配位环境可调的Cu单原子的合成及催化加氢性能研究※

doi:10.6023/A21100467

化学学报 ›› 2022, Vol. 80 ›› Issue (1): 16-21.DOI: 10.6023/A21100467 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究论文

配位环境可调的Cu单原子的合成及催化加氢性能研究^※

李玲玲^a^,^b, 刘宇^a^,^b, 宋术岩^a^,^b^,^*(), 张洪杰^a^,^b^,^c^,^*()

^a中国科学院长春应用化学研究所稀土资源利用国家重点实验室长春130022
^b中国科学技术大学应用化学与工程学院合肥 230026
^c清华大学化学系北京 100084

投稿日期:2021-10-20 发布日期:2021-12-06
通讯作者: 宋术岩, 张洪杰
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
项目受科技部重点研发计划(2020YFE0204500); 国家自然科学基金(21771173); 国家自然科学基金(22020102003); 国家自然科学基金(22025506)

Synthesis of Cu Single Atom with Adjustable Coordination Environment and Its Catalytic Hydrogenation Performance^※

Lingling Li^a^,^b, Yu Liu^a^,^b, Shuyan Song^a^,^b(), Hongjie Zhang^a^,^b^,^c()

^aState Key Laboratory of Rare Earth Resources Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
^bSchool of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
^cDepartment of Chemistry, Tsinghua University, Beijing 100084, China

Received:2021-10-20 Published:2021-12-06
Contact: Shuyan Song, Hongjie Zhang
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Science and Technology Major Project(2020YFE0204500); National Natural Science Foundation of China(21771173); National Natural Science Foundation of China(22020102003); National Natural Science Foundation of China(22025506)

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摘要/Abstract

具有可控配位环境的高催化活性和选择性的稳定单金属位点催化剂的合成仍然具有挑战性. 本工作采用阳离子交换策略合成了两种具有不同配位结构的Cu单原子催化材料. 该策略主要依赖于硫化物的阴离子骨架和富含 N 的聚合物壳在高温退火过程中产生大量的S和N缺陷, 精确合成了富边缘S和N双修饰的单金属Cu位点催化材料. 在这两种材料, 一种Cu单原子具有硫(S)、氮(N)双配位, 一种Cu单原子只有单一的S配位. Cu中心原子的第一壳层配位数为4, Cu-S/N-C的结构为Cu-S₁N₃, Cu-S-C的结构为Cu-S₄. 实验表明, S、N双修饰的Cu单原子材料在室温下催化硝基苯加氢过程中表现出较高活性. 反应20 min后, 在Cu-S/N-C催化下, 硝基苯加氢转化率达到100%, 循环使用5次后活性未见显著下降. 该发现为调节中心金属配位环境以提高单原子催化材料的性能提供了一种可行的方法.

关键词: 单原子催化材料, 铜掺杂碳材料, 催化加氢, 非均相催化

The synthesis of stable single-metal site catalysts with high catalytic activity and selectivity with a controllable coordination environment is still challenging. Due to the different electronegativity of different coordination atoms (N, P, S, etc.), adjusting the coordination atom type of the active metal center is an effective and wise strategy to break the symmetry of the electron density. We adopted a cation exchange strategy to synthesize two Cu single-atom catalytic materials with different coordination structures. This strategy can change the coordination environment of Cu single atom by changing the different organics wrapped around Cu-CdS. This strategy mainly relies on the anion skeleton of sulfide and the N-rich polymer shell to produce a large number of S and N defects during the high-temperature annealing process, and the precise synthesis of a single-metal Cu site catalyst material with rich edge S and N double modification. In these two materials, one single Cu atom has double coordination of sulfur (S) and nitrogen (N), and the other single Cu atom has only a single S coordination. The first shell coordination number of Cu central atom is 4, the structure of Cu-S/N-C is Cu-S₁N₃, and the structure of Cu-S-C is Cu-S₄. The results show that the catalytic performance of Cu-S/N-C in the hydrogenation of nitrobenzene compounds is much better than that of Cu-S-C, that is, the Cu monoatomic materials with S and N double-modified metal sites has better hydrogenation activity than single S-modified metal sites. After 20 min of reaction, under the catalysis of Cu-S/N-C, the conversion rate of nitrobenzene reached 100%, and the activity did not decrease significantly after being recycled for 5 times. It shows that the Cu-S/N-C catalytic material with a single-atom structure we synthesized has good stability. This discovery not only provides a feasible method for adjusting the coordination environment of the central metal to improve the performance of single-atom catalytic materials, but also provides an understanding of the catalytic performance of heteroatom modification.

Key words: single-atom catalytic material, copper-doped carbon material, catalytic hydrogenation, heterogeneous catalysis

引用此文

李玲玲, 刘宇, 宋术岩, 张洪杰. 配位环境可调的Cu单原子的合成及催化加氢性能研究^※[J]. 化学学报, 2022, 80(1): 16-21.

Lingling Li, Yu Liu, Shuyan Song, Hongjie Zhang. Synthesis of Cu Single Atom with Adjustable Coordination Environment and Its Catalytic Hydrogenation Performance^※[J]. Acta Chimica Sinica, 2022, 80(1): 16-21.

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图/表 6

图式1. Cu-S/N-C (a)和Cu-S-C (b)的合成示意图

Scheme 1. Schematic illustration of the syntheses of Cu-S/N-C (a) and Cu-S-C (b)

图1. Cu-S/N-C单原子催化合成过程表征: (a, b)随Cu-CdS@PDA放大倍数增加的TEM图像; (c, d)随Cu-S/N-C放大倍数增加的TEM图像; (e) Cu-S/N-C的EDS元素映射图像; (f, g)催化反应后Cu-S/N-C放大倍数增加的TEM图像

Figure 1. Characterization of synthesis process of Cu-S/N-C single atom catalysis: (a, b) TEM images with increasing magnification of Cu-CdS@PDA; (c, d) TEM images with increasing magnification of Cu-S/N-C; (e) EDS elemental mapping images of Cu-S/N-C; (f, g) TEM images of Cu-S/N-C with increased magnification after catalytic reaction

图2. Cu-S/N-C单原子催化材料的详细表征: (a) Cu-S/N-C的TEM图; (b) Cu-S/N-C的HAADF-STEM图像; (c) Cu-S/N-C的XRD图

Figure 2. Detailed characterization of Cu-S/N-C single atom catalysis materials: (a) TEM image of Cu-S/N-C; (b) HAADF-STEM image of Cu-S/N-C; (c) XRD patterns of Cu-S/N-C

图3. (a) Cu-S/N-C的XPS图; (b) Cu-S/N-C中S的2p谱图; (c) Cu-S/N-C中Cu的2p谱图

Figure 3. (a) XPS spectra of Cu-S/N-C; (b) S 2p spectra of Cu-S/N-C; (c) Cu 2p spectra of Cu-S/N-C

图4. Cu-S/N-C和Cu-S-C的Cu K-edge XAFS表征: (a) EXAFS光谱的傅立叶变换(FT) k3加权χ(k)函数; (b) Cu K-edge XANES光谱

Figure 4. The Cu K-edge XAFS characterization of Cu-S/N-C and Cu-S-C: (a) Fourier transformed (FT) k3-weighted χ(k)-function of the EXAFS spectra; (b) Cu K-edge XANES spectra

图5. 单原子催化材料Cu-S/N-C和Cu-S-C的催化表征: (a) Cu-S/N-C和Cu-S-C的硝基苯加氢性能; (b) Cu-S/N-C和Cu-S-C的循环催化性能

Figure 5. The catalytic characterization of single atom catalyst Cu-S/N-C and Cu-S-C: (a) the performance of nitrobenzene hydrogenation of Cu-S/N-C and Cu-S-C; (b) cyclic catalytic performance of Cu-S/N-C and Cu-S-C

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配位环境可调的Cu单原子的合成及催化加氢性能研究^※

Synthesis of Cu Single Atom with Adjustable Coordination Environment and Its Catalytic Hydrogenation Performance^※

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配位环境可调的Cu单原子的合成及催化加氢性能研究※

Synthesis of Cu Single Atom with Adjustable Coordination Environment and Its Catalytic Hydrogenation Performance※

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参考文献 34

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配位环境可调的Cu单原子的合成及催化加氢性能研究^※

Synthesis of Cu Single Atom with Adjustable Coordination Environment and Its Catalytic Hydrogenation Performance^※