硼掺杂诱导d-p轨道杂化调节镍电子结构实现高效催化碱性氢氧化反应

doi:10.1016/S1872-2067(21)63955-4

催化学报 ›› 2022, Vol. 43 ›› Issue (6): 1527-1534.DOI: 10.1016/S1872-2067(21)63955-4

硼掺杂诱导d-p轨道杂化调节镍电子结构实现高效催化碱性氢氧化反应

韩鹏宇^a^,^†, 姚娜^a^,^†, 左为^a, 罗威^a^,^b^,^*()

^a武汉大学化学与分子科学学院, 湖北武汉430072
^b武汉大学苏州研究院, 江苏苏州215123

收稿日期:2021-08-27 接受日期:2021-08-27 出版日期:2022-06-18 发布日期:2022-04-14
通讯作者: 罗威
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家重点研发计划(2018YFB1502302);国家自然科学基金(21972107);国家自然科学基金(21633008);江苏省自然科学基金(BK20191186);湖北省自然科学基金(2020CFA095)

Manipulating the electronic structure of Ni electrocatalyst through d-p orbital hybridization induced by B-doping for efficient alkaline hydrogen oxidation reaction

Pengyu Han^a^,^†, Na Yao^a^,^†, Wei Zuo^a, Wei Luo^a^,^b^,^*()

^aCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China
^bSuzhou Institute of Wuhan University, Suzhou 215123, Jiangsu, China

Received:2021-08-27 Accepted:2021-08-27 Online:2022-06-18 Published:2022-04-14
Contact: Wei Luo
About author:First author contact:
† Contributed equally to this work.
Supported by:
National Key Research and Development Program of China(2018YFB1502302);National Natural Science Foundation of China(21972107);National Natural Science Foundation of China(21633008);Natural Science Foundation of Jiangsu Province(BK20191186);Natural Science Foundation of Hubei Province(2020CFA095)

摘要/Abstract

摘要：

与质子交换膜燃料电池相比, 碱性交换膜燃料电池(AEMFC)能够同时在阳极和阴极使用非贵金属, 从而显著降低燃料电池的成本. 目前, 在阴极氧还原反应(ORR)已经开发出可以媲美Pt/C的非贵金属催化剂, 而阳极氢氧化反应(HOR)最有希望的非贵金属催化剂仅限于镍基催化剂, 且其催化性能却远落后于铂基电催化剂. 因此, 开发高效、稳定的碱性HOR镍基催化剂对于推动AEMFC的实际应用具有重要意义.
本文通过对负载在XC-72上的无定型硼化镍(NiB/C)进行煅烧, 得到了硼掺杂的镍(B-Ni/C). 粉末X射线晶体衍射结果表明, 煅烧后催化剂的晶体形式为fcc相的Ni. 透射电子显微镜结果表明, 催化剂呈分散的纳米颗粒状态, 能量色散光谱图也证明了Ni、B元素均匀分布于C上. 在0.1 mol/L KOH条件下进行HOR活性测试, B-Ni/C样品的比面积交换电流密度和在50 mV过电位下的比质量交换电流密度分别为0.035 mA cm_Ni^-2和27.95 mA mg_Ni^-1, 与未掺杂硼的镍碳(Ni/C)催化剂相比, 其质量活性提高了10倍. 在加速耐久性测试中, B-Ni/C催化剂在氩气中1000圈电位循环后仍具有一定的氢氧化活性, 表明其具有较好的抗氧化稳定性. 在含有万分之一浓度CO的H₂中进行长时间计时电流法测试结果表明, 相比于Pt/C, NiB/C活性仅有轻微损失, 表现出出色的抗CO能力. 此外B-Ni/C在1 mol/L KOH条件下也具有较好的HER性能, 仅需128 mV的过电位就可以达到10 mA cm^‒2的电流密度. 实验和密度泛函理论计算表明, B掺杂后, B的p轨道和Ni的d轨道之间会形成d-p杂化, 从而促进Ni表面对OH的吸附, 同时优化了其表面的氢结合能, 降低了水物种的形成能, 有助于提高碱性条件下的HOR性能. 综上, 本文通过简单方法设计了一种杂原子掺杂的镍基催化剂, 其表现出较好的氢氧化活性, 为开发低成本、高效的非铂碱性HOR催化剂提供了新的视角.

关键词: 氢气氧化反应, 氢气析出反应, d-p杂化, 硼掺杂, 密度泛函理论

Abstract:

Developing highly efficient platinum-group-metal-free electrocatalysts towards hydrogen oxidation reaction (HOR) under alkaline electrolyte is critical for the development of alkaline exchange member fuel cells. Herein, we reported the synthesis of boron doped Ni electrocatalyst (B-Ni/C) and its remarkable alkaline HOR performance, with a 10-fold mass activity enhancement compared with that of undoped Ni catalyst. Experimental results and density functional theory calculations indicate the d-p hybridization between the p orbital of B and the d orbital of Ni via B-doping could lead to promoted OH adsorption and optimized hydrogen binding energy on Ni surface, which together with the reduced formation energy of water species, contributes to the enhanced HOR performance under alkaline electrolyte.

Key words: Hydrogen oxidation reaction, Hydrogen evolution reaction, d-p hybridization, Boron doping, Density functional theory

韩鹏宇, 姚娜, 左为, 罗威. 硼掺杂诱导d-p轨道杂化调节镍电子结构实现高效催化碱性氢氧化反应[J]. 催化学报, 2022, 43(6): 1527-1534.

Pengyu Han, Na Yao, Wei Zuo, Wei Luo. Manipulating the electronic structure of Ni electrocatalyst through d-p orbital hybridization induced by B-doping for efficient alkaline hydrogen oxidation reaction[J]. Chinese Journal of Catalysis, 2022, 43(6): 1527-1534.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63955-4

https://www.cjcatal.com/CN/Y2022/V43/I6/1527

图/表 4

Fig. 1. (a) XRD patterns of NiB/C and B-Ni/C-X; TEM (b) and HRTEM (c) images of B-Ni/C-2; STEM image (d) and EDS maps of elemental Ni (e), B (f), C (g), and overplay (h) in B-Ni/C-2.

Fig. 2. (a) HOR polarization curves of Ni/C, B-Ni/C-1, B-Ni/C-2, and B-Ni/C-3 in H2-saturated 0.1 mol/L KOH solution at a rotating speed of 2500 r/min. (b) Polarization curves of B-Ni/C-2 in H2-saturated 0.1 mol/L KOH solution at the rotating speeds varied from 2500 to 400 r/min. Inset shows the Koutecky-Levich plot at 50 mV (vs. RHE). (c) Tafel plots derived from (a) as well as the corresponding fits to the Butler-Volmer equation. (d) Comparison of jk at the overpotential of 50 mV (unpatterned) and j0 (patterned) of the four catalysts.

Fig. 3. (a) HER polarization curves of Ni/C, B-Ni/C-X and Pt/C in Ar-saturated 1 mol/L KOH at the rotating speed of 1600 r/min. (b) HER Tafel slopes measured according to the HER performance in (a). (c) EIS of Ni/C, B-Ni/C-X and Pt/C. (d) chronopotentiometry curves of Pt/C and B-Ni/C-2 under current density of 10 mA cm?2.

Fig. 4. (a) Schematic diagram of d-p hybrid orbital and adsorption of OH. (b) The d-orbital and p-orbital partial density of states in B-Ni and Ni. (c,d) Isosurface diagram of OH adsorption surface of Ni and B-Ni. (e) Free energy diagram of HOR on B-Ni and Ni.

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硼掺杂诱导d-p轨道杂化调节镍电子结构实现高效催化碱性氢氧化反应

Manipulating the electronic structure of Ni electrocatalyst through d-p orbital hybridization induced by B-doping for efficient alkaline hydrogen oxidation reaction

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