原位负载Pt-Co高指数晶面催化剂的制备及其电催化性能

doi:10.15541/jim20220298

无机材料学报 ›› 2023, Vol. 38 ›› Issue (1): 71-78.DOI: 10.15541/jim20220298

原位负载Pt-Co高指数晶面催化剂的制备及其电催化性能

姚仪帅¹^,²^,³(), 郭瑞华¹^,²^,³(), 安胜利¹^,²^,³, 张捷宇⁴, 周国治⁴, 张国芳¹, 黄雅荣¹, 潘高飞¹

1.内蒙古科技大学材料与冶金学院, 包头 014010
2.内蒙古科技大学内蒙古自治区先进陶瓷材料与器件重点实验室, 包头 014010
3.内蒙古科技大学轻稀土资源绿色提取与高效利用教育部重点实验室, 包头 014010
4.上海大学材料科学与工程学院, 上海 200072

收稿日期:2022-05-27 修回日期:2022-08-01 出版日期:2022-08-24 网络出版日期:2022-08-26
通讯作者: 郭瑞华, 教授. E-mail: grh7810@163.com
作者简介:姚仪帅(1996-), 男, 硕士研究生. E-mail: 2563607693@qq.com
基金资助:
国家自然科学基金(51864040);国家自然科学基金(51962028);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项目(2022MS05018)

In-situ Loaded Pt-Co High Index Facets Catalysts: Preparation and Electrocatalytic Performance

YAO Yishuai¹^,²^,³(), GUO Ruihua¹^,²^,³(), AN Shengli¹^,²^,³, ZHANG Jieyu⁴, CHOU Kuochih⁴, ZHANG Guofang¹, HUANG Yarong¹, PAN Gaofei¹

1. School of Material and Metallurgy, 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
4. College of Materials Science and Engineering, Shanghai University, Shanghai 200072, China

Received:2022-05-27 Revised:2022-08-01 Published:2022-08-24 Online:2022-08-26
Contact: GUO Ruihua, professor. E-mail: grh7810@163.com
About author:YAO Yishuai(1996-), male, Master candidate. E-mail: 2563607693@qq.com
Supported by:
National Natural Science Foundation of China(51864040);National Natural Science Foundation of China(51962028);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)

摘要/Abstract

摘要：

直接乙醇燃料电池(DEFC)具有燃料易得、绿色高效的优点, 得到了广泛的研究, 但是DEFC催化剂存在催化效率低、稳定性差的问题, 制约了其快速发展。本研究采用液相水热合成法, 以聚乙烯吡咯烷酮(PVP k-25)为分散剂和还原剂、甘氨酸为表面控制剂和共还原剂, 通过调控Pt-Co金属前驱体的摩尔比, 一步制备了XC-72R炭黑负载的Pt₁Co_x/C高指数晶面纳米催化剂, 实现了催化剂晶粒在碳载体上的原位生长。Pt₁Co_1/3/C纳米催化剂暴露的高指数晶面主要包括(410)、(510)和(610)晶面。在晶体生长过程中, Pt₁Co_1/3/C纳米催化剂晶粒由“类球体”转变立方块, 最终得到具有高指数晶面取向的内凹形貌。Pt₁Co_1/3/C高指数晶面纳米催化剂的电催化活性最高, 其电化学活性表面积为18.46 m²/g, 对乙醇氧化峰电流密度为48.70 mA/cm², 稳态电流密度为8.29 mA/cm², CO氧化峰的电位为0.610 V。这说明具有高指数晶面的催化剂表面存在的台阶、扭结等缺陷原子, 可增加活性位点, 进而显示出优异的电催化性能。本研究可为高指数晶面催化剂材料的开发及工业化应用提供理论依据。

关键词: 水热法, Pt-Co催化剂, 高指数晶面, 原位生长, 直接乙醇燃料电池

Abstract:

Direct ethanol fuel cell (DEFC) has been widely studied because of its advantages of easy fuel availability, green and high effiency. However, DEFC catalysts are still frustrated with low catalytic efficiency and poor catalyst stability, which restrict its rapid development. In this work, XC-72R carbon black-loaded Pt₁Co_x/C high-index crystalline nanocatalysts were prepared in one step by liquid-phase hydrothermal synthesis, using polyvinylpyrrolidone (PVP k-25) as dispersant and reducing agent, glycine as surface control agent and co-reducing agent, and modulating the molar ratio of Pt-Co metal precursors to achieve the in-situ growth of catalyst particles on carbon carriers. The exposed high index crystalline facets of the Pt₁Co_1/3/C nanocatalyst mainly consisted of (410), (510) and (610) crystalline facets. The growth pattern of the Pt₁Co_1/3/C nanocatalyst grains varied from 'sphere-like' to cubic, and eventually to concave with high index grain orientation. The Pt₁Co_1/3/C nanocatalyst with high index crystalline surface has the highest electrocatalytic activity with an electrochemically active surface area of 18.46 m²/g, a current density of 48.70 mA/cm² for the ethanol oxidation peak, a steady state current density of 8.29 mA/cm² and a potential of 0.610 V for the CO oxidation peak. This indicates that the defect atoms such as steps and kinks on the surface of the catalyst with high index crystal plane can increase the active sites, thus showing excellent electrocatalytic performance. This study may provide a theoretical basis for the development and industrial application of high index crystalline catalyst materials.

Key words: hydrothermal method, Pt-Co catalyst, high index crystal plane, in-situ growth, direct ethanol fuel cell

中图分类号:

TM911

姚仪帅, 郭瑞华, 安胜利, 张捷宇, 周国治, 张国芳, 黄雅荣, 潘高飞. 原位负载Pt-Co高指数晶面催化剂的制备及其电催化性能[J]. 无机材料学报, 2023, 38(1): 71-78.

YAO Yishuai, GUO Ruihua, AN Shengli, ZHANG Jieyu, CHOU Kuochih, ZHANG Guofang, HUANG Yarong, PAN Gaofei. In-situ Loaded Pt-Co High Index Facets Catalysts: Preparation and Electrocatalytic Performance[J]. Journal of Inorganic Materials, 2023, 38(1): 71-78.

图/表 9

图1 催化剂的XRD图谱

Fig. 1 XRD patterns of catalysts

图2 Pt1Co1/3/C高指数晶面纳米催化剂的表面形貌

Fig. 2 Surface morphologies of Pt1Co1/3/C high-index crystalline nanocatalyst (a) TEM and (b) HRTEM images; (c) SAED image; (d-f) EDS surface sweep mapping images; (g-i) High-index crystalline atomic model for Pt1Co1/3/C high-index crystalline nanocatalysts; Colorful spheres in (g-i) represent different layers of atoms

图S1 Pt1Cox/C高指数晶面纳米催化剂TEM、HRTEM照片及粒径分布直方图

Fig. S1 TEM, HRTEM images and histograms of particle size distributions for Pt1Cox/C high index crystalline nanocatalysts (a1-a3) Pt/C; (b1-b3) Pt1Co1/4/C; (c1-c3) Pt1Co1/3/C; (d1-d3) Pt1Co1/2/C; (e1-e3) Pt1Co1/C

表S1 Pt1Cox/C高指数晶面催化剂的凹陷角度与暴露晶面

Table 1 Pt1Cox/C high index crystalline surface catalyst depression angle vs. exposed crystal surface

Catalyst	Angle of depression/(°)	Exposure of crystalline surfaces
Pt/C	8.1, 6.5, 5.9, 10.2, 9.3, 7.8, 7.1, 7.4	(610), (710), (810)
Pt₁Co_1/4/C	9.7, 9.6, 8.4, 10.7, 11.8, 11.7, 11.9, 13.3	(410), (510), (610), (710)
Pt₁Co_1/3/C	14.4, 11.3, 10.6, 12.7, 10.1, 14.6, 11.9, 11.2	(410), (510), (610)
Pt₁Co_1/2/C	10.0, 14.7, 10.5, 13.9, 13.4, 12.1, 14.1, 14.0	(410), (510), (610)
Pt₁Co₁/C	9.4, 10.1, 9.6, 10.3, 7.3, 14.1, 14.2, 9.7	(410), (610), (810)

图3 (a)Pt/C和(b)Pt1Co1/3/C催化剂的Pt4f XPS图谱

Fig. 3 Pt4f XPS spectra of (a) Pt/C and (b) Pt1Co1/3/C

表1 Pt/C与Pt1Co1/3/C催化剂的XPS拟合结果

Table 1 XPS fitting results for Pt/C and Pt1Co1/3/C catalysts

Catalyst	Pt(0)/eV	Relative ratio/%	Pt(II)/eV	Relative ratio/%
Pt/C	70.30,73.60	52.67	70.95,74.45	47.33
Pt₁Co_1/3/C	70.15,73.55	53.04	70.85,74.35	46.96

图S2 Pt1Co1/3/C高指数晶面催化剂在不同保温时间的TEM照片及粒径分布直方图

Fig. S2 TEM images and histograms of particle size distributions of Pt1Co1/3/C high index crystalline catalysts at different holding time (a1, a2) 1 h; (b1, b2) 3 h; (c1, c2) 5h; (d1, d2) 7 h; (e1, e2) 9 h; (f1, f2) 10 h

图4 催化剂的电催化性能

Fig. 4 Electrocatalytic performance of catalysts (a) H adsorption-desorption curves of the catalysts in 0.5 mol/L H2SO4 saturated with N2; (b) Cyclic voltammetric curves of the catalysts in 0.5 mol/L H2SO4+1 mol/L CH3CH2OH Colorful figures are available on website

图5 催化剂的稳定性和抗中毒性能

Fig. 5 Stability and anti-poisoning performance of catalysts (a) Timing current curves of the catalysts in 0.5 mol/L H2SO4+1 mol/L CH3CH2OH; (b) CO dissolution curves of catalysts in 0.5 mol/L H2SO4 Colorful figures are available on website

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原位负载Pt-Co高指数晶面催化剂的制备及其电催化性能

In-situ Loaded Pt-Co High Index Facets Catalysts: Preparation and Electrocatalytic Performance

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