通过金属间化合物PdBi纳米片调控Pd基催化剂电催化CO2还原为甲酸盐

doi:10.1016/S1872-2067(21)63999-2

催化学报 ›› 2022, Vol. 43 ›› Issue (7): 1680-1686.DOI: 10.1016/S1872-2067(21)63999-2

• 二氧化碳催化转化专栏 • 上一篇下一篇

通过金属间化合物PdBi纳米片调控Pd基催化剂电催化CO₂还原为甲酸盐

谢林峰^a^,^†, 刘轩^a^,^†, 黄凡洋^b, 梁嘉顺^a, 刘健云^a, 王谭源^a, 杨利明^c, 曹瑞国^b, 李箐^a^,^*()

^a华中科技大学材料科学与工程学院, 材料加工与模具技术国家重点实验室, 湖北武汉430074
^b中国科学技术大学材料科学与工程系, 中国科学院能量转化材料重点实验室, 安徽合肥230026
^c华中科技大学化学与化工学院, 湖北武汉430074

收稿日期:2021-09-28 接受日期:2021-12-07 出版日期:2022-07-18 发布日期:2022-05-20
通讯作者: 李箐
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家自然科学基金(22122202);国家自然科学基金(21972051);中央高校基本科研业务费专项资金资助(20121yjscxcy021);中央高校基本科研业务费专项资金资助(20121yjscxcy030)

Regulating Pd-catalysis for electrocatalytic CO₂ reduction to formate via intermetallic PdBi nanosheets

Linfeng Xie^a^,^†, Xuan Liu^a^,^†, Fanyang Huang^b, Jiashun Liang^a, Jianyun Liu^a, Tanyuan Wang^a, Liming Yang^c, Ruiguo Cao^b, Qing Li^a^,^*()

^aState Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^bKey Laboratory of Materials for Energy Conversion Chinese Academy of Science (CAS), Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China
^cSchool of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2021-09-28 Accepted:2021-12-07 Online:2022-07-18 Published:2022-05-20
Contact: Qing Li
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Nature Science Foundation of China(22122202);National Nature Science Foundation of China(21972051);Fundamental Research Funds for the Central Universities(20121yjscxcy021);Fundamental Research Funds for the Central Universities(20121yjscxcy030)

摘要/Abstract

摘要：

电催化CO₂还原(CO₂RR)对于降低大气中CO₂浓度、减缓温室效应具有重要意义. 在众多CO₂还原产物中, 甲酸盐是有机化工生产的重要原料. CO₂是一个线性分子, 有两个等量的C=O键, 打破它们需要较大的能量势垒和过电位. 此外, CO₂还原涉及复杂的质子耦合, 电子转移步骤和催化剂上多个结合能相近的反应中间体, 导致产物分布广泛、选择性低. Pd催化剂能在较低的负电位下有效催化CO₂还原生成甲酸盐, 然而, 在高负电位下的CO毒化和CO₂还原的竞争反应(析氢反应, HER)阻碍了甲酸盐的生成. 考虑到大多数单金属催化剂对CO₂RR的效率和选择性都不理想, 双金属合金催化剂被广泛研究. *OCHO是甲酸盐生产的关键中间体, 它能较好地生成并吸附在以p电子为主的主族金属(如Bi, In, Sn及其氧化物)上, 可高选择性获得甲酸盐. 因此, 通过引入主族金属, 可在较宽的电位范围内提高Pd基催化剂的甲酸盐选择性.

本文采用模板法、有机相合成策略制备了具有六方相结构的有序PdBi双金属纳米片催化剂. 通过调节合成温度, 可以很容易地控制制备不同有序度的PdBi纳米片, 并系统地研究了它们的结构与CO₂RR性能之间的关系. 有序PdBi纳米片催化剂具有较大的二维尺寸和比表面积, 且丰富的缺陷结构可以提供更多的活性位点.

X射线衍射结果表明, 随着温度的升高, PdBi双金属纳米片的结构从面心立方转变为六方相. 透射电子显微镜和原子力显微镜结果表明有序PdBi纳米片的厚度较薄(约3.5 nm), 纳米片表面具有丰富的褶皱和晶界, 为反应中间体的吸附提供了更多的活性位点. X射线光电子能谱结果表明, 随着Bi元素的引入, PdBi中Pd的结合能向正偏移, 并且偏移程度与PdBi合金的有序度成正比. Pd的结合能的正偏移可以归因于电子从Pd转移到Bi. 在CO₂RR反应性能测试中, 有序PdBi纳米片的电催化活性明显高于有序PdBi纳米片以及商业化Pd/C催化剂. 在-1.0 V过电位下, 有序的PdBi纳米片的甲酸盐法拉第效率(FE)可达到91.9%, 优于无序PdBi和纯Pd催化剂. 在10 h稳定性测试中, 有序的PdBi纳米片的甲酸法拉第效率可高于80%, 催化剂的形貌在测试前后基本未发生改变, 表明其具有良好的稳定性. 密度泛函理论计算表明, 与无序的PdBi纳米片相比, 完全有序的PdBi纳米片可使*OCHO(生成甲酸盐的关键中间体)的自由能垒降低, 并抑制H₂产生, 从而提高催化甲酸盐产物的活性和选择性. Bi的引入在一定程度上降低了*CO在Pd表面的结合能, 减缓了Pd被毒化的趋势.

关键词: CO₂还原, 电催化, 甲酸, 钯, 金属间化合物, 纳米片

Abstract:

Electrocatalytic CO₂ reduction plays an important role in the reduction of the CO₂ concentration in atmosphere and consequently the mitigation of greenhouse effects. Pd has been extensively investigated as an electrocatalyst for the CO₂ reduction to formate, which is an important raw material in the production of organic chemicals. However, the low selectivity and competitive reaction (hydrogen evolution reaction (HER)) have hindered the performance of monometallic Pd catalysts. In this paper, intermetallic PdBi nanosheets (NSs) are prepared for efficient CO₂ reduction to formate. The highest Faradaic efficiency (FE) of formate on fully ordered PdBi NSs reaches 91.9% at -1.0 V vs. RHE, which outperforms that of the disordered PdBi and pure Pd catalysts. Density functional theory calculations suggest that compared to disordered PdBi NSs, the ordered structure can decrease the free energy barrier of *OCHO (a key intermediate of formate formation) and inhibit H₂ evolution as well, thereby enhancing the activity and selectivity for formate production.

Key words: CO₂ reduction, Electrocatalysis, Formate, Palladium, Intermetallic compound, Nanosheet

谢林峰, 刘轩, 黄凡洋, 梁嘉顺, 刘健云, 王谭源, 杨利明, 曹瑞国, 李箐. 通过金属间化合物PdBi纳米片调控Pd基催化剂电催化CO₂还原为甲酸盐[J]. 催化学报, 2022, 43(7): 1680-1686.

Linfeng Xie, Xuan Liu, Fanyang Huang, Jiashun Liang, Jianyun Liu, Tanyuan Wang, Liming Yang, Ruiguo Cao, Qing Li. Regulating Pd-catalysis for electrocatalytic CO₂ reduction to formate via intermetallic PdBi nanosheets[J]. Chinese Journal of Catalysis, 2022, 43(7): 1680-1686.

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图/表 5

Scheme 1. Schematic of the synthesis of fully ordered (o-), partially ordered (p-), and disordered (d-) PdBi NSs.

Fig. 1. TEM images of Pd (a) and o-PdBi NSs (b). (c) Height profile of o-PdBi NSs and the corresponding measuring AFM image. (d) HRTEM image of o-PdBi NSs. The inset illustrates the FFT patterns of the corresponding area, where (1) and (2) are the enlarged views of the corresponding regions in Fig. (d). (e) HAADF-STEM image of o-PdBi NSs.

Fig. 2. (a) XRD patterns of Pd, d-PdBi/C, p-PdBi/C, and o-PdBi/C NSs. (b) XPS spectra of the Pd 3d electrons of Pd/C and o-PdBi/C NSs.

Fig. 3. (a) LSV curves of Pd/C, d-PdBi/C, p-PdBi/C, and o-PdBi/C NSs and commercial Pd/C. (b) FE of formate on d-PdBi/C, p-PdBi/C, and o-PdBi/C NSs and (c) corresponding partial current density of formate at -0.8 V, -0.9 V, -1.0 V, -1.1 V vs. RHE. (d) FEs of formate, CO, and H2 on o-PdBi/C NSs in the potential range of -0.4 to -1.1 V. (e) Durability test of o-PdBi/C NSs at -0.9 V for 10 h. The inset diagram is corresponding formate FEs at -0.9 V for 10 h. All CO2RR tests were conducted in a CO2-saturated 0.5 mol/L KHCO3 solution.

Fig. 4. Free energy diagrams for the CO2 reduction to HCOOH on d-PdBi and o-PdBi with Pd (a) and Bi (b) surface exposed (the schematic corresponding to each step is shown below, where the blue, yellow, black, red, and green atoms are Pd, Bi, C, O, and H, respectively). The free energy diagrams for the CO2 reduction to HCOOH on the o-PdBi (0001) facets with Pd and Bi exposed at 0 V (c) and -0.9 V (d) vs. RHE.

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通过金属间化合物PdBi纳米片调控Pd基催化剂电催化CO₂还原为甲酸盐

Regulating Pd-catalysis for electrocatalytic CO₂ reduction to formate via intermetallic PdBi nanosheets

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