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    10 May 2022, Volume 43 Issue 5
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.43 No.5(2022)
    2022, 43(5):  1-4. 
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    Review
    Electrocatalytic CO2 Reduction over Single-atom Catalysts
    JIN Xiangyuan, ZHANG Libing, SUN Xiaofu, HAN Buxing
    2022, 43(5):  20220035.  doi:10.7503/cjcu20220035
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    Electrochemical CO2 reduction reaction(e-CO2RR) is a promising and facile method to achieve carbon-neutral economy and sustainable development due its simple device and capability to consume renewable energy to produce high value-added chemicals. However, e-CO2RR suffers from low selectivity and low current density because of its sluggish kinetics and the weak activity of the catalysts. Hence, single-atom catalysts are one of the most ideal materials for e-CO2RR by virtue of its maximum atom utilization and well-defined catalytic active sites. Single atoms derived from transition metal and main group metal are comprehensively reviewed. Heteroatom coordination, dual-atom site, metal-support interactions, spatial confinement and molecular bridging to tailor the microenvironment of single atom to realize a better catalytic performance are also included. Single-atom catalysts extremely accelerate electrocatalytic CO2 reduction kinetics, which is ascribed to its unique electronic structure and enormous intrinsic highly active sites, indicating its state-of-the-art merits and broad application prospects. Reductive products that involve multi-electrons are desired for single-atom catalysts. Finally, research trends and hotspots in this field are also discussed.

    Current Advances and Future Challenges of Single-atom Catalysis
    ZHUANG Jiahao, WANG Dingsheng
    2022, 43(5):  20220043.  doi:10.7503/cjcu20220043
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    Single-atom catalysts(SACs), which combines the advantages of homogeneous and heterogeneous catalysts, have attracted great research interest due to their maximum atomic utilization efficiency, superior catalytic performance and easy separation from reaction systems. However, due to the high surface energy and thus instability of single atoms, it remains a great challenge to rational design and fabricate stable SACs. In this review, we summarized and discussed the advances of stabilizing strategies, high-loading synthesis and batch preparation for SACs in recent years. We also envisioned the challenges on the future development of SACs. Finally, the research prospect of single-atom catalysis was forecasted.

    Atomically Dispersed Metal-Nitrogen-Carbon Catalysts for Oxygen Reduction Reaction
    XU Siran, YIN Hengbo, XUE Dongping, XIA Huicong, ZHAO Shuyan, YAN Wenfu, MU Shichun, ZHANG Jianan
    2022, 43(5):  20220028.  doi:10.7503/cjcu20220028
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    To further accelerate the large-scale development and application of proton exchange membrane fuel cell(PEMFC) energy conversion technology, improving the cost-effectiveness of the catalyst is a prerequisite. Currently, atomically dispersed metal-nitrogen-carbon(M-N-C) catalysts also take tremendous potential in terms of increased active site density, atomic utilization and catalytic activity compared to noble metal-based catalysts such as platinum-based catalysts, and are the most promising candidate of platinum-based catalysts. During the preparation of atomically dispersed M-N-C catalysts, the contribution of the uniform dispersion and the optimal structural system of all active sites are the challenge issues. On this basis, we focused on the preparation of various M-N-C catalysts with favorable atomic dispersion and the effect of chemical environment modulation of atoms in different catalysts on the catalytic sites. Herein, we provide an in-depth discussion on the synthesis and characterization of M-N-C catalysts, reaction mechanism, and density functional theory calculations, focusing on the regulation of the chemical environment of catalytic sites by bimetallic sites, atomic cluster structure and heteroatoms. Finally, the problems of the large-scale application of atomically dispersed M-N-C catalysts and the development directions for further optimization are presented.

    Progress of the Structure-property Correlation of Heteroatomic Coordination Structured Carbon-based Single-atom Electrocatalysts
    XIA Tian, WAN Jiawei, YU Ranbo
    2022, 43(5):  20220162.  doi:10.7503/cjcu20220162
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    Single-atom catalysts are a class of supported catalysts with high atomic economy and high activity using mutually isolated single metal atoms as the catalytic active center, which have been widely used in energy electrocatalysis. In recent years, researchers have constructed single-atom electrocatalysts with heteroatomic coordination structures by using two or more heteroatoms coordinated to the active center metal atom. It was found that this asymmetric coordination structure effectively modulated the electronic structure of the central metal atom, optimizing the adsorption and desorption energies of the catalytic reaction, and improving the electrocatalytic performance. This paper presents a comprehensive review of the synthesis strategies and characterization techniques of carbon-based single-atom electrocatalysts with heteroatomic coordination structures, and their structure-property correlation for energy electrocatalysis. We give prospects of the future research for this field at the end of the review.

    Structure Regulation of Single-atom Catalysts in Oxygen Reduction Reactions
    GU Yu, XI Baojuan, LI Jiangxiao, XIONG Shenglin
    2022, 43(5):  20220036.  doi:10.7503/cjcu20220036
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    Oxygen reduction reaction(ORR) plays an important role in the clean synthesis of electrochemical energy storage and conversion systems. However, the kinetics of the ORR process is slow and requires platinum group noble metal catalysts to accelerate the reaction. The high cost of platinum-based catalysts has severely hindered their large-scale commercialization. Single atom catalysts(SACs) has the specific structure, high intrinsic activity and efficient atomic utilization. It is expected to replace platinum group noble metal catalysts. In order to improve the ORR activity of SACs, many strategies have been developed, including customizing the coordination structure of the metal center, enriching the concentration of the metal center, and designing the electronic structure and porosity of the substrate. In this review, we summarized recent advances of SACs in ORR performance and the application research progress of H2O2, metal-air batteries, fuel cells. Relevant progress on adjustment of the coordination structure of isolated metal centers by doping other metals or ligands, increasing the concentration of single-atom sites by increasing metal loading, and optimizing the porosity of the carrier to optimize mass and electron transport. Perspectives on future directions and challenges of SACs are presented.

    Synthesis and Applications of Graphdiyne Based Zerovalent Atomic Catalysts
    CHEN Zhaoyang, XUE Yurui, LI Yuliang
    2022, 43(5):  20220063.  doi:10.7503/cjcu20220063
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    Atomic catalysts(ACs) are new types of catalysts with the characteristics of zerovalent metal atoms anchored on the substrates, and have been the research frontier in the field of catalysis due to their unique and fascinating properties such as higher atomic utilization, higher selectivity, excellent catalytic activity and stability. Graphdiyne(GDY) based zerovalent ACs are stabilized by the unique incomplete charge transfer between metal atoms and GDY, which solves the problem of easy migration and aggregation of traditional singe-atom catalysts. In this review, the synthesis, structures and characterizations of GDY based zerovalent atomic catalysts were first introduced. Next, the latest research advances of GDY based zerovalent atomic catalysts in many fields(e. g., the ammonia production, hydrogen production, overall water splitting, CO2 fixation and conversion, etc.) were discussed. This review provides an important research idea for the design and synthesis of new concept high-performance catalytic materials.

    Research Progress of Zeolite-encaged Single-atom Metal Catalysts
    LI Jiafu, ZHANG Kai, WANG Ning, SUN Qiming
    2022, 43(5):  20220032.  doi:10.7503/cjcu20220032
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    Zeolites are considered as ideal supports for encapsulating ultrasmall metal species due to their uniform microporous channels, large specific surface areas, and excellent thermal stability. In recent years, thanks to the superhigh metal dispersion, nearly 100% metal utilization efficiency and unique electronic structure, zeolite-encaged single-atom metal catalysts have been widely used in many important catalytic reactions and gas adsorption/separation processes. In this review, we present a comprehensive summary of the state-of-the-art synthetic strategies of zeolite-encaged different kinds of single-atom metal catalysts and their applications in heterogeneous catalysis and gas separation. In the last part of this review, some future perspectives on the challenge and opportunity for this subject are pointed out. We hope that this review will provide reference for researchers to carry out more innovative research works in the future.

    Rational Design of Graphdiyne-based Atomic Electrocatalysts: DFT and Self-validated Machine Learning
    WONG Honho, LU Qiuyang, SUN Mingzi, HUANG Bolong
    2022, 43(5):  20220042.  doi:10.7503/cjcu20220042
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    Although atomic catalysts(ACs) have attracted intensive attention in recent years, the current progress of this area is limited by the use of noble metal as well as single atomic catalysts(SACs). Here, we summarize the recent works in screening highly-efficient graphdiyne-ACs(GDY-ACs) with the utilization of density functional theory(DFT) calculations and machine learning(ML). Our studies showed that the Pd, Co, Pt and Hg could form stable zero-valence transition metal-GDY(TM-GDY), whereas the lanthanide-TM DAC(Ln-TM DAC) systems were also demonstrated as the promising electrocatalyst candidates because of their long-range site-to-site f-d orbital interactions. The further analysis revealed that the combination of main group elements with TM and Ln metals can achieve high stable GDY-DAC and preserve the high electroactivity due to the long-range p-orbital coupling, while the role of the s- and p-orbitals was studied via ML algorithm. In addition, the DFT calculation and ML techniques also showed great potential in screening possible GDY-based ACs with excellent hydrogen evolution reaction(HER) performances, and the potential of rare-earth-based GDY-ACs for HER has been predicted for the first time. This review has supplied an advanced strategy for future exploration of atomic catalyst.

    Research Progress of Single-atom Catalysts in Photocatalytic Reduction of Carbon Dioxide
    TAO Yu, OU Honghui, LEI Yongpeng, XIONG Yu
    2022, 43(5):  20220143.  doi:10.7503/cjcu20220143
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    The conversion of carbon dioxide into value-added carbon-containing chemicals or fuels through photo-catalytic technology is one of the sustainable ways to solve the energy crisis and greenhouse effect. However, it is a great challenge to pursue catalysts with high efficiency, low price, and high stability for improving the efficiency of photocatalytic reduction reaction of CO2(CO2RR). Single atom catalysts(SACs) have been widely studied in the field of catalysis because of their high atomic utilization and adjustable electronic environment. In photocatalysis of CO2RR, the addition of single metal atoms can not only adjust the energy band structure and the light adsorption ability of catalysts, but also effectively improve the efficiency of photogenerated charge transfer, and provide an ideal platform for the study of photocatalytic reaction mechanism. In recent years, the research of SACs in CO2RR has developed rapidly. In this paper, the progress of SACs of photocatalytic CO2RR is summarized, and the typical research results of SACs with different supports are introduced, and the future research trend is prospected.

    Research Progress of Single Atom Catalysts in Electrochemical Hydrogen Cycling
    CHEN Changli, MI Wanliang, LI Yujing
    2022, 43(5):  20220065.  doi:10.7503/cjcu20220065
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    Single-atom-catalysts(SACs) represents a family of catalysts that contain single metal atom as the catalytic active site, which is widely used in the field of electrochemical catalysis and electric energy conversion equipment due to its advantages high atomic utilization efficiency. In this review, the design rationale and synthetic strategies of SAC catalysts are reviewed. Their implementations in the hydrogen circle, including the electrolysis of water and hydrogen fuel cells, are systematically analyzed, along with the prospected main challenges and the future research of SACs.

    Self-supported Film Electrodes Decorated with Single Atoms for Energy Electrocatalysis
    WU Jun, HE Guanchao, FEI Huilong
    2022, 43(5):  20220051.  doi:10.7503/cjcu20220051
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    Single-atom catalysts(SACs) have been widely studied in energy electrocatalysis due to their high catalytic activity, excellent selectivity and maximized atom utilization efficiency. However, the powdery SACs were mostly evaluated at small current densities(typically<100 mA/cm2) with low electrode loading(typically<1.0 mg/cm2) due to the complex preparation process of the working electrode, the addition of polymeric binder that would decrease the electrical conductivity and bury the active sites. In contrast, self-supported single-atom film electrodes not only possess the merits of SACs, but also have the advantages of monolithic structure, such as the omission of polymeric and conductive additives, improved electrical conductivity, enhanced exposure of single-atom sites and adjustable morphology and porosity, making them highly promising to be applied in high-current-density catalytic reactions and high-energy/power-density batteries. In this review, the recent advances of self-supported film-based SACs in energy electrocatalysis are presented. Firstly, the advantages of self-supported film-based SACs are discussed. Sub- sequently, their synthetic approaches are summarized, including in situ preparation on a self-supported substrate, electrostatic spinning, self-assembly, chemical vapor deposition and solid phase diffusion. Then, the applications of self-supported film-based SACs in various energy-related electrocatalytic processes are introduced, including hydrogen evolution reaction, oxygen evolution reaction, H2O2 electrosynthesis, zinc-air batteries, carbon dioxide reduction reaction and lithium sulfur batteries. Finally, the development direction of self-supported film-based SACs is prospected.

    Research Progress of Single Atomic Catalysts in Lithium-sulfur Batteries
    YIN Xiaoju, SUN Xun, ZHAO Chenghao, JIANG Bo, ZHAO Chenyang, ZHANG Naiqing
    2022, 43(5):  20220076.  doi:10.7503/cjcu20220076
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    Lithium-sulfur batteries have become one of the most promising development directions of prospective high-energy-density storage devices due to their outstanding features such as high energy density and low material cost. However, the crucial problems, such as low sulfur utilization rate, short cycle life, and poor rate performance, need to be solved in lithium-sulfur batteries. Single-atom catalysts exhibit high atom utilization and structural adjus-tability at atomic scale. This review summarizes the latest research progress of single-atom catalysts in lithium-sulfur batteries from three aspects: cathode, anode, and separator/interlayer. Finally, we prospect the future development direction and the scientific and technological issues of single-atom catalysts in lithium-sulfur batteries, in order to promote their further widespread applications.

    Recent Advances in Single-atom Materials for Enzyme-like Catalysis and Biomedical Applications
    SHA Meng, XU Weiqing, WU Zhichao, GU Wenling, ZHU Chengzhou
    2022, 43(5):  20220077.  doi:10.7503/cjcu20220077
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    Nanozymes featuring with economic cost, high stability, tunable properties, have captured broad interest to break through the limitations of enzymes in practice. The emergency of single-atom materials pushes forward the nanozymes research into the atomic level. Single-atom materials with high atomic utilization efficiency, unique coordination environments and strong metal-support interactions offer great opportunities to reveal their structure-activity relationship and regulate their enzyme-like activities. In this review, recent advances of single-atom materials for enzyme mimicking and biomedical applications were depicted. First, the regulation strategies and catalytic mechanisms of enzyme-like activities were discussed in detail. Then, the applications of single-atom nanomaterials for enzyme mimicking were elucidated in terms of cancer treatment, antioxidant therapy, antibacterial and biosensing. Finally, the limitations, challenges and development prospects of single-atom nanomaterials for enzyme-like catalysis were proposed.

    Research Progress of Single Atom Catalysts in Electrochemistry
    ZHANG Hongwei, CHEN Wen, ZHAO Meiqi, MA Chao, HAN Yunhu
    2022, 43(5):  20220129.  doi:10.7503/cjcu20220129
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    At present, the research on single-atom catalysts has shown an explosive growth and has become a star material and research hotspot in the field of materials science and catalysis. Previously reported studies on single- atom catalysts were mainly focused on a certain application direction, and the bifunctional or multifunctional applications of catalysts were seldom studied. In recent years, researchers have gradually devoted more interest to the design and development of bifunctional and multifunctional single-atom catalysts, so as to expand the application of single-atom catalysts in more fields and directions. In this paper, the research progress of bifunctional single-atom catalysts in recent years is comprehensively reviewed, with emphasis on the latest application research in the field of electrochemistry. Finally, the existing problems in the development of bifunctional single-atom catalysts are briefly analyzed, and the future development prospects are prospected.