MOF衍生的分层多孔三维N-CoPx/Ni2P大电流密度下加速析氢

doi:10.1016/S1872-2067(21)63982-7

摘要/Abstract

摘要：

氢气(H₂)具有能量密度高、环境友好等优点, 是一种很有前景的清洁能源载体. 目前, 电催化水裂解大规模制氢被认为是一种理想可行的方法. 析氢反应(HER)涉及多个步骤, 首先形成吸附的氢(Volmer步骤), 然后是脱附步骤(Heyrovsky步骤)或两个相邻的吸附氢形成H₂(Tafel步骤). 与酸性介质相比, 碱性介质中的HER可与现有的析氧反应(OER)催化剂偶合, 降低电解水的设备成本, 因此研究碱性条件下HER更具应用价值. 但是, HER在碱性介质中不可避免地需要打破较强的共价键H-O-H, 动力学缓慢, 导致需要高过电位驱动反应. 因此, 开发适用于广泛的pH范围, 特别是碱性介质高催化活性的催化剂, 成为当务之急. 金属铂是最高效的HER催化剂, 但昂贵的价格严重阻碍了其在电解水中的大规模商业化应用. 因此, 开发过电位低和稳定性持久的非贵金属催化剂, 特别是可以在大电流密度(>500 mA cm^-2的质子交换膜和碱性电解槽)下稳定工作的催化剂, 对实际工业应用至关重要. 过渡金属磷化物(TMPs), 尤其是CoP和Ni₂P在HER中表现出了较好的催化活性, 引起广泛关注. 但是, 有限的电子结构、低电导率和大电流密度测试过程中的团聚仍然是限制其实际应用的瓶颈. 近年来, 具有金属可调性、多孔型结构、高比表面积和多交叉开放通道的金属有机骨架(MOFs)已被证明是制备TMPs的理想前驱体. 但是, 在高温煅烧过程中无法避免MOF结构坍塌, 导致开放通道和电导率降低, 限制了电子/离子的传输以及在高电流密度下的电催化活性.
本文通过TMPs和Co-MOF之间的简单拓扑化学转化制备了一种自支撑结构的N掺杂二元TMPs电催化剂(N-CoP_x/ Ni₂P), 以Co-MOF作为模板和前驱体, 一部分泡沫镍原位磷化成Ni₂P, 形成异质结构的双金属磷化物. 扫描电镜和透射电镜结果表明, 该催化剂呈三维多孔结构, 有利于充分暴露活性位点. 通过X射线光电子能谱分析了催化剂表面化学状态, 发现形成了Co-N键, 说明N掺杂成功. 通过电化学测试结果表明, N-CoP_x/Ni₂P在全pH范围内表现出较好的HER活性, 尤其在碱性介质中, 当电流密度为650 mA cm^-2时, 仅需要152 mV过电位. 催化剂转化率为3.2 s^-1, 法拉第效率接近100%, 该催化剂在200 mA cm^-2电流密度下连续工作24 h无明显衰减. 密度泛函理论计算表明, N-CoP_x/Ni₂P催化活性的增强归因于氮掺杂及双金属磷化物的协同作用提高了催化剂的本征活性位点, 从而优化了氢吸附能和水结合能. 综上, 本文为廉价电催化剂的工业化应用提供了一种有前景的策略.

关键词: 析氢反应, 金属有机骨架模板, N-CoP_x/Ni₂P, 三维导电网络, 大电流密度

Abstract:

Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production. However, developing effective and stable non-noble-metal electrocatalysts which work well at high current densities demanded by industry still remain great challenge. Herein, taking advantage of the highly tunable metal-organic framework (MOF) templates, nitrogen doped binary transition metal phosphides electrocatalysts (N-CoP_x/Ni₂P) with three-dimensional (3D) conductive network structure were successfully synthesized. The 3D open porous channels could expose more catalytically active sites; nitrogen doping and the synergistic effect between CoP and Ni₂P can increase the electron density of Co atoms at active sites, further optimizing the Gibbs free energy of hydrogen (ΔG_H*) and water (ΔG_H2O*). As a result, the obtained N-CoP_x/Ni₂P catalyst exhibits extraordinary electrocatalytic activity in a wide pH range. Especially, it requires an extremely low overpotential of 152 mV to deliver a high current density of 650 mA cm^-2in alkaline media. This work may shed some light on the rational design of cheap electrocatalysts and electrode materials that work well at high current densities.

Key words: Hydrogen evolution reaction, MOF templates, N-CoP_x/Ni₂P, Three-dimensional conductive network, High current density

王兰, 公宁, 周洲, 张启成, 彭文朝, 李阳, 张凤宝, 范晓彬. MOF衍生的分层多孔三维N-CoP_x/Ni₂P大电流密度下加速析氢[J]. 催化学报, 2022, 43(4): 1176-1183.

Lan Wang, Ning gong, Zhou Zhou, Qicheng Zhang, Wenchao Peng, Yang Li, Fengbao Zhang, Xiaobin Fan*. A MOF derived hierarchically porous 3D N-CoP_x/Ni₂P electrode for accelerating hydrogen evolution at high current densities[J]. Chinese Journal of Catalysis, 2022, 43(4): 1176-1183.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63982-7

https://www.cjcatal.com/CN/Y2022/V43/I4/1176

图/表 5

Scheme 1. Schematic illustration shows the fabrication process for N-CoPx/Ni2P nanowall through converting the Co-MOF upon phosphorization.

Fig. 1. (a,b) SEM images of the Co-MOF/NF; SEM (c) and TEM (d-g) images of the N-CoPx/Ni2P; (h-k) EDS elemental mappings of N-CoPx/Ni2P.

Fig. 2. High resolution XPS spectra of Co 2p (a), Ni 2p (b), P 2p (c), and N 1s (d) for N-CoPx/Ni2P and CoPx/Ni2P.

Fig. 3. (a,b) HER polarization curves and the corresponding Tafel plots of N-CoPx/Ni2P, CoPx/Ni2P and Ni2P in 0.5 mol/L H2SO4, 1.0 mol/L PBS and 1.0 mol/L KOH with iR-corrected; (c) The corresponding HER overpotential required for j = 10, 100, 200 mA cm-2; (d) The corresponding Cdl values. (e) iR-corrected polarization curves recorded before and after 10000 accelerated degradation test CV cycles; (f) Time dependence of the current density for N-CoPx/Ni2P at static overpotentials of 63 mV (in 0.5 mol/L H2SO4), 80 mV (in 1.0 mol/L PBS) and 53 mV (in 1.0 mol/L KOH) for 24 h; (g) TOFs for Ni2P, CoPx/Ni2P, and N-CoPx/Ni2P at an overpotential of 100 mV in 1.0 mol/L KOH; (h) Theoretical and measured amount of H2 during electrolysis at 30 mA cm-2in 1.0 mol/L KOH; (i) Comparison of the overpotential and Tafel slope of N-CoPx/Ni2P with other recently reported TMP catalysts in 1.0 mol/L KOH.

Fig. 4. (a) iR-corrected HER polarization curves of N-CoPx/Ni2P in 0.5 mol/L H2SO4, 1.0 mol/L PBS and 1.0 mol/L KOH at high current density 650 mA cm-2; (b) Time dependence of the current density (200 mA cm-2) for N-CoPx/Ni2P at static overpotentials of 138 mV (in 0.5 mol/L H2SO4), 264 mV (in 1.0 mol/L PBS) and 134 mV (in 1.0 mol/L KOH) for 24 h; (c) Top view of the optimized heterogeneous structure of H and H2O adsorption on N-CoP/Ni2P surface. Color denotation: pink (Co), brown (Ni), blue (P), cyan-blue (N), red (O) and white (H); (d) The calculated HER free-energy; (e) Water adsorption energy.

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MOF衍生的分层多孔三维N-CoP_x/Ni₂P大电流密度下加速析氢

A MOF derived hierarchically porous 3D N-CoP_x/Ni₂P electrode for accelerating hydrogen evolution at high current densities

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