不同尺寸钴基催化剂稳定策略研究进展

王倩; 王丽萍; 龚志远; 王一丹; 孟凡会; 李忠

doi:10.12434/j.issn.2097-2547.20240118

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不同尺寸钴基催化剂稳定策略研究进展

C1化学与催化转化

- 不同尺寸钴基催化剂稳定策略研究进展
- Research progress on stabilization strategies for cobalt-based catalysts with different sizes
- 低碳化学与化工 2025, 50(1): 1-12.
- 作者机构：
  
  太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
- 作者简介：
  
  王倩（1999—），硕士研究生，研究方向为CO2催化转化，E-mail：wangqian0720@link.tyut.edu.cn。
  孟凡会（1981—），博士，副教授，研究方向为碳一化学与化工，E-mail：mengfanhui@tyut.edu.cn；
  李忠（1964—），博士，教授，研究方向为煤化工，E-mail：lizhong@tyut.edu.cn。
- 基金信息：
  
  国家重点研发计划(2023YFB4103302;2023YFB4103304);国家自然科学基金(22278293);山西省重点研发计划(2022ZDYF064)
- DOI：10.12434/j.issn.2097-2547.20240118
  中图分类号： TQ426
- 纸质出版日期：2025-01-25，
  
  收稿日期：2024-03-22，
  
  修回日期：2024-04-22，
- 稿件说明：
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王倩, 王丽萍, 龚志远, 等. 不同尺寸钴基催化剂稳定策略研究进展[J]. 低碳化学与化工, 2025,50(1):1-12.

WANG QIAN, WANG LIPING, GONG ZHIYUAN, et al. Research progress on stabilization strategies for cobalt-based catalysts with different sizes. [J]. Low-carbon chemistry and chemical engineering, 2025, 50(1): 1-12.
王倩, 王丽萍, 龚志远, 等. 不同尺寸钴基催化剂稳定策略研究进展[J]. 低碳化学与化工, 2025,50(1):1-12. DOI： 10.12434/j.issn.2097-2547.20240118.

WANG QIAN, WANG LIPING, GONG ZHIYUAN, et al. Research progress on stabilization strategies for cobalt-based catalysts with different sizes. [J]. Low-carbon chemistry and chemical engineering, 2025, 50(1): 1-12. DOI： 10.12434/j.issn.2097-2547.20240118.

摘要

在多相催化反应中，金属催化剂的尺寸效应对其催化活性、产物选择性和稳定性具有较大影响。将金属催化剂的尺寸从纳米颗粒减小到亚纳米团簇，甚至原子尺度，可有效提高其活性中心利用率，从而大幅提高催化活性。钴（Co）基催化剂因其独特的电子结构和优异的催化活性，在众多反应中受到关注。根据Co基催化剂的研究现状，介绍了不同尺寸（纳米颗粒、团簇、单原子和双原子）Co基催化剂的结构及特点，阐述了提高不同尺寸Co基催化剂稳定性的策略，包括空间限域、金属-载体相互作用和金属-金属相互作用等，分析了这些策略对不同催化反应性能的影响及其优缺点，并对未来Co基催化剂的研究进行了展望。

Abstract

In heterogeneous catalytic reactions

the size effect of metal catalysts has a significant impact on their catalytic activity

product selectivity and stability. Reducing the size of metal catalysts from nanoparticles to sub-nanoclusters

or even to atomic-scale

can effectively increase the utilization of active sites

thereby greatly enhancing catalytic activity. Cobalt (Co)-based catalysts have attracted attention in many reactions due to their unique electronic structure and excellent catalytic activity. Based on the current research status of Co-based catalysts

the structures and characteristics of Co-based catalysts of different sizes (nanoparticles

clusters

single atoms

and diatomic species) were introduced. Strategies for improving the stability of Co-based catalysts with different sizes

including spatial confinement

metal-support interactions

and metal-metal interactions were elaborated. The impacts of these strategies on the performance of different catalytic reactions

as well as their advantages and disadvantages

were analyzed. Prospects for future research on Co-based catalysts were discussed.

关键词

Co基催化剂团聚稳定策略限域相互作用

Keywords

Co-based catalystsagglomerationstabilization strategiesconfinementinteractions

references

ZHANG Y, TIAN X, JI M Y, et al. Research progress of transition metal anode catalysts for direct borohydride fuel cells [J]. Journal of Nanoparticle Research, 2023, 25(12): 240.

GUPTA S, FERNANDES R, PATEL R, et al. A review of cobalt-based catalysts for sustainable energy and environmental applications [J]. Applied Catalysis A: General, 2023, 661: 119254.

LUO H H, TIAN S N, LIANG H L, et al. Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis [J]. Nature Communications, 2023, 14(1): 2981.

ZHAO Q, ZHENG Y F, SONG C F, et al. Novel monolithic catalysts derived from in-situ decoration of Co3O4 and hierarchical Co3O4@MnOx on Ni foam for VOC oxidation [J]. Applied Catalysis B: Environmental, 2020, 265(15): 118552.

CHU K, LIU Y P, LI Y B, et al. Efficient electrocatalytic N2 reduction on CoO quantum dots [J]. Journal of Materials Chemistry A, 2019, 7(9): 4389-4394.

HAN X P, LING X F, WANG Y, et al. Generation of nanoparticle, atomic-cluster and single-atom cobalt catalysts from zeolitic imidazole frameworks by spatial isolation and their use in zinc-air batteries [J]. Angewandte Chemie International Edition, 2019, 58(16): 5359-5364.

ZHAO H Q, CHENG Y, ZHANG Z, et al. Rational design of core-shell Co@C nanotubes towards lightweight and high-efficiency microwave absorption [J]. Composites Part B: Engineering, 2020, 196(1): 108119.

YAO S Y, LIN L L, LIAO W J, et al. Exploring metal-support interactions to immobilize subnanometer Co clusters on γ-Mo2N: A highly selective and stable catalyst for CO2 activation [J]. ACS Catalysis, 2019, 9(10): 9087-9097.

WU T, LI S, LIU S J, et al. Biomass-assisted approach for large-scale construction of multi-functional isolated single-atom site catalysts [J]. Nano Research, 2022, 15(5): 3980-3990.

HU S L, LI W X. Sabatier principle of metal-support interaction for design of ultrastable metal nanocatalysts [J]. Science, 2021, 374(6573): 1360-1365.

曹敏, 毛玉娇, 王倩倩, 等. 金属催化剂烧结机制及抗烧结策略[J]. 化工进展, 2023, 42(2): 744-755.

CAO M, MAO Y J, WANG Q Q, et al. Sintering mechanism and sintering-resistant strategies for metal-based catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 744-755.

冯翀, 俞金山, 刘甜甜, 等. 基于限域效应的铜基草酸二甲酯加氢催化剂研究进展[J]. 天然气化工—C1化学与化工, 2020, 45(3): 96-101.

FENG C, YU J S, LIU T T, et al. Research progress in confinement Cu-based catalysts for hydrogenation of dimethyl oxalate to ethylene glycol [J]. Natural Gas Chemical Industry, 2020, 45(3): 96-101.

YIN P, HU S L, QIAN K, et al. Quantification of critical particle distance for mitigating catalyst sintering [J]. Nature Communications, 2021, 12(1): 4865.

YING L, HAN Y, ZHU B E, et al. Exploration of structure sensitivity of gold nanoparticles in low-temperature CO oxidation [J]. Industrial Chemistry & Materials, 2024, 2(2): 321-327.

杨晓丽, 苏雄, 杨小峰, 等. 负载型金属催化剂的热稳定机制[J]. 化工学报, 2016, 67(1): 73-82.

YANG X L, SU X, YANG X F, et al. Stabilization mechanism of supported metal catalyst [J]. CIESC Journal, 2016, 67(1): 73-82.

LIU L C, ZAKHAROV D N, ARENAL R, et al. Evolution and stabilization of subnanometric metal species in confined space by in situ TEM [J]. Nature Communications, 2018, 9(1): 574.

WANG H W, GU X K, ZHENG X S, et al. Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity [J]. Science Advances, 2019, 5(1): eaat6413.

LIU L C, CORMA A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles [J]. Chemical Reviews, 2018, 118(10): 4981-5079.

JI S F, CHEN Y J, WANG X L, et al. Chemical synthesis of single atomic site catalysts [J]. Chemical Reviews, 2020, 120(21): 11900-11955.

ZHAO J J, QUAN X, CHEN S, et al. Cobalt nanoparticles encapsulated in porous carbons derived from core-shell ZIF67@ZIF8 as efficient electrocatalysts for oxygen evolution reaction [J]. ACS Applied Materials & Interfaces, 2017, 9(34): 28685-28694.

YOO J M, SHIN H J, CHUNG D Y, et al. Carbon shell on active nanocatalyst for stable electrocatalysis [J]. Accounts of Chemical Research, 2022, 55(9): 1278-1289.

CHEN Z L, WU R B, LIU Y, et al. Ultrafine Co nanoparticles encapsulated in carbon-nanotubes-grafted graphene sheets as advanced electrocatalysts for the hydrogen evolution reaction [J]. Advanced Materials, 2018, 30(30): 1802011.

WANG B L, FU Y G, LI J, et al. Yolk-shelled Co@SiO2@mesoporous carbon microspheres: Construction of multiple heterogeneous interfaces for wide-bandwidth microwave absorption [J]. Journal of Colloid and Interface Science, 2022, 607(2): 1540-1550.

丁邦琴, 周杰, 朱蓓蓓, 等. 费托合成钴基催化剂载体研究进展[J]. 天然气化工—C1化学与化工, 2017, 42(4): 108-113.

DING B Q, ZHOU J, ZHU B B, et al. Research progress in supports for Fischer-Tropsch cobalt-based catalysts [J]. Natural Gas Chemical Industry, 2017, 42(4): 108-113.

ZENG B, HOU B, JIA L T, et al. Studies of obalt pcarticle size effects on Fischer-Tropsch synthesis over core-shell-structured catalysts [J]. ChemCatChem, 2013, 5(12): 3794-3801.

QIN C, HOU B, WANG J G, et al. Stabilizing optimal crystalline facet of cobalt catalysts for Fischer-Tropsch dynthesis [J]. ACS Applied Materials & Interfaces, 2019, 11(37): 33886-33893.

ZHOU Y Y, LIU J C, SUN F Y, et al. Incorporating metal nanoparticles in porous materials via selective heating effect using microwave [J]. Nano Research, 2023, 17: 3175-3179.

HOU J F, LIN J L, FU H Y, et al. Vitamin B12 derived CoCNx composite confined in SBA-15 as highly effective catalyst to activate peroxymonosulfate for naproxen degradation [J]. Chemical Engineering Journal, 2020, 389(1): 124344.

LEE M H, DEKA J R, CHENG C J, et al. Synthesis of highly dispersed ultra-small cobalt nanoparticles within the cage-type mesopores of 3D cubic mesoporous silica via double agent reduction method for catalytic hydrogen generation [J]. Applied Surface Science, 2019, 470(15): 764-772.

TAVASOLI A, TRéPANIER M, DALAI A, et al. Effects of confinement in carbon nanotubes on the activity, selectivity and lifetime of Fischer-Tropsch Co/carbon nanotube catalysts [J]. Journal of Chemical & Engineering Data, 2010, 55(8): 2757-2763.

SUN C F, TEO B K, DENG C L, et al. Hydrido-coinage-metal clusters: Rational design, synthetic protocols and structural characteristics [J]. Coordination Chemistry Reviews, 2021, 427(15): 213576.

YU Y Z, GUO Y H, ZHANG Y R, et al. Tetrahedral μ4-chloride and in situ generated octahedral μ6-sulfide templating Co8 complexes with different distortions of the cube [J]. Chemical Communications, 2020, 56(30): 4236-4239.

LIU L C, DÍAZ U, ARENAL R, et al. Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D [J]. Nature Materials, 2016, 16(1): 132-138.

ZHANG W Y, CHAO Y G, ZHANG W S, et al. Emerging dual-atomic-site catalysts for efficient energy catalysis [J]. Advanced Materials, 2021, 33(36): 2102576.

ZHU Q X, LU X W, JI S Q, et al. Fully exposed cobalt nanoclusters anchored on nitrogen-doped carbon synthesized by a host-guest strategy for semi-hydrogenation of phenylacetylene [J]. Journal of Catalysis, 2022, 405: 499-507.

SHI G D, XIE Y L, DU L L, et al. Stabilization of cobalt clusters with graphdiyne enabling efficient overall water splitting [J]. Nano Energy, 2020, 74: 104852.

ZHOU T P, SHAN H, YU H, et al. Nanopore confinement of electrocatalysts optimizing triple transport for an ultrahigh-power-density zinc-air fuel cell with robust stability [J]. Advanced Materials, 2020, 32(47): 2003251.

GE X L, DI H X, WANG P, et al. metal-organic framework-derived nitrogen-doped cobalt nanocluster inlaid porous carbon as high-efficiency catalyst for advanced potassium-sulfur batteries [J]. ACS Nano, 2020, 14(11): 16022-16035.

WAN J W, CHEN W X, JIA C Y, et al. Defect effects on TiO2 nanosheets: Stabilizing single atomic site Au and promoting catalytic properties [J]. Advanced Materials, 2018, 30(11): 1705369.

吴博涵, 孙晓然, 任小亮. 单原子催化中的活性位构建方法研究进展[J]. 分子催化, 2023, 37(6): 587-600.

WU B H, SUN X R, REN X L. Research progress on the synthesis and assembly of active sites in single-atom catalysts [J]. Journal of Molecular Catalysis (China), 2023, 37(6): 587-600.

WU X, ZHANG H B, ZUO S W, et al. Engineering the coordination sphere of isolated active sites to explore the intrinsic activity in single-atom catalysts [J]. Nano-Micro Letters, 2021, 13(1): 136.

ZHANG L J, JIN N J, YANG Y B, et al. Advances on axial coordination design of single-atom catalysts for energy electrocatalysis: A review [J]. Nano-Micro Letters, 2023, 15(1): 228.

ZHANG H B, LIU G J, SHI L, et al. single-atom catalysts: Emerging multifunctional materials in heterogeneous catalysis [J]. Advanced Energy Materials, 2017, 8(1): 1701343.

CHEN Y J, JI S F, CHEN C, et al. single-atom catalysts: Synthetic strategies and electrochemical applications [J]. Joule, 2018, 2(7): 1242-1264.

WAN J W, ZHAO Z H, SHANG H S, et al. In situ phosphatizing of triphenylphosphine encapsulated within metal-organic frameworks to design atomic Co1-P1N3 interfacial dtructure for promoting catalytic performance [J]. Journal of the American Chemical Society, 2020, 142(18): 8431-8439.

CAO E P, CHEN Z M, WU H, et al. Boron-induced electronic-structure reformation of CoP nanoparticles drives enhanced pH-universal hydrogen evolution [J]. Angewandte Chemie International Edition, 2020, 59(10): 4154-4160.

LI X, WEN X, LANG J Y, et al. CoN1O2 single-atom catalyst for efficient peroxymonosulfate activation and selective cobalt(IV)==O generation [J]. Angewandte Chemie International Edition, 2023, 62(27): e202303267.

TANG C, JIAO Y, SHI B Y, et al. Coordination tunes selectivity: Two-electron oxygen reduction on high-loading molybdenum single-atom catalysts [J]. Angewandte Chemie International Edition, 2020, 59(23): 9171-9176.

LI J J, ZHANG L, DOYLE D K, et al. Recent advances and strategies in the stabilization of single-atom catalysts for electrochemical applications [J]. Carbon Energy, 2020, 2(4): 488-520.

LI Y H, ZHAO Z A, LU W, et al. Single-atom Co-N-C catalysts for high-efficiency reverse water-gas shift reaction [J]. Applied Catalysis B: Environmental, 2023, 324(5): 122298.

LIU W G, ZHANG L L, YAN W S, et al. Single-atom dispersed Co-N-C catalyst: Structure identification and performance for hydrogenative coupling of nitroarenes [J]. Chemical Science, 2016, 7(9): 5758-5764.

FANG D L, SUN P, HUANG S Z, et al. An exfoliatioe-evaporation strategy to regulate N coordination number of Co single-atom catalysts for high-performance lithium-sulfur batteries [J]. ACS Materials Letters, 2022, 4(1): 1-10.

HUANG K, WEI Z X, LIU J B, et al. Engineering the morphology and microenvironment of a graphene-supported Co-N-C single-atom electrocatalyst for enhanced hydrogen evolution [J]. Small, 2022, 18(19): 2201139.

PAN Y, LIN R, CHEN Y J, et al. Design of single-atom Co-N5 catalytic site: A robust electrocatalyst for CO2 reduction with nearly 100% CO selectivity and remarkable stability [J]. Journal of the American Chemical Society, 2018, 140(12): 4218-4221.

LIANG S, ZOU L C, ZHENG L J, et al. Highly stable Co single atom confined in hierarchical carbon molecular sieve as efficient electrocatalysts in metal-air batteries [J]. Advanced Energy Materials, 2022, 12(11): 2103097.

HU Z P, QIN G, HAN J, et al. Atomic insight into the local structure and microenvironment of isolated Co-motifs in MFI zeolite frameworks for propane dehydrogenation [J]. Journal of the American Chemical Society, 2022, 144(27): 12127-12137.

WANG J, ZHAO C X, LIU J N, et al. Dual-atom catalysts for oxygen electrocatalysis [J]. Nano Energy, 2022, 104(15): 107927.

ZHANG J, HUANG Q A, WANG J, et al. Supported dual-atom catalysts: Preparation, characterization, and potential applications [J]. Chinese Journal of Catalysis, 2020, 41(5): 783-798.

齐美丽, 李勉拓, 张梦娟, 等. 双原子催化剂在电催化领域的应用研究进展[J]. 材料导报, 2021, 35(S1): 481-484.

QI M L, LI M T, ZHANG M J, et al. Progress in the application of dual-atom catalysts in electrocatalytic field [J]. Materials Reports, 2021, 35(S1): 481-484.

HU Y F, LI Z S, LI B L, et al. Recent progress of diatomic catalysts: General design fundamentals and diversified catalytic applications [J]. Small, 2022, 18(46): 2203589.

LI R Z, WANG D S. Superiority of dual-atom catalysts in electrocatalysis: One step further than single-atom catalysts [J]. Advanced Energy Materials, 2022, 12(9): 2103564.

ZHOU Q, SONG J J, LV N, et al. Fully dispersed cobalt diatomic site with significantly improved Fenton-like catalysis performance for organic pollutant degradation [J]. Journal of Colloid and Interface Science, 2024, 662(15): 1005-1015.

PENG X B, CAI H F, ZHOU Y L, et al. Studies of a highly active cobalt atomic cluster catalyst for ammonia synthesis [J]. ACS Sustainable Chemistry & Engineering, 2022, 10(5): 1951-1960.

FAN M M, CUI J W, WU J J, et al. Improving the catalytic activity of carbon-supported single atom catalysts by polynary metal or heteroatom doping [J]. Small, 2020, 16(22): 1906782.

QIN R X, LIU P X, FU G, et al. Strategies for stabilizing atomically dispersed metal catalysts [J]. Small Methods, 2017, 2(1): 1700286.

CHAI Y C, CHEN S H, CHEN Y, et al. Dual-atom catalyst with N-colligated Zn1Co1 species as dominant active sites for propane dehydrogenation [J]. Journal of the American Chemical Society, 2024, 146(1): 263-273.

HE Q, LIU D B, LEE J H, et al. Electrochemical conversion of CO2 to syngas with controllable CO/H2 ratios over Co and Ni single-atom catalysts [J]. Angewandte Chemie International Edition, 2020, 59(8): 3033-3037.

LIU M, LI N, CAO S F, et al. A “pre-constrained metal twins” strategy to prepare efficient dual-metal-atom catalysts for cooperative oxygen electrocatalysis [J]. Advanced Materials, 2022, 34(7): 2107421.

YI J D, GAO X P, ZHOU H, et al. Design of Co-Cu diatomic site catalysts for high-efficiency synergistic CO2 electroreduction at industrial-level current density [J]. Angewandte Chemie International Edition, 2022, 61(47): e202212329.

OU H, WANG D LI Y. How to select effective electrocatalysts: Nano or single atom? [J]. Nano Select, 2021, 2(3): 492-511.

CHENG T Y, YU H, PENG F, et al. Identifying active sites of CoNC/CNT from pyrolysis of molecularly defined complexes for oxidative esterification and hydrogenation reactions [J]. Catalysis Science & Technology, 2016, 6(4): 1007-1015.

LIU L C, CONCEPCIÓN P, CORMA A. Non-noble metal catalysts for hydrogenation: A facile method for preparing Co nanoparticles covered with thin layered carbon [J]. Journal of Catalysis, 2016, 340: 1-9.

LIU L, MEIRA D M, ARENAL R, et al. Determination of the evolution of heterogeneous single metal atoms and nanoclusters under reaction conditions: which are the working catalytic sites? [J]. ACS Catalysis, 2019, 9(12): 10626-10639.

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