高熵磷化物双功能催化剂的制备及高效电解水性能

doi:10.15541/jim20240074

无机材料学报 ›› 2024, Vol. 39 ›› Issue (11): 1265-1274.DOI: 10.15541/jim20240074 CSTR: 32189.14.10.15541/jim20240074

所属专题：【能源环境】氢能材料(202409)

高熵磷化物双功能催化剂的制备及高效电解水性能

张文宇¹^,²^,³(), 郭瑞华¹^,²^,³(), 岳全鑫¹^,²^,³, 黄雅荣¹, 张国芳¹, 关丽丽¹^,²

1.材料科学与工程学院内蒙古科技大学, 包头 014010
2.内蒙古自治区先进陶瓷材料与器件重点实验室内蒙古科技大学, 包头 014010
3.轻稀土资源绿色提取与高效利用教育部重点实验室内蒙古科技大学, 包头 014010

收稿日期:2024-02-21 修回日期:2024-05-23 出版日期:2024-11-20 网络出版日期:2024-06-24
通讯作者: 郭瑞华, 教授. E-mail: grh7810@163.com
作者简介:张文宇(1997-), 男, 硕士研究生. E-mail: zhangwenyu529@qq.com
基金资助:
国家自然科学基金(51864040);国家自然科学基金(51962028);国家自然科学基金(52162010);内蒙古自治区科技计划(2021GG0042);内蒙古自治区高等学校青年科技英才(NJYT22064);内蒙古自治区自然科学基金(2022MS05018);内蒙古自治区自然科学基金(2022LHMS05021)

High-entropy Phosphide Bifunctional Catalyst: Preparation and Performance of Efficient Water Splitting

ZHANG Wenyu¹^,²^,³(), GUO Ruihua¹^,²^,³(), YUE Quanxin¹^,²^,³, HUANG Yarong¹, ZHANG Guofang¹, GUAN Lili¹^,²

1. School of Materials Science and Engineering, Inner Mongolia University of Science & Technology, Baotou 014010, China
2. Inner Mongolia Key Laboratory of Advanced Ceramic Materials and Devices, Inner Mongolia University of Science & Technology, Baotou 014010, China
3. Key Laboratory of Green Extraction & Efficient Utilization of Light Rare-Earth Resources, Ministry of Education, Inner Mongolia University of Science & Technology, Baotou 014010, China

Received:2024-02-21 Revised:2024-05-23 Published:2024-11-20 Online:2024-06-24
Contact: GUO Ruihua, professor. E-mail: grh7810@163.com
About author:ZHANG Wenyu (1997-), male, Master candidate. E-mail: zhangwenyu529@qq.com
Supported by:
National Natural Science Foundation of China(51864040);National Natural Science Foundation of China(51962028);National Natural Science Foundation of China(52162010);Inner Mongolia Autonomous Region Science and Technology Program(2021GG0042);Inner Mongolia Autonomous Region Youth Science and Technology Excellence in Higher Education(NJYT22064);Inner Mongolia Autonomous Region Natural Science Foundation Program(2022MS05018);Inner Mongolia Autonomous Region Natural Science Foundation Program(2022LHMS05021)

摘要/Abstract

摘要：

在电解水制氢过程中, 析氢反应(HER)和析氧反应(OER)的缓慢电催化动力学限制了其能量转换效率。高熵材料具有独特的结构特征和优异的性能, 是一种潜在的电解水催化剂, 有可能取代传统的金属氧化物和贵金属。由于金属与非金属之间的不相容性, 关于高熵化合物特别是高熵金属磷化物合成的报道很少。本研究以柠檬酸为络合剂、磷酸二氢铵为磷源, 采用低温溶胶-凝胶法, 通过添加不同组元金属合成了一系列以碳为基底的高熵合金磷化物纳米颗粒。在1 mol·L^-1的KOH介质中, FeCoNiMoCeP/C表现出良好的电解水性能, 在电流密度为10 mA·cm^-2条件下, FeCoNiMoCeP/C电极电催化HER和OER所需的过电位分别为119和240 mV。在全解水研究中, FeCoNiMoCeP/C表现出优异的催化活性。在电流密度为10 mA·cm^-2条件下, FeCoNiMoCeP/C同时用作阴极和阳极的电解水反应所需过电位仅为1.53 V。这是由于高熵磷化物催化剂原子之间的协同作用可以提供更多的反应位点, 增加反应活性和选择性。本研究可拓展高熵合金在电催化领域的潜在应用范围。

关键词: 高熵金属磷化物, 双功能催化剂, 全解水, 协同效应

Abstract:

In the process of electrolyzing water to produce hydrogen, the sluggish electrocatalytic kinetics of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) limit the energy conversion efficiency. High-entropy materials have been considered as potential catalysts due to their unique structural features and excellent performance, which could potentially replace traditional metal oxides and precious metals for energy conversion and water electrolysis. Due to the incompatibility between different metals and non-metals, there have been few reports on the synthesis of high-entropy compounds, especially high-entropy metal phosphides. In this study, a series of carbon-based high-entropy alloy phosphide nanoparticles were synthesized using citric acid as complexing agent and ammonium dihydrogen phosphate as phosphorus source via a low-temperature Sol-Gel method with different elemental metals. In 1 mol·L^-1 KOH solution, FeCoNiMoCeP/C exhibited good water electrolysis performance at a current density of 10 mA·cm^-2, with overpotentials of 119 and 240 mV for the HER and OER, respectively. Similarly, in overall water splitting studies, FeCoNiMoCeP/C also showed excellent catalytic activity. When operating at a current density of 10 mA·cm^-2, FeCoNiMoCeP/C required only 1.53 V as the combined anode and cathode voltage for electrolyzing water. This is due to the synergistic effects among the atoms of high-entropy phosphide catalysts which provide more reaction sites to increase reaction activity and selectivity. This study is expected to expand the potential applications of high-entropy alloys in the field of electrocatalysis.

Key words: high-entropy metal phosphide, bifunctional catalyst, overall water splitting, synergistic effect

中图分类号:

TQ116

张文宇, 郭瑞华, 岳全鑫, 黄雅荣, 张国芳, 关丽丽. 高熵磷化物双功能催化剂的制备及高效电解水性能[J]. 无机材料学报, 2024, 39(11): 1265-1274.

ZHANG Wenyu, GUO Ruihua, YUE Quanxin, HUANG Yarong, ZHANG Guofang, GUAN Lili. High-entropy Phosphide Bifunctional Catalyst: Preparation and Performance of Efficient Water Splitting[J]. Journal of Inorganic Materials, 2024, 39(11): 1265-1274.

图/表 13

图1 不同催化剂的(a)XRD图谱和(b~f)拉曼光谱图

Fig. 1 (a) XRD patterns and (b-f) Raman spectra of different catalysts

图2 不同放大倍数下FeCoNiMoCeP/C的SEM照片

Fig. 2 SEM images of FeCoNiMoCeP/C at different magnifications

图3 FeCoNiMoCeP/C的TEM和高分辨TEM照片

Fig. 3 TEM and high-resolution TEM (HRTEM) images of FeCoNiMoCeP/C (a) TEM image; (b) HRTEM image and selected-area electron diffraction (SAED) image (inset) of the square region in (a); (c) HRTEM image of the circular region in (b); (d) Fast Fourier transform (FFT) and (e) inverse fast Fourier transform (IFFT) images of the square region in (c)

图4 不同样品的高角度环形暗场扫描透射电子显微镜(HAADF-STEM)照片及其相应的EDS元素分布图

Fig. 4 High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images and corresponding EDS elemental mappings of different samples (a) FeP/C; (b) FeCoP/C; (c) FeCoNiP/C; (d) FeCoNiMoP/C; (e) FeCoNiMoCeP/C

图5 FeCoNiMoCeP/C的XPS谱图

Fig. 5 XPS spectra of FeCoNiMoCeP/C (a) Surve; (b) Fe2p; (c) Co2p; (d) Ni2p; (e) Mo3d; (f) Ce3d; (g) P2p

图6 不同催化剂的OER及HER性能

Fig. 6 OER and HER performance of different catalysts (a) OER LSV curves; (b) OER Tafel plots; (c) HER LSV curves; (d) HER Tafel plots. Colorful figures are available on website

图7 不同催化剂的(a)双层电容(Cdl)曲线、(b) SECSA归一化后的OER LSV曲线、(c) SECSA归一化后的HER LSV曲线; (d) FeCoNiMoCeP/C 催化剂的电流-时间(I-t)曲线

Fig. 7 (a) Double-layer capacitance (Cdl) curves, (b) SECSA-normalized OER LSV curves, and (c) SECSA-normalized HER LSV curves for different catalysts; (d) Current-time (I-t) curve of FeCoNiMoCeP/C catalyst Inset in (d): LSV curves of FeCoNiMoCeP/C before and after 72 h stability test at 1.5 V. Colorful figures are available on website

图8 FeCoNiMoCeP/C || FeCoNiMoCeP/C全解水性能分析

Fig. 8 Performance analysis of FeCoNiMoCeP/C || FeCoNiMoCeP/C for overall water splitting (a) LSV curves of FeCoNiMoCeP/C || FeCoNiMoCeP/C and Pt/C || RuO2 with inset showing photograph of overall water splitting equipment with two electrodes; (b) I-t curve of FeCoNiMoCeP/C || FeCoNiMoCeP/C

图S1 通过 ICP-OES 测量FeCoNiMoCeP/C 催化剂中金属元素Fe、Co、Ni、Mo和Ce的原子分数

Fig. S1 Atomic percentages of metal elements Fe, Co, Ni, Mo, and Ce in FeCoNiMoCeP/C catalyst measured by ICP-OES

图S2 不同催化剂的XPS谱图

Fig. S2 XPS spectra of different catalysts (a) Fe2p; (b) Co2p; (c) Ni2p; (d) Mo2p

图S3 催化剂在不同扫描速率下的CV曲线

Fig. S3 CV curves at different scan rates (a) FeCoNiMoCeP/C; (b) FeCoNiMoP/C; (c) FeCoNiP/C; (d) FeCoP/C; (e) FeP/C

图S4 FeCoNiMoCeP/C在72 h稳定性测试后的结构形貌以及EDS元素分布图

Fig. S4 Structure morphology and EDS elemental mappings of FeCoNiMoCeP/C after stability test for 72 h (a) SEM image; (b) HRTEM image; (c) Crystallographic planes and interplanar spacing marked by dashed boxes in (b); (d) IFFT pattern corresponding to the selected area marked by the dashed array in (c); (e) Elemental mappings

表S1 FeCoNiMoCeP/C与文献报道催化剂在10 mA·cm-2条件下的OER、HER和全解水性能比较

Table S1 OER, HER, and overall water splitting performance of the FeCoNiMoCeP/C and catalysts in literature at 10 mA·cm-2

Sample	Electrolyte solvent	η_{10 OER}/ mV	η_{10 HER}/ mV	OER Tafel slope/ (mV·dec^-1)	HER Tafel slope/ (mV·dec^-1)	η_{10 overall water splitting}/V	Stability/h	Ref.
FeCoNiMoCeP/C	1.0 mol·L^-1 KOH	240	119	63.4	82.7	1.53	72	This work
NiCoFeMnCrP	1.0 mol·L^-1 KOH	270	220	52.5	94.5	1.55	24	[13]
FeNiCoMnCu@CNT	1.0 mol·L^-1 KOH+Sea water	380	290	130.0	171.0	1.60	40	[35]
CoNiCuMnAl@C 2 h	1.0 mol·L^-1 KOH+Sea water	290	-	66.8	-	1.54	30	[36]
CoCrFeNiMo	1.0 mol·L^-1 KOH	270	157	62.5	46.7	1.86	22	[37]
CoZnCdCuMnS@CF	1.0 mol·L^-1 KOH	220	173	69.8	98.5	1.63	70	[38]
La-HEO@NiFeOOH(1 : 3)	1.0 mol·L^-1 KOH	262	-	38.0	-	1.57	30	[39]

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高熵磷化物双功能催化剂的制备及高效电解水性能

High-entropy Phosphide Bifunctional Catalyst: Preparation and Performance of Efficient Water Splitting

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