高熵合金金属烯用于酸性条件下全水分解

doi:10.1016/S1872-2067(22)64166-4

催化学报 ›› 2023, Vol. 45: 174-183.DOI: 10.1016/S1872-2067(22)64166-4

• 论文 • 上一篇

高熵合金金属烯用于酸性条件下全水分解

张丹^a^,^b, 石月^a, 陈希磊^b, 赖建平^a^,^*(), 黄勃龙^c^,^*(), 王磊^a^,^b^,^*()

^a青岛科技大学化学与分子工程学院, 生态化工国家重点实验室基地, 生态化工程与绿色制造国际科技合作基地, 山东青岛266042
^b青岛科技大学环境与安全工程学院, 山东省海洋环境腐蚀与安全防护工程研究中心, 山东青岛266042
^c香港理工大学应用生物及化学科技学系, 香港九龙999077

收稿日期:2022-07-04 接受日期:2022-08-09 出版日期:2023-02-18 发布日期:2023-01-10
通讯作者: 赖建平,黄勃龙,王磊
基金资助:
国家自然科学基金(22001143);国家自然科学基金(52072197);山东省高校青年创新技术基金(2019KJC004);山东省杰出青年基金(ZR2019JQ14);泰山学者青年专家计划(tsqn201909114);泰山学者青年专家计划(tsqn201909123);山东省优秀青年基金(ZR2020YQ34);重大科技创新项目(2019JZZY020405);山东省自然科学基金重大基础研究项目(ZR2020ZD09)

High-entropy alloy metallene for highly efficient overall water splitting in acidic media

Dan Zhang^a^,^b, Yue Shi^a, Xilei Chen^b, Jianping Lai^a^,^*(), Bolong Huang^c^,^*(), Lei Wang^a^,^b^,^*()

^aState Key Laboratory Base of Eco-Chemical Engineering, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
^bShandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
^cDepartment of Applied Biology and Chemical Technology, the Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, China

Received:2022-07-04 Accepted:2022-08-09 Online:2023-02-18 Published:2023-01-10
Contact: Jianping Lai, Bolong Huang, Lei Wang
Supported by:
National Natural Science Foundation of China(22001143);National Natural Science Foundation of China(52072197);Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China(2019KJC004);Outstanding Youth Foundation of Shandong Province, China(ZR2019JQ14);Taishan Scholar Young Talent Program(tsqn201909114);Taishan Scholar Young Talent Program(tsqn201909123);Natural Science Foundation of Shandong Province(ZR2020YQ34);Major Scientific and Technological Innovation Project(2019JZZY020405);Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09)

摘要/Abstract

摘要：

质子交换膜水电解槽(PEMWE)因其在低温下的高效率和高功率密度, 成为新一代电解槽的发展方向. 在水的电解过程中, 设计高效稳定的析氢反应(HER)和析氧反应(OER)催化剂是进一步提高电解槽应用的前提. 根据HER和OER“火山型”分布曲线, 贵金属(Ir, Ru等)依然是主要的基准电催化剂. 对于酸性条件下全水分解, Ir基和Ru基双功能催化剂仍然是最常见的选择. 然而, 与Ir基催化剂相比, Ru基催化剂在酸性条件下的高溶解速率易导致催化剂快速失活, 大大降低了其实际应用价值. 目前, 酸性条件下全水分解的Ir基催化剂也取得了一些成果, 如合金(如PdCu/Ir, Au@AuIr₂, IrTe纳米棒和IrNi合金纳米花)、钙钛矿(如AIrO₃)、硒化物(如Li-IrSe₂)和团簇(如Ir纳米团簇, IrNi纳米团簇)等. 然而, Ir基材料在高电流密度下仍然面临质量活性低和稳定性有限的挑战(100 mA cm^-2时的过电位超过420 mV, 酸性整体水分解在高电流密度下的长期稳定性差). 上述问题使得电催化剂无法满足PEMWE的应用要求. 因此, 开发具有优异电化学活性和稳定性的新型Ir基电催化剂成为当务之急.
近年来, 至少由五种元素组成的高熵合金(HEAs)材料具有在极端条件下的硬度、韧性、腐蚀性和热稳定性等的强耐受性, 因而引起了研究者的广泛兴趣. 同时, 不同组分的可控性也赋予了HEAs固有的晶格畸变和可调电子结构的协同效应, 在催化领域也发挥着重要作用. 目前, 尚未见使用HEAs催化剂进行酸性条件下全水分解的相关报道. 从形貌上看, 金属烯具有表面金属原子体积比大、表面金属缺陷丰富、稳定性较好等优点, 从而表现出较好的催化性能. 因此, 结合HEAs协同效应和金属烯结构优点的电催化剂, 有望解决酸性条件下全水分解电催化剂的设计问题.
本文成功制备了具有丰富的无定形和晶体结构的IrPdRhMoW HEA金属烯作为一种高效的双功能电催化剂, 用于酸性条件下全水分解. 在0.5 mol L^-1 H₂SO₄溶液中, IrPdRhMoW/C在10 mA cm^-2下HER和OER的过电位分别为15和188 mV, 远强于商业催化剂(HER: Pt/C, 47 mV和OER: RuO₂, 305 mV)和大部分已报道的贵金属基催化剂. 使用IrPdRhMoW/C进行全水分解, 只需1.48 V的电池电压即可获得10 mA cm^-2的电流密度, 而实现100 mA cm^-2的电流密度所需的电池电压为1.59 V. IrPdRhMoW/C在100 mA cm^-2水分解100 h后仍保持较好的电活性和结构稳定性, 这也是在高电流密度下实现酸性条件下全水分解的长期稳定性. 密度泛函理论计算结果表明, 由于晶体和非晶结构的共存, HEA中电子结构的具有自平衡效应. 强轨道耦合不仅最大限度地提高了对HER和OER的电活性, 而且稳定了金属位点的价态, 以实现持久的电催化全水分解. 综上, 本工作不仅成功制备了HEA金属烯, 而且将其应用于酸性条件下全水分解. 此外, 电荷自平衡效应可以解决酸性条件下全水分解过程中活性与稳定性之间的问题, 且有望进一步应用到其他电催化剂的设计和合成中.

关键词: 高熵合金, 金属烯, 结晶/非晶, 全水解, 酸性介质

Abstract:

The preparation of stable and efficient acidic overall water splitting catalysts is crucial to advance the progress of proton exchange membrane water electrolyzers. Herein, we successfully prepared IrPdRhMoW HEA metallene with rich amorphous and crystalline structures. In 0.5 mol L^-1 H₂SO₄, the extraordinary catalytic performance (the overpotentials for hydrogen evolution (HER) and oxygen evolution (OER) of IrPdRhMoW/C at 10 mA cm^-2 are 15 mV and 188 mV, respectively) is far stronger than that of commercial catalysts (HER: Pt/C, 47 mV and OER: RuO₂, 305 mV) and even other reported noble metal-based catalysts. Using IrPdRhMoW/C for the overall water splitting, only a cell voltage of 1.48 V is required to achieve 10 mA cm^-2 and 1.59 V required to achieve 100 mA cm^-2, which is the best voltage under high current density reported so far. More importantly, the IrPdRhMoW/C still maintains excellent electroactivity and structural stability after 100 h of water splitting at 100 mA cm^-2. Theory calculations reveal the self-balanced effect of electronic structures in the HEA due to the co-existence of crystalline and amorphous lattice structures. The strong orbital couplings not only maximize the electroactivity towards both HER and OER but also stabilize the valence states of metal sites for durable electrocatalysis.

Key words: High-entropy alloy, Metallene, Crystalline/amorphous, Overall water splitting, Acidic media

张丹, 石月, 陈希磊, 赖建平, 黄勃龙, 王磊. 高熵合金金属烯用于酸性条件下全水分解[J]. 催化学报, 2023, 45: 174-183.

Dan Zhang, Yue Shi, Xilei Chen, Jianping Lai, Bolong Huang, Lei Wang. High-entropy alloy metallene for highly efficient overall water splitting in acidic media[J]. Chinese Journal of Catalysis, 2023, 45: 174-183.

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图/表 5

Fig. 1. TEM image (a), XRD pattern (b), HRTEM images (c,d), HAADF-STEM and corresponding EDX mapping images (e) of IrPdRhMoW/C.

Fig. 2. (a) HER polarization curves. (b) Overpotentials at 10 mA cm-2. (c) The corresponding Tafel plots. (d) Exchange current density. (e) TOF values. (f) Estimation of the ECSA using the Cu-UPD method of IrPdRhMoW/C and Pt/C.

Fig. 3. (a) OER polarization curves. (b) Overpotentials at 10 mA cm-2. (c) The corresponding Tafel plots. (d) TOF values. (e) Electrochemical impedance spectra of IrPdRhMoW/C. (f) Polarization curves of IrPdRhMoW/C before and after 10000 CV cycles.

Fig. 4. (a) The top view of the IrPdRhMoW structure. (b) 3D contour plot of electronic distribution near Fermi level of IrPdRhMoW. Dark green balls = Pd, purple balls = Rh, orange balls = Mo, pink balls = Ir and grey balls = W. Blue isosurface = bonding orbitals and green isosurface = anti-bonding orbitals. (c) The PDOS of IrPdRhMoW HEA. (d) The simulated RDF of IrPdRhMoW HEA. The inset is the RDF of crystalline IrPdRhMoW. The site-dependent PDOS of Ir-5d (e), Pd-4d (f), Rh-4d (g), Mo-4d (h) and W-5d (i). (j) The formation energy of different metal vacancies. (k) The energy change of OER at U = 0 V. (l) The energy change of OER at U = 1.23 V. (m) The binding energy comparisons of the proton.

Fig. 5. (a) The digital photo of two-electrode configuration with bubbles on both electrodes. (b) Polarization curves of the two-electrode overall water splitting cells. (c) The amount of H2 and O2 theoretically calculated and experimentally measured for IrPdRhMoW/CP||IrPdRhMoW/CP for 60 minutes. (d) Chronopotentiometry curve of IrPdRhMoW/CP||IrPdRhMoW/CP at 100 mA cm?2.

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高熵合金金属烯用于酸性条件下全水分解

High-entropy alloy metallene for highly efficient overall water splitting in acidic media

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