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Catalysts
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Synthesis and Applications of Copper-Based Catalysts
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Synthesis and Applications of Copper-Based Catalysts

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 29287

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Prof. Dr. Yongjun Ji

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Guest Editor
School of Light Industry, Beijing Technology and Business University, Beijing 100048, China
Interests: copper; heterogeneous catalysis; catalyst synthesis; catalytic performance; nanocatalysis; electrocatalysis; single-atom catalysis
Special Issues, Collections and Topics in MDPI journals
Dr. Liwen Xing

E-Mail Website
Guest Editor
Department of Materials Science and Engineering, College of Chemistry and Materials Engineering, Beijing Technology and Business University, Beijing 100048, China
Interests: carbon-supported metal catalysts; catalyst synthesis; catalyst structure; catalytic application; nanocatalysis; electrocatalysis
Dr. Ke Wu

E-Mail Website
Guest Editor
Beijing National Laboratory for Molecule Sciences, State Key Lab of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Lab in Rare Earth Materials and Bioinorganic Chemistry, Peking University, Beijing 100871, China
Interests: nanoscale chemistry; inorganic synthesis; heterogeneous catalysis; biomass conversion; environmental engineering

Special Issue Information

Dear Colleagues,

Copper-based catalysts possess important applications in diverse reactions and have received considerable attention from material and catalysis researchers. A great challenge in this field is the facile synthesis of copper-based catalysts with enhanced catalytic activity, selectivity, and durability. This Special Issue of Catalysts, entitled “Synthesis and Applications of Copper-based Catalysts” aims to present state-of-the-art synthetic strategies for various copper-based catalysts, their structure and catalytic use in heterogeneous and homogeneous catalysis, which is helpful for developing novel high-efficiency Cu-based catalysts and synthetic methodology, and also for exploring their new catalytic applications.

Original research papers and topical reviews are welcome in this Special Issue of Catalysts. Submit your paper and select the journal “Catalysts” and the Special Issue “Synthesis and Applications of Copper-based Catalysts” via MDPI‘s submission system. Please contact the Guest Editor or the journal editor for any queries. Our papers will be published on a rolling basis and we will be pleased to receive your submission once you have finished it.

Prof. Dr. Yongjun Ji
Dr. Liwen Xing
Dr. Ke Wu
Guest Editors

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

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Keywords

  • copper
  • heterogeneous catalysis
  • homogenous catalysis
  • catalyst synthesis
  • catalytic performance
  • nanocatalysis
  • electrocatalysis
  • single-atom catalysis

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Published Papers (11 papers)

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Editorial

Jump to: Research, Review

4 pages, 186 KiB  
Editorial
Synthesis and Applications of Copper-Based Catalysts
by Ke Wu, Liwen Xing and Yongjun Ji
Catalysts 2023, 13(6), 973; https://doi.org/10.3390/catal13060973 - 5 Jun 2023
Cited by 1 | Viewed by 1911
Abstract
The increasing demand for fine and high-value-added chemicals has motivated the lasting exploration of high-performance catalysts with desirable activity, selectivity, and durability [...] Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)

Research

Jump to: Editorial, Review

13 pages, 2979 KiB  
Article
In-Situ Catalytic Preparation of Two-Dimensional BCN/Graphene Composite for Anti-Corrosion Application
by Chunyang Duan, Xiaojie Li, Yongjun Ji, Liuyang He, Jianhua Qian and Zenghua Zhao
Catalysts 2022, 12(12), 1618; https://doi.org/10.3390/catal12121618 - 9 Dec 2022
Cited by 6 | Viewed by 2461
Abstract
In-situ catalytic growth of two-dimensional materials shows great potential for metal surface protection because of the impermeability and strong interaction of the materials with metal surfaces. Two-dimensional hexagonal boron-carbon nitrogen (h-BCN) is composed of alternating boron, carbon, and nitrogen atoms in a two-dimensional [...] Read more.
In-situ catalytic growth of two-dimensional materials shows great potential for metal surface protection because of the impermeability and strong interaction of the materials with metal surfaces. Two-dimensional hexagonal boron-carbon nitrogen (h-BCN) is composed of alternating boron, carbon, and nitrogen atoms in a two-dimensional honeycomb lattice, which is similar to graphene. The corrosion caused by defects such as grain boundary of two-dimensional materials can be weakened by dislocation overlap via the transfer method. However, two-dimensional composite films prepared using the transfer method have problems, such as the introduction of impurities and poor adhesion, which limit their corrosion resistance. In this study, a layer of BCN/Gr two-dimensional composite was directly grown on the surface of copper foil using the CVD in-situ catalysis method, and its anti-corrosion performance was characterized by electrochemical and salt spray experiments. The results showed that the directly grown two-dimensional composite had better adhesion to the substrate and the advantage of grain boundary dislocation, thus showing a better anti-corrosion capability. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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19 pages, 3657 KiB  
Article
Copper–Cerium–Tin Oxide Catalysts for Preferential Oxidation of CO in Hydrogen: Effects of Synthesis Method and Copper Content
by Igor Yu. Kaplin, Ekaterina S. Lokteva, Artem V. Tikhonov, Konstantin I. Maslakov, Oksana Ya. Isaikina and Elena V. Golubina
Catalysts 2022, 12(12), 1575; https://doi.org/10.3390/catal12121575 - 3 Dec 2022
Cited by 6 | Viewed by 2023
Abstract
Copper was incorporated into the Ce-Sn and comparative Ce-Zr oxide supports by one-pot precipitation in the presence of CTAB template and by the impregnation of templated Ce-Sn and Ce-Zr oxides. The synthesized Cu-Ce-Sn and Cu-Ce-Zr catalysts were tested in the continuous-flow preferential oxidation [...] Read more.
Copper was incorporated into the Ce-Sn and comparative Ce-Zr oxide supports by one-pot precipitation in the presence of CTAB template and by the impregnation of templated Ce-Sn and Ce-Zr oxides. The synthesized Cu-Ce-Sn and Cu-Ce-Zr catalysts were tested in the continuous-flow preferential oxidation of CO in hydrogen excess. The one-pot synthesized tin- and zirconium-doped catalysts demonstrated better CO conversion and CO2 selectivity than their impregnated counterparts. For the tin-modified ternary system that showed the best catalytic performance, the copper content was further optimized. The structure, reducibility, surface chemical state and textural properties of the catalysts were analyzed by SEM-EDX, XRD, H2-TPR, Raman spectroscopy, XPS and TEM. The nonmonotonic changes in the specific surface area, Cu+/Cu2+ ratio and ratio of lattice and non-lattice oxygen with increasing the Cu content are discussed in terms of copper distribution in the catalysts. The influence of the interaction between copper oxide species and the cerium–tin/cerium–zirconium oxide support on the performance of the ternary catalysts was thoroughly analyzed and discussed. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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8 pages, 1613 KiB  
Article
Ab Initio Investigation of the Adsorption and Dissociation of O2 on Cu-Skin Cu3Au(111) Surface
by Yanlin Yu, Zhiming Liu, Wenxian Huang, Shan Zhou, Zuofu Hu and Ligen Wang
Catalysts 2022, 12(11), 1407; https://doi.org/10.3390/catal12111407 - 10 Nov 2022
Cited by 4 | Viewed by 1653
Abstract
Surface adsorption and dissociation processes can have a decisive impact on the catalytic properties of metal alloys. We have used density functional theory to investigate the adsorption and dissociation of O2 on Cu-skin Cu3Au(111) surface. The calculated results show that [...] Read more.
Surface adsorption and dissociation processes can have a decisive impact on the catalytic properties of metal alloys. We have used density functional theory to investigate the adsorption and dissociation of O2 on Cu-skin Cu3Au(111) surface. The calculated results show that the b-f(h)-b adsorption configuration is the most energetically favorable on the Cu-skin Cu3Au(111) surface. For O2 dissociation, there are two thermodynamically favorable dissociation paths. One path is from b-f-b to two O atoms in hcp sites, and the other path is from b-h-b to two O atoms in fcc sites. Moreover, the stability of O2 adsorption is higher and the dissociation energy barrier of the adsorbed O2 is lower as compared to those on the Cu(111) surface. This theoretical work provides valuable guidance for the practical application of Cu-Au alloys as highly efficient CO oxidation catalysts. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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12 pages, 3616 KiB  
Article
Hydride Generation on the Cu-Doped CeO2(111) Surface and Its Role in CO2 Hydrogenation Reactions
by Zhi-Qiang Wang, Hui-Hui Liu, Xin-Ping Wu, Peijun Hu and Xue-Qing Gong
Catalysts 2022, 12(9), 963; https://doi.org/10.3390/catal12090963 - 29 Aug 2022
Cited by 12 | Viewed by 2620
Abstract
Ceria-based catalysts exhibit great activity in catalyzing selective hydrogenation of CO2 to methanol. However, the underlying mechanism of this reaction, especially the generation of active H species, remains unclear. In this work, we performed extensive density functional theory calculations corrected by on-site [...] Read more.
Ceria-based catalysts exhibit great activity in catalyzing selective hydrogenation of CO2 to methanol. However, the underlying mechanism of this reaction, especially the generation of active H species, remains unclear. In this work, we performed extensive density functional theory calculations corrected by on-site Coulomb interaction (DFT + U) to investigate the H2 dissociation and the reaction between the active H species and CO2 on the pristine and Cu-doped CeO2(111) (denoted as Cu/CeO2(111)) surfaces. Our calculations evidenced that the heterolytic H2 dissociation for hydride generation can more readily occur on the Cu/CeO2(111) surface than on the pristine CeO2(111) surface. We also found that the Cu dopant can facilitate the formation of surface oxygen vacancies, further promoting the generation of hydride species. Moreover, the adsorption of CO2 and the hydrogenation of CO2 to HCOO* can be greatly promoted on the Cu/CeO2(111) surface with hydride species, which can lead to the high activity and selectivity toward CO2 hydrogenation to methanol. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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12 pages, 3639 KiB  
Article
Synthesis of Self-Supported Cu/Cu3P Nanoarrays as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction
by Rui Dang, Xiufeng Xu, Mengmeng Xie and Jian Liu
Catalysts 2022, 12(7), 762; https://doi.org/10.3390/catal12070762 - 9 Jul 2022
Cited by 4 | Viewed by 2180
Abstract
Owing to the energy crisis and environmental pollution, it is essential to develop cheap, environmentally friendly and sustainable energy to replace noble metal electrocatalysts for use in the hydrogen evolution reaction (HER). We report herein that a Cu/Cu3P nanoarray catalyst was [...] Read more.
Owing to the energy crisis and environmental pollution, it is essential to develop cheap, environmentally friendly and sustainable energy to replace noble metal electrocatalysts for use in the hydrogen evolution reaction (HER). We report herein that a Cu/Cu3P nanoarray catalyst was directly grown on the surfaces of Cu nanosheets from its Cu/CuO nanoarray precursor by a low-temperature phosphidation process. In particular, the effects of phosphating distance, mass ratio and temperature on the morphology of Cu/Cu3P nanoarrays were studied in detail. This nanoarray, as an electrocatalyst, displays excellent catalytic performance and long-term stability in an acid solution for electrochemical hydrogen generation. Specifically, the Cu/Cu3P nanoarray-270 exhibits a low onset overpotential (96 mV) and a small Tafel slope (131 mV dec−1). Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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12 pages, 3611 KiB  
Article
Low-Temperature Selective NO Reduction by CO over Copper-Manganese Oxide Spinels
by Fenglan Fan, Lingjuan Wang, Lei Wang, Jinyu Liu and Minghui Wang
Catalysts 2022, 12(6), 591; https://doi.org/10.3390/catal12060591 - 29 May 2022
Cited by 15 | Viewed by 2354
Abstract
Selective catalytic reduction of NO with CO (CO-SCR) has been suggested as an attractive and promising technology for removing NO and CO simultaneously from flue gas. Manganese-copper spinels are a promising CO−SCR material because of the high stability and redox properties of the [...] Read more.
Selective catalytic reduction of NO with CO (CO-SCR) has been suggested as an attractive and promising technology for removing NO and CO simultaneously from flue gas. Manganese-copper spinels are a promising CO−SCR material because of the high stability and redox properties of the spinel structure. Here, we synthesized CuxMn3−xO4 spinel by a citrate-based modified pechini method combining CuO and MnOx, controlling the molar Cu/Mn concentrations. All the samples were characterized by SEM, EDX, XRD, TEM, H2−TPR, XPS and nitrogen adsorption measurements. The Cu1.5Mn1.5O4 catalyst exhibits 100% NO conversion and 53.3% CO conversion at 200 °C. The CuxMn3−xO4 catalyst with Cu-O-Mn structure has a high content of high valence Mn, and the high mass transfer characteristics of the foam-like structure together promoted the reaction performance. The CO-SCR catalytic performance of Cu was related to the spinel structure with the high ratio of Mn4+/Mn, the synergistic effect between the two kinds of metal oxides and the multistage porous structure. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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14 pages, 3035 KiB  
Article
Metal-Organic Frameworks Decorated Cu2O Heterogeneous Catalysts for Selective Oxidation of Styrene
by Mengyi Han, Xue Tang, Peng Wang, Zhiyong Zhao, Xiaohua Ba, Yu Jiang and Xiaowei Zhang
Catalysts 2022, 12(5), 487; https://doi.org/10.3390/catal12050487 - 26 Apr 2022
Cited by 11 | Viewed by 3315
Abstract
The selective oxidation of styrene with highly efficient, environmentally benign, and cost-effective catalysts are of great importance for sustainable chemical processes. Here, we develop an in situ self-assembly strategy to decorate Cu-based metal-organic framework (MOF) Cu-BDC-NH2 nanocrystals on Cu2O octahedra [...] Read more.
The selective oxidation of styrene with highly efficient, environmentally benign, and cost-effective catalysts are of great importance for sustainable chemical processes. Here, we develop an in situ self-assembly strategy to decorate Cu-based metal-organic framework (MOF) Cu-BDC-NH2 nanocrystals on Cu2O octahedra to construct a series of Cu2O@Cu-BDC-NH2 catalysts for selective oxidation of styrene. Using H2O2 as green oxidants, the optimized sample of Cu2O@Cu-BDC-NH2-8h could achieve 85% styrene conversion with 76% selectivity of benzaldehyde under a mild condition of 40 °C. The high performance of the as-prepared heterogeneous catalysts was attributed to the well-designed Cu+/Cu2+ interface between Cu2O and Cu-BDC-NH2 as well as the porous MOF shells composed of the uniformly dispersed Cu-BDC-NH2 nanocrystals. The alkaline properties of Cu2O and the –NH2 modification of MOFs enable the reaction to be carried out in a base-free condition, which simplifies the separation process and makes the catalytic system more environmentally friendly. Besides the Cu2O octahedra (od-Cu2O), the Cu2O cuboctahedrons (cod-Cu2O) were synthesized by adjusting the added polyvinyl pyrrolidone, and the obtained cod-Cu2O@Cu-BDC-NH2 composite also showed good catalytic performance. This work provides a useful strategy for developing highly efficient and environmentally benign heterogeneous catalysts for the selective oxidation of styrene. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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Review

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24 pages, 12609 KiB  
Review
Recent Achievements in the Copper-Catalyzed Arylation of Adamantane-Containing Amines, Di- and Polyamines
by Alexei D. Averin, Svetlana P. Panchenko, Arina V. Murashkina, Varvara I. Fomenko, Daria S. Kuliukhina, Anna S. Malysheva, Alexei A. Yakushev, Anton S. Abel and Irina P. Beletskaya
Catalysts 2023, 13(5), 831; https://doi.org/10.3390/catal13050831 - 1 May 2023
Cited by 5 | Viewed by 2835
Abstract
Rapid development of the copper-catalyzed amination of aryl halides in the beginning of the 21st century, known as the Renaissance of the Ullmann chemistry, laid foundations for the use of this method as a powerful tool for the construction of the C(sp2 [...] Read more.
Rapid development of the copper-catalyzed amination of aryl halides in the beginning of the 21st century, known as the Renaissance of the Ullmann chemistry, laid foundations for the use of this method as a powerful tool for the construction of the C(sp2)-N bond and became a rival of the Buchwald–Hartwig amination reaction. Various applications of this approach are well-documented in a number of comprehensive and more specialized reviews, and this overview in the form of a personal account of the Cu-catalyzed arylation and heteroarylation of the adamantane-containing amines, and di- and polyamines, covers a more specific area, showing the possibilities of the method and outlining general regularities, considering reagents structure, copper source and ligands, scope, and limitations. The material of the last decade is mainly considered, and recent data on the application of the unsupported copper nanoparticles and possibilities of the Chan-Lam reaction as an alternative to the use of aryl halides are also discussed. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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16 pages, 5687 KiB  
Review
Progress on the Cu-Catalyzed 1,4-Conjugate Addition to Thiochromones
by Fenghai Guo, Jayla A. Young, Mina S. Perez, Holden A. Hankerson and Alex M. Chavez
Catalysts 2023, 13(4), 713; https://doi.org/10.3390/catal13040713 - 8 Apr 2023
Cited by 4 | Viewed by 4091
Abstract
Carbon–carbon bond formation is one of the most important tools in synthetic organic chemists’ toolbox. It is a fundamental transformation that allows synthetic chemists to synthesize the carbon framework of complex molecules from inexpensive simple starting materials. Among the many synthetic methodologies developed [...] Read more.
Carbon–carbon bond formation is one of the most important tools in synthetic organic chemists’ toolbox. It is a fundamental transformation that allows synthetic chemists to synthesize the carbon framework of complex molecules from inexpensive simple starting materials. Among the many synthetic methodologies developed for the construction of carbon–carbon bonds, organocopper reagents are one of the most reliable organometallic reagents for this purpose. The versatility of organocuprate reagents or the reactions catalyzed by organocopper reagents were demonstrated by their applications in a variety of synthetic transformations including the 1,4-conjugate addition reactions. Sulfur-containing heterocyclic compounds are a much less studied area compared to oxygen-containing heterocycles but have gained more and more attention in recent years due to their rich biological activities and widespread applications in pharmaceuticals, agrochemicals, and material science. This paper will provide a brief review on recent progress on the synthesis of an important class of sulfur-heterocycles-2-alkylthiochroman-4-ones and thioflavanones via the conjugate additions of Grignard reagents to thiochromones catalyzed by copper catalysts. Recent progress on the synthesis of 2-substituted thiochroman-4-ones via alkynylation and alkenylation of thiochromones will also be covered in this review. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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14 pages, 2395 KiB  
Review
Recent Advances of Cu-Based Catalysts for NO Reduction by CO under O2-Containing Conditions
by Xiaoli Chen, Yaqi Liu, Yan Liu, Dianxing Lian, Mohaoyang Chen, Yongjun Ji, Liwen Xing, Ke Wu and Shaomian Liu
Catalysts 2022, 12(11), 1402; https://doi.org/10.3390/catal12111402 - 9 Nov 2022
Cited by 13 | Viewed by 2473
Abstract
Selective catalytic reduction of NOx by CO (CO-SCR) to both N2 and CO2 is a promising way to simultaneously remove two harmful gases, CO and NOx, in automobile and factory exhaust gases. The development of efficient catalysts is [...] Read more.
Selective catalytic reduction of NOx by CO (CO-SCR) to both N2 and CO2 is a promising way to simultaneously remove two harmful gases, CO and NOx, in automobile and factory exhaust gases. The development of efficient catalysts is the key challenge for the technology to be commercialized. The low-cost Cu-based catalysts have shown promising performance in CO-SCR, but there are some technical problems that obstruct their practical implementation, such as high reduction temperature and low O2, H2O, and SO2 resistance. This paper provides a comprehensive overview and insights into CO-SCR under O2-containing conditions over the Cu-based catalysts, including catalytic performances of non-supported, supported mono-metallic, supported bimetallic, and supported multi-metallic Cu-based catalysts. In addition, the effects of O2 concentration, reaction temperature, H2O, and SO2 on the catalytic performance are discussed. Furthermore, the reaction mechanism of CO-SCR on Cu-based catalysts is briefly summarized. Lastly, challenges and perspectives with respect to this reaction are discussed. We hope this work can provide theoretical guidance for the rational design of efficient Cu-based catalysts in the CO-SCR reaction for commercial applications. Full article
(This article belongs to the Special Issue Synthesis and Applications of Copper-Based Catalysts)
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