Pt-Fe/GO纳米催化剂的制备及其电催化乙醇氧化性能研究

doi:10.15541/jim20240402

无机材料学报 ›› 2025, Vol. 40 ›› Issue (4): 379-387.DOI: 10.15541/jim20240402 CSTR: 32189.14.10.15541/jim20240402

Pt-Fe/GO纳米催化剂的制备及其电催化乙醇氧化性能研究

信震宇¹^,²^,³(), 郭瑞华¹^,²^,³(), 乌仁托亚¹^,²^,³, 王艳⁴, 安胜利¹^,²^,³, 张国芳¹, 关丽丽¹^,²

1.内蒙古科技大学材料科学与工程学院, 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.包头稀土研究院, 包头 014020

收稿日期:2024-09-09 修回日期:2024-11-29 出版日期:2025-04-20 网络出版日期:2024-12-12
通讯作者: 郭瑞华, 教授. E-mail: grh7810@163.com
作者简介:信震宇(1998-), 男, 硕士研究生. E-mail: 2670680269@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)

Pt-Fe/GO Nanocatalysts: Preparation and Electrocatalytic Performance on Ethanol Oxidation

XIN Zhenyu¹^,²^,³(), GUO Ruihua¹^,²^,³(), WUREN Tuoya¹^,²^,³, WANG Yan⁴, AN Shengli¹^,²^,³, ZHANG Guofang¹, GUAN Lili¹^,²

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. Baotou Research Institute of Rare Earths, Baotou 014020, China

Received:2024-09-09 Revised:2024-11-29 Published:2025-04-20 Online:2024-12-12
Contact: GUO Ruihua, professor. E-mail: grh7810@163.com
About author:XIN Zhenyu (1998-), male, Master candidate. E-mail: 2670680269@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：

直接乙醇燃料电池(DEFC)因其能量转换效率高、噪声低以及友好环境而受到广泛关注。然而, 这类电池仍面临催化剂成本高、稳定性差及催化活性低等问题。本研究选用氧化石墨烯(GO)作为载体, 以乙二醇为还原剂, 六水合氯铂酸为前驱体, 并引入非贵金属Fe, 通过调节Pt与Fe的摩尔比, 利用微波加热合成法制备出二元合金催化剂PtFe_x/GO(x=1/6、1/5、1/4、1/3、1/2、1), 在GO载体上原位负载纳米晶粒。原子半径小的Fe固溶到Pt晶格中, 导致Pt晶格的相邻原子间距缩小, 晶格收缩, 从而形成Pt-Fe合金。当x=1/3时, 催化剂表现出最优的催化活性, 其电催化活性面积为69.84 m²/g, 氧化峰值电流密度为858.42 A/g, 并且Tafel斜率较小。1100 s的计时电流测试下, PtFe_1/3/GO催化剂的稳态电流密度为194.80 A/g, CO的氧化峰电位为0.554 V, 活化能为18.37 kJ/mol, 800圈测试后电流密度保持率为80.48%, 优于商业Pt/C(JM)催化剂。研究表明, 引入非贵金属Fe能够显著提升Pt基催化剂的催化活性和稳定性, 为Pt基催化剂材料的设计与潜在应用提供了重要的理论依据。

关键词: 直接乙醇燃料电池(DEFC), 原位负载, 二元合金催化剂, 微波加热合成法

Abstract:

Direct ethanol fuel cells (DEFC) have garnered significant attention due to their high energy conversion efficiency, low noise levels, and environmental friendliness. However, these fuel cells still face challenges such as high catalyst costs, poor stability, and low catalytic activity. In this study, graphene oxide (GO) was utilized as support, glycol as reducing agent, and hexahydrate chloroplatinic acid as precursor to introduce non-noble metal iron (Fe). By adjusting the molar ratio of Pt to Fe, a series of PtFeₓ/GO (x=1/6, 1/5, 1/4, 1/3, 1/2, 1) binary alloy catalysts were synthesized using microwave-assisted heating, and nanocrystals were in situ loaded on GO support. Fe with small atomic radii was incorporated into the lattice of Pt, resulting in reduction in spacing between adjacent atoms and lattice contraction, forming Pt-Fe alloy. Electrochemical performance tests demonstrated that the catalyst specifically at x=1/3 exhibited optimal catalytic activity with an electrocatalytic active area of 69.84 m²/g, an oxidation peak current density of 858.42 A/g, and a smaller Tafel slope. Its 1100 s steady stable current was 194.80 A/g, with CO oxidation peak potential of 0.554 V, activation energy of 18.37 kJ/mol, and current density retention rate of 80.48% after 800 cycles, all surpassing the performance of commercial Pt/C(JM). This study shows that incorporating the less expensive Fe can significantly enhance the catalytic activity and stability of Pt-based catalysts, providing important theoretical foundations for the design and potential applications of Pt-based catalyst materials.

Key words: direct ethanol fuel cell (DEFC), in situ load, binary alloy catalyst, microwave heating synthesis

中图分类号:

TM911

信震宇, 郭瑞华, 乌仁托亚, 王艳, 安胜利, 张国芳, 关丽丽. Pt-Fe/GO纳米催化剂的制备及其电催化乙醇氧化性能研究[J]. 无机材料学报, 2025, 40(4): 379-387.

XIN Zhenyu, GUO Ruihua, WUREN Tuoya, WANG Yan, AN Shengli, ZHANG Guofang, GUAN Lili. Pt-Fe/GO Nanocatalysts: Preparation and Electrocatalytic Performance on Ethanol Oxidation[J]. Journal of Inorganic Materials, 2025, 40(4): 379-387.

图/表 14

图1 (a)催化剂的XRD图谱; (b) Pt/GO和PtFe1/3/GO催化剂的拉曼光谱图

Fig. 1 (a) XRD patterns of catalysts; (b) Raman spectra of Pt/GO and PtFe1/3/GO catalysts

图2 PtFe1/3/GO催化剂的(a)面扫TEM照片、(b~e) EDS元素图和(f) SAED图案

Fig. 2 (a) Surface scaning TEM image, (b-e) EDS elemental mappings and (f) SAED pattern of PtFe1/3/GO catalyst

图3 催化剂的XPS图谱

Fig. 3 XPS spectra of catalysts (a) Survey spectra of Pt/GO and PtFe1/3/GO; (b-d) Pt4f spectra of (b) Pt/C(JM), (c) Pt/GO, and (d) PtFe1/3/GO

表1 催化剂的Pt(0)和Pt(II)含量拟合结果

Table 1 Fitting results of Pt(0) and Pt(II) contents in catalysts

Catalyst	Pt(0)/eV	Relative ratio/%	Pt(II)/eV	Relative ratio/%
Pt/C(JM)	71.56, 74.94	61.22	72.39, 76.28	38.78
Pt/GO	71.30, 74.77	56.10	71.97, 76.50	43.89
PtFe_1/3/GO	71.25, 74.63	57.41	71.87, 75.17	42.59

图4 不同催化剂样品的(a)活性表面积曲线、(b)循环伏安曲线、(c) Tafel 斜率、(d) I-t曲线和(e) CO溶出曲线; (f)本研究与文献的峰值电流密度比较[6,33⇓⇓⇓ -37]

Fig. 4 (a) Active surface area curves, (b) cyclic voltammetry curves, (c) Tafel slopes, (d) I-t curves, and (e) CO dissolution curves for different catalyst samples; (f) Peak current density of this work compared with literature[6,33⇓⇓⇓ -37] Colorful figures are available on website

图5 不同催化剂的(a)变温循环伏安拟合曲线和(b)衰竭循环伏安拟合曲线

Fig. 5 (a) Variable temperature cyclic voltammetry fitting curves and (b) depletion cyclic voltammetry fitting curves for different catalysts Colorful figures are available on website

图S1 催化剂的拉曼光谱图

Fig. S1 Raman spectra of catalysts

图S2 PtFe1/3/GO催化剂的ICP-OES结果

Fig. S2 ICP-OES result of PtFe1/3/GO catalyst

图S3 Pt/GO和PtFex/GO催化剂的TEM、HRTEM照片及粒径分布直方图

Fig. S3 TEM, HRTEM images and particle size distribution histograms of Pt/GO and PtFex/GO catalysts (a1-a3) Pt/GO; (b1-b3) PtFe1/6/GO; (c1-c3) PtFe1/5/GO; (d1-d3) PtFe1/4/GO; (e1-e3) PtFe1/3/GO; (f1-f3) PtFe1/2/GO; (g1-g3) PtFe1/GO

图S4 催化剂的变温循环伏安曲线

Fig. S4 Variable temperature cyclic voltammetry curves of catalysts (a) Pt/C(JM); (b) Pt/GO; (c) PtFe1/6/GO; (d) PtFe1/5/GO; (e) PtFe1/4/GO; (f) PtFe1/3/GO; (g) PtFe1/2/GO; (h) PtFe1/GO

图S5 催化剂的衰竭循环伏安曲线

Fig. S5 Attenuated cyclic voltammetry curves of catalysts (a) Pt/C(JM); (b) Pt/GO; (c) PtFe1/6/GO; (d) PtFe1/5/GO; (e) PtFe1/4/GO; (f) PtFe1/3/GO; (g) PtFe1/2/GO; (h) PtFe1/GO

表S1 本研究与文献报道的Pt催化剂性能对比

Table S1 Comparison of performance of Pt-catalysts in this work and in literature

Sample	Active area/(m²·g^-1)	Peak current density/(A·g^-1)	Steady-state current density/(A·g^-1)	Ref.
PtFe_1/3/GO	69.84	858.42	194.80	This Work
PtNiCeO₂/C	90.41	837.67	178.33	[S1]
Pt/Fe₂P	80	721	-	[S2]
Pt-Sn/NC-E	121.5	81.25	-	[S3]
SnO₂@PtRhNi	18	90	-	[S4]
Pt-CeO₂/TiNNTs	-	670	-	[S5]
NP-Pt-Si	-	785.23	87.56	[S6]

图S6 循环测试后PtFe1/3/GO催化剂的TEM照片

Fig. S6 TEM images of PtFe1/3/GO after cyclic testing (a) Surface scanning TEM image; (b-e) Surface EDS elemental mappings; (f) SAED pattern

图S7 循环测试后PtFe1/3/GO催化剂的(a)TEM、(b)HRTEM照片及(c)粒径分布直方图

Fig. S7 (a) TEM, (b) HRTEM images and (c) particle size distribution histogram of PtFe1/3/GO catalyst after cyclic testing

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Pt-Fe/GO纳米催化剂的制备及其电催化乙醇氧化性能研究

Pt-Fe/GO Nanocatalysts: Preparation and Electrocatalytic Performance on Ethanol Oxidation

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