Li, Chao Cai, Kang Liu, Junwei Fu, Shanyong Chen, Tao Luo, Shiguo Zhang, Wenzhang Li, Yifa Sheng, Jun Liu, Min Liu. Cooperative alkaline hydrogen evolution via inducing local electric field and electron localization[J]. Chinese Journal of Catalysis, 2023, 54: 229-237.

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图/表 6

Fig. 1. Electric field distribution around the surface of HC-CoS2 (a) and LC-CoS2 (c). OH- concentration distributions around the surface of HC-CoS2 (b) and LC-CoS2 (d).

Fig. 2. Comparison of schematic diagram of electron localization for bare CoS2 (a) and Cu-CoS2 (b). Blue, cobalt; brown, copper; yellow, sulfur; white, hydrogen. (c) The charge density differences analysis. Green, depletion; red, accumulation. (d) PDOS and d-band center for Co. (e) Free energy diagram.

Fig. 3. (a) Schematic illustration of the preparation for catalysts. SEM images of Cu-CoS2 NNs (b) and Cu-CoS2 NWs (c). (d) HRTEM image of Cu-CoS2 NNs. TEM image of Cu-CoS2 NNs (e) and Cu-CoS2 NWs (f). (g) EDS mapping images of Cu-CoS2 NNs.

Fig. 4. High-resolution XPS of S 2p (a), Co 2p (b), and Cu 2p (c). (d) Cu LMM auger spectra.

Fig. 5. (a) OH- concentration on the surface of the catalysts at -0.07 V vs. RHE. In situ ATR-IR spectra of Cu-CoS2 NNs (b) and Cu-CoS2 NWs (c). (d) Current densities of Cu-CoS2 NNs (b) and Cu-CoS2 NWs electrodes in the electro-response measurements under Ar and H2.

Fig. 6. (a) HER polarization curves with a scan rate of 5 mV s-1 in 1.0 mol L-1 KOH solution. (b) Tafel plots originated from the corresponding polarization curves. (c) Overpotentials at a current density of -10 mA cm-2 and -100 mA cm-2. (d) Stability test at -0.18 V vs. RHE in 1.0 mol L-1 KOH solution. (e) Comparison of performance for different catalysts at a current density of -10 mA cm-2.

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通过诱导局域电场和电子局域化协同碱性析氢

Cooperative alkaline hydrogen evolution via inducing local electric field and electron localization

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