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

doi:10.6023/A21100467

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (1): 16-21.DOI: 10.6023/A21100467 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Article

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)

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

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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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Fig. & Tab. 6

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

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

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

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

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

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※

RichHTML

PDF

Knowledge

Abstract

Cite this article

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Fig. & Tab. 6

References 34

Related Articles 15

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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^※