石墨烯/二氧化钛/磷化铁复合低铂催化剂用于高效甲醇氧化

doi:10.6023/A24010013

摘要/Abstract

铁钛双金属由于其强烈的协同效应以及双功能机理, 在电化学领域中展现出了优秀的催化活性. 针对目前甲醇燃料电池铂基催化剂成本高、抗CO中毒能力低以及循环稳定性差等制约其商业化应用的关键瓶颈问题, 采用了一种简单的水热、低温磷化以及油浴方法, 成功合成了在石墨烯上负载的低铂/二氧化钛修饰磷化铁复合材料(Pt@rGO/TiO₂-FeP)用于甲醇电池阳极催化剂. 循环伏安法(CV)、计时电流法(CA)和多电位阶跃方法(STEP)等研究表明, 使用低温磷化法可以有效提升催化剂的甲醇氧化性能, 在Pt负载量仅为4.3% (w)时, 催化剂的峰电流密度达到2319.5 mA•mg⁻¹, 是商用Pt/C催化剂(390.5 mA•mg⁻¹)的5.9倍. 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能量色散X射线光谱(EDX)、X射线电子衍射(XRD)和X射线光电子能谱(XPS)等表征方法对催化剂进行一系列分析, 发现二氧化钛、磷化铁以及铂纳米颗粒在石墨烯上均匀分布, 因为过渡双金属的负载, 促进Pt的d带中心降低, 有效提升了催化剂的甲醇氧化性能. 本工作合成的Pt@rGO/TiO₂-FeP纳米复合材料, 具有优异的甲醇氧化性能和抗CO中毒能力, 为高性能甲醇燃料电池的研发提供了一个全新的思路和实践.

关键词: 过渡双金属, 石墨烯, 低温磷化, 甲醇氧化, 低铂负载

Due to the strong synergistic effect and bifunctional mechanism, Fe-Ti bimetallic catalysts have shown excellent catalytic activity in electro-chemistry. In order to solve the catalyst problems of high cost, low anti-toxicity, and poor cycling stability, a simple hydrothermal and low-temperature phosphating method was explored to prepare the graphene/titanium dioxide/iron phosphide composite with low platinum contents (Pt@rGO/TiO₂-FeP) for methanol battery anode. Through the cyclic voltammetry (CV), chronoamperometry (CA), and the multipotential step method (STEP), the methanol oxidation performance was effectively enhanced by the low-temperature phosphatization. When the Pt loading at 4.3% (w), the catalyst peak current density reached 2319.5 mA•mg⁻¹, which was 5.9 times higher than that of the commercial Pt/C catalyst (390.5 mA•mg⁻¹). With a series of characterization methods such as scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray electron diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), it was found that the titanium dioxide, iron phosphide and Pt nanoparticles were uniformly distributed on the surface of reduced graphene oxide (rGO). The methanol oxidation performance of this catalyst was improved because of the Fe-Ti bimetallic loading. The Pt@rGO/TiO₂-FeP nanocomposites have excellent methanol oxidation performance and CO poisoning resistance, which provide a new idea and practice for the research and development of high-performance methanol fuel cells.

Key words: transition bimetallic, graphene, low-temperature phosphating, methanol oxidation, low platinum loading

引用此文

汪子航, 钱静雯, 许佳慧, 邱浩渝, 晏梦珑, 刘芸, 罗杰, 盛毓泰, 陈易, 王贤保. 石墨烯/二氧化钛/磷化铁复合低铂催化剂用于高效甲醇氧化[J]. 化学学报, 2025, 83(3): 221-228.

Zihang Wang, Jingwen Qian, Jiahui Xu, Haoyu Qiu, Menglong Yan, Yun Liu, Jie Luo, Yutai Sheng, Yi Chen, Xianbao Wang. Graphene/Titanium dioxide/Iron Phosphide Composite with Low Platinum Catalysts for Efficient Methanol Oxidation[J]. Acta Chimica Sinica, 2025, 83(3): 221-228.

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图/表 8

图1. (a) TiO2和(b) Pt@rGO/TiO2-FeP的X射线衍射图

Figure 1. X-ray diffraction patterns of (a) TiO2 and (b) Pt@rGO/TiO2-FeP

图2. (a) TiO2, (b) FeP和(c) Pt@rGO/TiO2-FeP的不同分辨率SEM形貌图

Figure 2. SEM morphology images of (a) TiO2, (b) FeP and (c) Pt@rGO/TiO2-FeP with different resolutions

图3. (a), (b)为Pt@rGO/TiO2-FeP的不同分辨率TEM形貌图; (c) Pt@rGO/TiO2-FeP电子衍射光斑图; (d~f)分别为Pt@rGO/TiO2-FeP中, FeP, TiO2, Pt的高分辨TEM晶格图; (g~l)分别为Pt@rGO/TiO2-FeP的EDS元素分布图

Figure 3. (a), (b) TEM morphology images of Pt@rGO/TiO2-FeP with different resolutions; (c) Electron diffraction spot pattern of Pt@rGO/TiO2-FeP; (d~f) Electron diffraction spot pattern of FeP, TiO2 and Pt; (g~l) EDS element distribution map of Pt@rGO/TiO2-FeP

图4. (a) Pt@rGO/TiO2-FeP的X射线光电子能谱图; (b~f)分别为C 1s, P 2p, Fe 2p, Ti 2p, Pt 4f的高分辨光电子能谱

Figure 4. (a) X-ray photoelectron spectroscopy of Pt@rGO/TiO2-FeP; (b~f) X-ray photoelectron spectra of C 1s, P 2p, Fe 2p, Ti 2p and Pt 4f

图5. Pt@rGO/TiO2-FeP, Pt@rGO/TiO2, Pt@rGO/FeP和商业Pt/C催化剂在0.5 mol?L?1 KOH和1.0 mol?L?1 CH3OH混合溶液的电化学测试: (a)甲醇氧化单位质量电流密度的循环伏安曲线(CV); (b)分别在－0.008 V, －0.086 V, －0.124 V和－0.131 V时测试的计时电流曲线(CA); (c)不同的钛铁比在0.5 mol?L?1 KOH和1.0 mol?L?1 CH3OH混合溶液的甲醇氧化单位质量电流密度CV曲线; (d)分别在－0.008 V, －0.038 V, －0.056 V, －0.060 V和－0.104 V时测试的CA曲线

Figure 5. CVs of Pt@rGO/TiO2-FeP, Pt@rGO/TiO2, Pt@rGO/FeP and commercial Pt/C Catalysts in 0.5 mol?L?1 KOH＋1.0 mol?L?1 CH3OH: (a) CV curve of unit mass current density for methanol oxidation; (b) Chronoamperometry curves of －0.008 V, －0.086 V, －0.124 V and －0.131 V; (c) CV curves of methanol oxidation unit mass current density in a mixed solution of 0.5 mol?L?1 KOH and 1.0 mol?L?1 CH3OH with different titanium iron ratios; (d) Chronoamperometry curves of －0.008 V, －0.038 V, －0.056V, －0.060 V and －0.104 V

图6. Pt@rGO/TiO2-FeP, Pt@rGO/TiO2, Pt@rGO/FeP和商业Pt/C催化剂在0.5 mol?L?1 KOH和1.0 mol?L?1 CH3OH混合溶液中的峰值单位质量和单位面积电流密度

Figure 6. The Peak unit mass and unit area current density of Pt@rGO/TiO2-FeP, Pt@rGO/TiO2, Pt@rGO/FeP and commercial Pt/C Catalysts in 0.5 mol?L?1 KOH＋1.0 mol?L?1 CH3OH

图7. (a) Pt@rGO/TiO2-FeP和(b)商业Pt/C催化剂在0.5 mol?L?1 KOH溶液中的一氧化碳溶出伏安测试

Figure 7. Carbon monoxide stripping voltammetry test of (a) Pt@rGO/TiO2-FeP and (b) commercial Pt/C catalyst in 0.5 mol?L?1 KOH solution

图8. Pt@rGO/TiO2-FeP合成流程图

Figure 8. The synthesis flowchart of Pt@rGO/TiO2-FeP

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