分级结构AgAu纳米合金用于高效电催化乙醇氧化

doi:10.1016/S1872-2067(21)63895-0

催化学报 ›› 2022, Vol. 43 ›› Issue (3): 851-861.DOI: 10.1016/S1872-2067(21)63895-0

分级结构AgAu纳米合金用于高效电催化乙醇氧化

王彩琴^a^,^b, Danil Bukhvalov^a, M. Cynthia Goh^b^,^#(), 杜玉扣^c, 杨小飞^a^,^*()

^a南京林业大学理学院, 材料物理化学研究所, 江苏南京 210037, 中国
^b多伦多大学化学系, 多伦多, 加拿大
^c苏州大学材料与化学化工学部, 江苏苏州 215123, 中国

收稿日期:2021-06-02 修回日期:2021-06-02 出版日期:2022-03-18 发布日期:2022-02-18
通讯作者: M. Cynthia Goh,杨小飞
基金资助:
江苏省自然科学基金(BK20190762);南京林业大学杰出青年基金(JC2019002)

Hierarchical AgAu alloy nanostructures for highly efficient electrocatalytic ethanol oxidation

Caiqin Wang^a^,^b, Danil Bukhvalov^a, M. Cynthia Goh^b^,^#(), Yukou Du^c, Xiaofei Yang^a^,^*()

^aCollege of Science & Institute of Materials Physics and Chemistry, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
^bDepartment of Chemistry, University of Toronto, Toronto, Canada
^cCollege of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, China

Received:2021-06-02 Revised:2021-06-02 Online:2022-03-18 Published:2022-02-18
Contact: M. Cynthia Goh, Xiaofei Yang
Supported by:
Natural Science Foundation of Jiangsu Province(BK20190762);Science Fund for Distinguished Young Scholars, Nanjing Forestry University(JC2019002)

摘要/Abstract

摘要：

乙醇由于具有无毒、理论能量密度高、易存储等优点, 被广泛用于直接醇类燃料电池研究. 乙醇电氧化是直接醇类燃料电池中重要的阳极反应, 通常涉及C1和C2反应路径. C1路径中乙醇分子主要转化成二氧化碳, 但该过程涉及C‒C键断裂, 会有CO_ad和CH(x)_ad等中间体产生; C2路径中乙醇分子转化成乙醛, 最终转化成乙酸或乙酸根. 为提升醇类氧化反应效率, 通常在电池阳极上负载Pt, 使乙醇发生C1路径电氧化. 然而, C1反应路径产生的中间产物CO_ad容易使Pt发生毒化而失活, 进而导致乙醇电氧化反应动力学不足. 因此, 开发高效的阳极催化剂是推动直接醇类燃料电池发展的关键因素之一. 研究表明, 具有纳米尺寸的Au粒子能催化乙醇氧化反应, 尤其在碱性条件下, Au纳米材料的催化活性甚至能超过Pt(表现为峰电流); 而且乙醇在Au上的电氧化反应遵循C2路径, 避免了催化剂因中间体中毒而失活.
本文采用部分置换法合成具有分级结构的AgAu合金纳米结构催化剂, 扫描电子显微镜结果表明, 通过调控置换反应时间可以获得不同精细结构的AgAu合金纳米催化剂. 电化学性能测试结果表明, 不同置换时间制备出的AgAu合金纳米材料对乙醇电氧化反应的催化性能差异较大, 置换时间为40 min时得到的AgAu-40纳米粒子表现出最佳的电催化乙醇氧化活性, 其峰电流密度高达1834 mA mg^‒1, 超过了传统的JM-Pt/C (1574 mA mg^‒1). 高分辨透射电镜以及电子能谱分析结果表明, AgAu-40纳米粒子边缘具有互相交错的纳米齿状结构, 且大部分Au原子均匀分布在纳米分级结构AgAu合金表面, 从而暴露出更多的Au催化活性位点.
为进一步阐明纳米材料表面构型对其催化性能的影响, 本文通过密度泛函理论计算研究了不同表面态的催化反应动力学. 根据原子吸收光谱检测得到的AgAu-40合金中Ag和Au的载量比, 建立了两种AgAu晶胞模型: 一种为表面无缺陷的晶胞, 另一种为表面含齿状缺陷(台阶)的晶胞. 基于Au纳米材料在碱性条件下乙醇电催化氧化反应机理, 计算出乙醇分子在Au(111)活性晶面上产生不同活性物种的反应自由能. 结果表明, 相比于无表面缺陷的构型, 乙醇在有缺陷的AgAu晶胞表面的反应自由能降低, AgAu合金的形成能也相对较低, 其中在AgAu-40上的反应自由能和形成能最低.

关键词: AgAu纳米杂合材料, 多级纳米结构, 表面缺陷, 密度泛函理论, 乙醇电氧化

Abstract:

The ethanol oxidation reaction is a significant anodic reaction for direct alcohol fuel cells. The most commonly used catalysts for this reaction are Pt-based materials; however, Pt-based electrocatalysts cause carbon monoxide poisoning with intermediates before the complete transformation of alcohol to CO₂. Herein, we present hierarchical AgAu bimetallic nanoarchitectures for ethanol electrooxidation, which were fabricated via a partial galvanic reduction reaction between Ag and HAuCl₄. The ethanol electrooxidation performance of the optimal AgAu nanohybrid was increased to 1834 mA mg^‒1, which is almost 10 times higher than that of the pristine Au catalyst (190 mA mg^‒1) in alkaline solutions. This was achieved by introducing Ag into the Au catalyst and controlling the time of the replacement reaction. The heterostructure also presents a higher current density than that of commercial Pt/C (1574 mA mg^‒1). Density functional theory calculations revealed that the enhanced activity and stability may stem from unavoidable defects on the surface of the integrated AgAu nanoarchitectures. Ethanol oxidation reactions over these defects are more energetically favorable, which facilitates the oxidative removal of carbonaceous poison and boosts the combination with radicals on adjacent Au active sites.

Key words: AgAu nanohybrids, Hierarchical nanostructures, Defected surface, DFT calculation, Ethanol electrooxidation

王彩琴, Danil Bukhvalov, M. Cynthia Goh, 杜玉扣, 杨小飞. 分级结构AgAu纳米合金用于高效电催化乙醇氧化[J]. 催化学报, 2022, 43(3): 851-861.

Caiqin Wang, Danil Bukhvalov, M. Cynthia Goh, Yukou Du, Xiaofei Yang. Hierarchical AgAu alloy nanostructures for highly efficient electrocatalytic ethanol oxidation[J]. Chinese Journal of Catalysis, 2022, 43(3): 851-861.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63895-0

https://www.cjcatal.com/CN/Y2022/V43/I3/851

图/表 9

Fig. 1. (a) SEM image of bare CF and a magnified SEM image of CF (inset); (b) SEM image of Ag/CF; (c,d) Representative TEM image of Ag nanoparticles; (e) HRTEM image of Ag nanoparticles; (f) EDX results of Ag nanoparticles.

Fig. 2. (a) Schematic representation of the preparation process of AgAu catalysts; SEM images of AgAu-10/CF (b), AgAu-20/CF (c), AgAu-40/CF (d), and AgAu-60/CF (e) at high magnification.

Fig. 3. (a) Cyclic voltammograms of AgAu-40/CF, Au/CF, and Ag/CF in a 1.0 mol/L KOH solution at a scan rate of 50 mV s-1; (b) Cyclic voltammograms of AgAu-10/CF, AgAu-20/CF, AgAu-40/CF, AgAu-60/CF, and Au/CF in a 1.0 mol/L C2H5OH/1.0 mol/L KOH solution at a scan rate of 50 mV s-1; (c) Chronoamperograms (CAs) of AgAu-10/CF, AgAu-20/CF, AgAu-40/CF, AgAu-60/CF, and Au/CF at 0.05 V in a 1.0 mol/L C2H5OH/1.0 mol/L KOH solution; (d) Nyquist plots of ethanol electrooxidation using AgAu-10/CF, AgAu-20/CF, AgAu-40/CF, AgAu-60/CF, and Au/CF electrodes in a 1.0 mol/L C2H5OH/1.0 mol/L KOH solution at an electrode potential of 0.1 V.

Table 1 Summary of the electrochemical properties of electrodes.

Electrode	CVs			CAs
Electrode	E_Onset/V (vs. SCE)	j_f/(mA mg^-1)	j_f/j_b	j_i/(mA mg^-1)
AgAu-10/CF	-0.21	938	2.4	364
AgAu-20/CF	-0.26	1240	2.3	597
AgAu-40/CF	-0.40	1834	3.7	935
AgAu-60/CF	-0.29	512	2.4	214
Au/CF	-0.11	190	6.3	67

Scheme 1. Proposed mechanism of ethanol oxidation using Au-based catalysts.

Fig. 4. Cyclic voltammograms of AgAu-40/CF and JM-Pt/C electrodes in a 1.0 mol/L C2H5OH/1.0 mol/L KOH solution. Scan rate: 50 mV s-1.

Fig. 5. (a) Representative TEM image of AgAu-40 nanoparticles; (b) the magnified TEM image of AgAu-40 nanoparticles; EDX line scan (c) and HRTEM image (d) of an AgAu-40 nanoparticle in the red rectangle in Fig. 5(b); the inset is the diffraction pattern calculated using an FFT of the HRTEM images; (e) EDX of the area inside the red rectangle in Fig. 5(b); (f-i) EDX element mapping of AgAu-40 nanoparticles: TEM image of AgAu-40 nanoparticles (f) and its corresponding STEM image (g); the element distribution of Ag (h) and Au (i).

Fig. 6. (a) XRD patterns of a bare CF substrate, Ag/CF, Au/CF, and AgAu-40 electrodes; XPS spectra of the Au 4f region (b) and Ag 3d region (c) in AgAu-40. The spectra were obtained via calibration based on the C 1s peak at 284.5 eV.

Fig. 7. Optimized atomic structure of perfect (a) and defected (b) AuxAgy slab with a gold cover and a quasi-random distribution of gold and silver atoms for AuxAgy with a molar ratio of 1:1 at first (CH3CH2OH + OH- → CH3CH2O-* + H2O, * representing substrate), followed by (CH3CH2O-* + OH- → CH3CHO-* + H2O) the most energetically favorable steps of the EOR. The free energies of those two EOR steps for various AuxAgy ratios in a perfect substrate (c) and a surface with defects (d).

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分级结构AgAu纳米合金用于高效电催化乙醇氧化

Hierarchical AgAu alloy nanostructures for highly efficient electrocatalytic ethanol oxidation

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