Computational catalysis on the conversion of CO₂ to methane—an update

Abstract

The reliance on fossil fuels intensifies CO₂ emissions, worsening political and environmental challenges. CO₂ capture and conversion present a promising solution, influenced by industrialization and urbanization. In recent times, catalytic conversion of CO₂ into fuels and chemical precursors, particularly methane, are gaining traction for establishing a sustainable, carbon-neutral economy due to methane’s advantages in renewable energy applications. Though homogeneous and heterogeneous catalysts are available for the conversion of CO₂ to methane, the efficiency is found to be higher in heterogeneous catalysts. Therefore, this review focuses only on the heterogeneous catalysts. In this context, the efficient heterogeneous catalysts with optimum utility are yet to be obtained. Therefore, the quest for suitable catalyst for the catalytic conversion of CO₂ to CH₄ is still continuing and designing efficient catalysts requires assessing their synthetic feasibility, often achieved through computational methods like density functional theory simulations, providing insights into reaction mechanisms, rate-limiting steps, catalytic cycle, activation of C=O bonds and enhancing understanding while lowering costs. In this context, this review examines the conversion of CO₂ to CH₄ using seven distinct types of catalysts, including single and double atom catalysts, metal organic frameworks, metalloporphyrins, graphdiyne and graphitic carbon nitrite and alloys with some case studies. The main focus of this review is to offer a detailed and extensive examination of diverse catalyst design approaches and their utilization in CH₄ production, with a specific emphasis on computational aspects. It explores the array of design methodologies used to identify reaction pathways and investigates the critical role of computational tools in their refinement and enhancement. We believe this review will help budding researchers to explore the possibilities of designing catalysts for the CO₂ to CH₄ conversion from computational framework.

Key words： computational catalysis; single atom catalyst; CO₂ reduction; metalloporphyrins; double-atom catalyst; graphitic carbon nitrite

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

The authors (YMK, AR & RVS) dedicate this review to their esteemed professor, Dr. J. Princy Merlin, Principal of Bishop Heber College, Tiruchirappalli, whose three decades of selfless service have inspired thousands of students. Prince Joby, of 2nd M. Sc. Chemistry, has done this work at DST-FIST Sponsored Professor Edward Barnes Computation and Instrumentation Facility (PEBCIF) of the Department of Chemistry, Madras Christian College. Dr. R. Vijay Solomon thanks the Department of Chemistry, MCC for the support and encouragement. Dr. Y. Manojkumar acknowledges the management of Bishop Heber College (Autonomous), Tiruchirappalli-620 017, Tamil Nadu, India, for the support (Ref. No. 18.04.2023 MRP/1005/2023 (BHC)). Dr. Antony Rajendrdan acknowledges the support provided by the National Key Research and Development Program of China (Grant No. 2022YFE0208400).

References

1 Takata T , Jiang J , Sakata Y , Nakabayashi M , Shibata N , Nandal V , Seki K , Hisatomi T , Domen K . Photocatalytic water splitting with a quantum efficiency of almost unity. Nature, 2020, 581(7809): 411–414

2 Albo J , Alvarez-Guerra M , Castaño P , Irabien A . Towards the electrochemical conversion of carbon dioxide into methanol. Green Chemistry, 2015, 17(4): 2304–2324

3 Zhao S , Jin R , Jin R . Opportunities and challenges in CO₂ reduction by gold-and silver-based electrocatalysts: from bulk metals to nanoparticles and atomically precise nanoclusters. ACS Energy Letters, 2018, 3(2): 452–462

4 Shi R , Wang Z , Zhao Y , Waterhouse G I , Li Z , Zhang B , Sun Z , Xia C , Wang H , Zhang T . Room-temperature electrochemical acetylene reduction to ethylene with high conversion and selectivity. Nature Catalysis, 2021, 4(7): 565–574

5 Sun Z , Ma T , Tao H , Fan Q , Han B . Fundamentals and challenges of electrochemical CO₂ reduction using two-dimensional materials. Chem, 2017, 3(4): 560–587

6 Ahmad T , Zhang D . A critical review of comparative global historical energy consumption and future demand: the story told so far. Energy Reports, 2020, 6: 1973–1991

7 SmolinkaTOjongE TGarcheJ. Hydrogen production from renewable energies—electrolyzer technologies, in electrochemical energy storage for renewable sources and grid balancing. Elsevier, 2015, 103–128

8 Yu Z Y , Duan Y , Feng X Y , Yu X , Gao M R , Yu S H . Clean and affordable hydrogen fuel from alkaline water splitting: past, recent progress, and future prospects. Advanced Materials, 2021, 33(31): 2007100

9 Woldu A R , Huang Z , Zhao P , Hu L , Astruc D . Electrochemical CO₂ reduction (CO₂RR) to multi-carbon products over copper-based catalysts. Coordination Chemistry Reviews, 2022, 454: 214340

10 DziejarskiBSerafinJAnderssonKKrzyżyńskaR. CO₂ capture materials: a review of current trends and future challenges. Materials Today Sustainability, 2023: 100483

11 Koerner B , Klopatek J . Anthropogenic and natural CO₂ emission sources in an arid urban environment. Environmental Pollution, 2002, 116: S45–S51

12 Zha W , Liu D , Ma Z , Wang Y , Wei Y , Ma X , Wang L , Zhang Q , Lou B , Yuan R . . Efficient electrochemical CO₂ reduction on C₂N monolayer supported transition metals trimer catalysts: a DFT study. Applied Surface Science, 2021, 564: 150331

13 Li Y , Sun Q . Recent advances in breaking scaling relations for effective electrochemical conversion of CO₂. Advanced Energy Materials, 2016, 6(17): 1600463

14 Tian Y , Wang Y , Yan L , Zhao J , Su Z . Electrochemical reduction of carbon dioxide on the two-dimensional M₃(hexaiminotriphenylene)₂ sheet: a computational study. Applied Surface Science, 2019, 467-468: 98–103

15 Wagner A , Sahm C D , Reisner E . Towards molecular understanding of local chemical environment effects in electro-and photocatalytic CO₂ reduction. Nature Catalysis, 2020, 3(10): 775–786

16 Todorova T K , Schreiber M W , Fontecave M . Mechanistic understanding of CO₂ reduction reaction (CO₂RR) toward multicarbon products by heterogeneous copper-based catalysts. ACS Catalysis, 2020, 10(3): 1754–1768

17 Spigarelli B P , Kawatra S K . Opportunities and challenges in carbon dioxide capture. Journal of CO₂ Utilization, 2013, 1: 69–87

18 Zhang S , Chen C , Ahn W S . Recent progress on CO₂ capture using amine-functionalized silica. Current Opinion in Green and Sustainable Chemistry, 2019, 16: 26–32

19 Kumar S , Srivastava R , Koh J . Utilization of zeolites as CO₂ capturing agents: advances and future perspectives. Journal of CO₂ Utilization, 2020, 41: 101251

20 Zhou Z , Qi Y , Xie M , Cheng Z , Yuan W . Synthesis of CaO-based sorbents through incorporation of alumina/aluminate and their CO₂ capture performance. Chemical Engineering Science, 2012, 74: 172–180

21 Didas S A , Choi S , Chaikittisilp W , Jones C W . Amine-oxide hybrid materials for CO₂ capture from ambient air. Accounts of Chemical Research, 2015, 48(10): 2680–2687

22 Veerabhadrappa M G , Maroto-Valer M M , Chen Y , Garcia S . Layered double hydroxides-based mixed metal oxides: development of novel structured sorbents for CO₂ capture applications. ACS Applied Materials & Interfaces, 2021, 13(10): 11805–11813

23 Avci G , Velioglu S , Keskin S . High-throughput screening of MOF adsorbents and membranes for H₂ purification and CO₂ capture. ACS Applied Materials & Interfaces, 2018, 10(39): 33693–33706

24 Ji Y , Zhang M , Guan K , Zhao J , Liu G , Jin W . High-performance CO₂ capture through polymer-based ultrathin membranes. Advanced Functional Materials, 2019, 29(33): 1900735

25 Abuelnoor N , AlHajaj A , Khaleel M , Vega L F , Abu-Zahra M R . Activated carbons from biomass-based sources for CO₂ capture applications. Chemosphere, 2021, 282: 131111

26 Yang Y , Liu W , Hu Y , Sun J , Tong X , Chen Q , Li Q . One-step synthesis of porous Li₄SiO₄-based adsorbent pellets via graphite moulding method for cyclic CO₂ capture. Chemical Engineering Journal, 2018, 353: 92–99

27 An L , Liu S , Wang L , Wu J , Wu Z , Ma C , Yu Q , Hu X . Novel nitrogen-doped porous carbons derived from graphene for effective CO₂ capture. Industrial & Engineering Chemistry Research, 2019, 58(8): 3349–3358

28 Dong H , Lin B , Gilmore K , Hou T , Lee S T , Li Y . B40 fullerene: an efficient material for CO₂ capture, storage and separation. Current Applied Physics, 2015, 15(9): 1084–1089

29 Ngoy J M , Wagner N , Riboldi L , Bolland O A . CO₂ capture technology using multi-walled carbon nanotubes with polyaspartamide surfactant. Energy Procedia, 2014, 63: 2230–2248

30 Jung S , Park Y K , Kwon E E . Strategic use of biochar for CO₂ capture and sequestration. Journal of CO₂ Utilization, 2019, 32: 128–139

31 Fagnani H M , da Silva C T , Pereira M M , Rinaldi A W , Arroyo P A , de Barros M A . CO₂ adsorption in hydrochar produced from waste biomass. SN Applied Sciences, 2019, 1(9): 1031

32 MarshHReinosoF R. Activated Carbon. Elsevier, 2006

33 Hu X , Radosz M , Cychosz K A , Thommes M . CO₂-filling capacity and selectivity of carbon nanopores: synthesis, texture, and pore-size distribution from quenched-solid density functional theory (QSDFT). Environmental Science & Technology, 2011, 45(16): 7068–7074

34 Drage T C , Blackman J M , Pevida C , Snape C E . Evaluation of activated carbon adsorbents for CO₂ capture in gasification. Energy & Fuels, 2009, 23(5): 2790–2796

35 Akten E D , Siriwardane R , Sholl D S . Monte Carlo simulation of single- and binary-component adsorption of CO₂, N₂, and H₂ in zeolite Na-4A. Energy & Fuels, 2003, 17(4): 977–983

36 Harlick P J , Sayari A . Applications of pore-expanded mesoporous silica. 5. Triamine grafted material with exceptional CO₂ dynamic and equilibrium adsorption performance. Industrial & Engineering Chemistry Research, 2007, 46(2): 446–458

37 Franchi R S , Harlick P J , Sayari A . Applications of pore-expanded mesoporous silica. 2. Development of a high-capacity, water-tolerant adsorbent for CO₂. Industrial & Engineering Chemistry Research, 2005, 44(21): 8007–8013

38 Jiménez V , Ramírez-Lucas A , Díaz J A , Sánchez P , Romero A . CO₂ capture in different carbon materials. Environmental Science & Technology, 2012, 46(13): 7407–7414

39 Cui S , Cheng W , Shen X , Fan M , Russell A T , Wu Z , Yi X . Mesoporous amine-modified SiO₂ aerogel: a potential CO₂ sorbent. Energy & Environmental Science, 2011, 4(6): 2070–2074

40 Rogelj J , Den Elzen M , Höhne N , Fransen T , Fekete H , Winkler H , Schaeffer R , Sha F , Riahi K , Meinshausen M . Paris Agreement climate proposals need a boost to keep warming well below 2 °C. Nature, 2016, 534(7609): 631–639

41 Ye R P , Ding J , Gong W , Argyle M D , Zhong Q , Wang Y , Russell C K , Xu Z , Russell A G , Li Q . . CO₂ hydrogenation to high-value products via heterogeneous catalysis. Nature Communications, 2019, 10(1): 5698

42 Wang H H , Hou L , Li Y Z , Jiang C Y , Wang Y Y , Zhu Z . Porous MOF with highly efficient selectivity and chemical conversion for CO₂. ACS Applied Materials & Interfaces, 2017, 9(21): 17969–17976

43 Lee J C , Kim J H , Chang W S , Pak D . Biological conversion of CO₂ to CH₄ using hydrogenotrophic methanogen in a fixed bed reactor. Journal of Chemical Technology and Biotechnology, 2012, 87(6): 844–847

44 Tu W , Zhou Y , Zou Z . Photocatalytic conversion of CO₂ into renewable hydrocarbon fuels: state-of-the-art accomplishment, challenges, and prospects. Advanced Materials, 2014, 26(27): 4607–4626

45 Genovese C , Ampelli C , Perathoner S , Centi G . Electrocatalytic conversion of CO₂ to liquid fuels using nanocarbon-based electrodes. Journal of Energy Chemistry, 2013, 22(2): 202–213

46 Li M , Wang H , Luo W , Sherrell P C , Chen J , Yang J . Heterogeneous single-atom catalysts for electrochemical CO₂ reduction reaction. Advanced Materials, 2020, 32(34): 2001848

47 Lim R J , Xie M , Sk M A , Lee J M , Fisher A , Wang X , Lim K H . A review on the electrochemical reduction of CO₂ in fuel cells, metal electrodes and molecular catalysts. Catalysis Today, 2014, 233: 169–180

48 Lu Q , Rosen J , Jiao F . Nanostructured metallic electrocatalysts for carbon dioxide reduction. ChemCatChem, 2015, 7(1): 38–47

49 Yaashikaa P , Kumar P S , Varjani S J , Saravanan A . A review on photochemical, biochemical and electrochemical transformation of CO₂ into value-added products. Journal of CO₂ Utilization, 2019, 33: 131–147

50 Huo S , Weng Z , Wu Z , Zhong Y , Wu Y , Fang J , Wang H . Coupled metal/oxide catalysts with tunable product selectivity for electrocatalytic CO₂ reduction. ACS Applied Materials & Interfaces, 2017, 9(34): 28519–28526

51 Kortlever R , Shen J , Schouten K J P , Calle-Vallejo F , Koper M T . Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide. Journal of Physical Chemistry Letters, 2015, 6(20): 4073–4082

52 Prabhu P , Jose V , Lee J M . Heterostructured catalysts for electrocatalytic and photocatalytic carbon dioxide reduction. Advanced Functional Materials, 2020, 30(24): 1910768

53 Roy S C , Varghese O K , Paulose M , Grimes C A . Toward solar fuels: photocatalytic conversion of carbon dioxide to hydrocarbons. ACS Nano, 2010, 4(3): 1259–1278

54 Das S , Daud W W . A review on advances in photocatalysts towards CO₂ conversion. RSC Advances, 2014, 4(40): 20856–20893

55 Tahir M , Amin N S . Recycling of carbon dioxide to renewable fuels by photocatalysis: prospects and challenges. Renewable & Sustainable Energy Reviews, 2013, 25: 560–579

56 Wang G , Chen J , Ding Y , Cai P , Yi L , Li Y , Tu C , Hou Y , Wen Z , Dai L . Electrocatalysis for CO₂ conversion: from fundamentals to value-added products. Chemical Society Reviews, 2021, 50(8): 4993–5061

57 Gao D , Liu T , Wang G , Bao X . Structure sensitivity in single-atom catalysis toward CO₂ electroreduction. ACS Energy Letters, 2021, 6(2): 713–727

58 Liu X , Wang Z , Tian Y , Zhao J . Graphdiyne-supported single iron atom: a promising electrocatalyst for carbon dioxide electroreduction into methane and ethanol. Journal of Physical Chemistry C, 2020, 124(6): 3722–3730

59 Ting L R L , Pique O , Lim S Y , Tanhaei M , Calle-Vallejo F , Yeo B S . Enhancing CO₂ electroreduction to ethanol on copper-silver composites by opening an alternative catalytic pathway. ACS Catalysis, 2020, 10(7): 4059–4069

60 Wang Y , Pham T N , Tian Y , Morikawa Y , Yan L . Density functional theory study on a nitrogen-rich carbon nitride material C₃N₅ as photocatalyst for CO₂ reduction to C1 and C2 products. Journal of Colloid and Interface Science, 2021, 585: 740–749

61 Yan Y , Dai Y , He H , Yu Y , Yang Y . A novel W-doped Ni-Mg mixed oxide catalyst for CO₂ methanation. Applied Catalysis B: Environmental, 2016, 196: 108–116

62 Kothandaraman J , Goeppert A , Czaun M , Olah G A , Prakash G S . Conversion of CO₂ from air into methanol using a polyamine and a homogeneous ruthenium catalyst. Journal of the American Chemical Society, 2016, 138(3): 778–781

63 Hidalgo D , Martín-Marroquín J . Power-to-methane, coupling CO₂ capture with fuel production: an overview. Renewable & Sustainable Energy Reviews, 2020, 132: 110057

64 Sun Y , Lin Z , Peng S H , Sage V , Sun Z . A critical perspective on CO₂ conversions into chemicals and fuels. Journal of Nanoscience and Nanotechnology, 2019, 19(6): 3097–3109

65 Ulmer U , Dingle T , Duchesne P N , Morris R H , Tavasoli A , Wood T , Ozin G A . Fundamentals and applications of photocatalytic CO₂ methanation. Nature Communications, 2019, 10(1): 3169

66 Al-Fatesh A , Singh S K , Kanade G , Atia H , Fakeeha A H , Ibrahim A A , El-Toni A M , Labhasetwar N K . Rh promoted and ZrO₂/Al₂O₃ supported Ni/Co based catalysts: high activity for CO₂ reforming, steam-CO₂ reforming and oxy-CO₂ reforming of CH₄. International Journal of Hydrogen Energy, 2018, 43(27): 12069–12080

67 Bremer J , Sundmacher K . Operation range extension via hot-spot control for catalytic CO₂ methanation reactors. Reaction Chemistry & Engineering, 2019, 4(6): 1019–1037

68 Panagiotopoulou P , Kondarides D I , Verykios X E . Selective methanation of CO over supported Ru catalysts. Applied Catalysis B: Environmental, 2009, 88(3–4): 470–478

69 Podrojková N , Sans V , Oriňak A , Oriňaková R . Recent developments in the modelling of heterogeneous catalysts for CO₂ conversion to chemicals. ChemCatChem, 2020, 12(7): 1802–1825

70 Zhang S , Fan Q , Xia R , Meyer T J . CO₂ reduction: from homogeneous to heterogeneous electrocatalysis. Accounts of Chemical Research, 2020, 53(1): 255–264

71 Nganga J K , Wolf L M , Mullick K , Reinheimer E , Saucedo C , Wilson M E , Grice K A , Ertem M Z , Angeles-Boza A M . Methane generation from CO₂ with a molecular rhenium catalyst. Inorganic Chemistry, 2021, 60(6): 3572–3584

72 Sun L , Reddu V , Fisher A C , Wang X . Electrocatalytic reduction of carbon dioxide: opportunities with heterogeneous molecular catalysts. Energy & Environmental Science, 2020, 13(2): 374–403

73 Tian Z , Priest C , Chen L . Recent progress in the theoretical investigation of electrocatalytic reduction of CO₂. Advanced Theory and Simulations, 2018, 1(5): 1800004

74 Xu S , Carter E A . Theoretical insights into heterogeneous (photo) electrochemical CO₂ reduction. Chemical Reviews, 2019, 119(11): 6631–6669

75 Zhu X , Li Y . Review of two-dimensional materials for electrochemical CO₂ reduction from a theoretical perspective. WIREs Computational Molecular Science, 2019, 9(6): e1416

76 Han M , Fu X , Cao A , Guo C , Chu W , Xiao J . Toward computational design of catalysts for CO₂ selective reduction via reaction phase diagram analysis. Advanced Theory and Simulations, 2019, 2(3): 1800200

77 Kibria M G , Edwards J P , Gabardo C M , Dinh C T , Seifitokaldani A , Sinton D , Sargent E H . Electrochemical CO₂ reduction into chemical feedstocks: from mechanistic electrocatalysis models to system design. Advanced Materials, 2019, 31(31): 1807166

78 Kovačič Z , Likozar B , Hus M . Photocatalytic CO₂ reduction: a review of ab initio mechanism, kinetics, and multiscale modeling simulations. ACS Catalysis, 2020, 10(24): 14984–15007

79 Morales-García Á , Viñes F , Gomes J R , Illas F . Concepts, models, and methods in computational heterogeneous catalysis illustrated through CO₂ conversion. WIREs Computational Molecular Science, 2021, 11(4): e1530

80 Masdeu-Bultó A M , Reguero M , Claver C . Mechanistic insights of photocatalytic CO₂ reduction: experimental versus computational studies. European Journal of Inorganic Chemistry, 2022, (14): e202100975

81 HussainSYangXYangJLiQ. Theoretical insights into the mechanism of photocatalytic reduction of CO₂ and water splitting over II–VI zinc chalcogenide semiconductor. Materials Today Sustainability, 2024: 100686

82 Alli Y A , Oladoye P O , Onawole A T , Anuar H , Adewuyi S , Ogunbiyi O D , Philippot K . Photocatalysts for CO₂ reduction and computational insights. Fuel, 2023, 344: 128101

83 AliS ASadiqIAhmadT. Deep insight of CO₂ reduction reaction mechanism through experimental and theoretical anticipations. Materials Today Sustainability, 2023: 100587

84 AmayaSuárez JRemesalE RPlataJ JMárquezA MFernándezSanz J. Computational modeling of carbon dioxide catalytic conversion. Engineering Solutions for CO₂ Conversion, 2021: 85–103

85 Li Y , Chan S H , Sun Q . Heterogeneous catalytic conversion of CO₂: a comprehensive theoretical review. Nanoscale, 2015, 7(19): 8663–8683

86 Weijing D , Weihong Z , Xiaodong Z , Baofeng Z , Lei C , Laizhi S , Shuangxia Y , Haibin G , Guanyi C , Liang Z . . The application of DFT in catalysis and adsorption reaction system. Energy Procedia, 2018, 152: 997–1002

87 Cheng D , Negreiros F R , Aprà E , Fortunelli A . Computational approaches to the chemical conversion of carbon dioxide. ChemSusChem, 2013, 6(6): 944–965

88 Hohenberg P , Kohn W . Inhomogeneous electron gas. Physical Review, 1964, 136(3B): B864–B871

89 Kohn W , Sham L J . Self-consistent equations including exchange and correlation effects. Physical Review, 1965, 140(4A): A1133–A1138

90 Kresse G , Furthmüller J . Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 1996, 6(1): 15–50

91 Kresse G , Joubert D . From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B: Condensed Matter, 1999, 59(3): 1758–1775

92 Delley B . An all-electron numerical method for solving the local density functional for polyatomic molecules. Journal of Chemical Physics, 1990, 92(1): 508–517

93 Delley B . From molecules to solids with the DMol³ approach. Journal of Chemical Physics, 2000, 113(18): 7756–7764

94 Nørskov J K , Rossmeisl J , Logadottir A , Lindqvist L , Kitchin J R , Bligaard T , Jonsson H . Origin of the overpotential for oxygen reduction at a fuel-cell cathode. Journal of Physical Chemistry B, 2004, 108(46): 17886–17892

95 Dao X Y , Guo J H , Zhang X Y , Wang S Q , Cheng X M , Sun W Y . Structure-dependent iron-based metal-organic frameworks for selective CO₂-to-CH₄ photocatalytic reduction. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2020, 8(48): 25850–25856

96 Wang Y L , Tian Y , Lang Z L , Guan W , Yan L K . A highly efficient Z-scheme B-doped g-C₃N₄/SnS₂ photocatalyst for CO₂ reduction reaction: a computational study. Journal of Materials Chemistry. A, 2018, 6(42): 21056–21063

97 Qiao B , Wang A , Yang X , Allard L F , Jiang Z , Cui Y , Liu J , Li J , Zhang T . Single-atom catalysis of CO oxidation using Pt1/FeO_x. Nature Chemistry, 2011, 3(8): 634–641

98 Thomas J M , Saghi Z , Gai P L . Can a single atom serve as the active site in some heterogeneous catalysts?. Topics in Catalysis, 2011, 54(10–12): 588–594

99 Ranocchiari M , Lothschütz C , Grolimund D , van Bokhoven J A . Single-atom active sites on metal-organic frameworks. Proceedings of Royal Society A: Mathematical, Physical and Engineering Sciences, 2012, 468(2143): 1985–1999

100 Yang X F , Wang A , Qiao B , Li J , Liu J , Zhang T . Single-atom catalysts: a new frontier in heterogeneous catalysis. Accounts of Chemical Research, 2013, 46(8): 1740–1748

101 Cheng N , Zhang L , Doyle-Davis K , Sun X . Single-atom catalysts: from design to application. Electrochemical Energy Reviews, 2019, 2(4): 539–573

102 Chen Q , Ke Q , Zhao X , Chen X . Ruthenium-doped boron nitride nanotubes as promising electrocatalysts for carbon dioxide reduction to methane. Diamond and Related Materials, 2023, 136: 109942

103 Zhang Y , Zeng Z , Li H . Design of 3d transition metal anchored B₅N₃ catalysts for electrochemical CO₂ reduction to methane. Journal of Materials Chemistry A, 2022, 10(17): 9737–9745

104 Lu S , Huynh H L , Lou F , Guo M , Yu Z . Electrochemical reduction of CO₂ to CH₄ over transition metal atom embedded antimonene: first-principles study. Journal of CO₂ Utilization, 2021, 51: 101645

105 Wang Y , Su H , He Y , Li L , Zhu S , Shen H , Xie P , Fu X , Zhou G , Feng C . . Advanced electrocatalysts with single-metal-atom active sites. Chemical Reviews, 2020, 120(21): 12217–12314

106 Yang Y , Liu J , Wu D , Ding J , Xiong B . Two-dimensional pyrite supported transition metal for highly-efficient electrochemical CO₂ reduction: a theoretical screening study. Chemical Engineering Journal, 2021, 424: 130541

107 Fu L , Wang R , Zhao C , Huo J , He C , Kim K H , Zhang W . Construction of Cr-embedded graphyne electrocatalyst for highly selective reduction of CO₂ to CH₄: a DFT study. Chemical Engineering Journal, 2021, 414: 128857

108 Chen C , Tang C , Xu W , Li Y , Xu L . Design of iron atom modified thiophene-linked metalloporphyrin 2D conjugated microporous polymer as CO₂ reduction photocatalyst. Physical Chemistry Chemical Physics, 2018, 20(14): 9536–9542

109 Chen Y Z , Zhang R , Jiao L , Jiang H L . Metal-organic framework-derived porous materials for catalysis. Coordination Chemistry Reviews, 2018, 362: 1–23

110 Lee J , Farha O K , Roberts J , Scheidt K A , Nguyen S T , Hupp J T . Metal-organic framework materials as catalysts. Chemical Society Reviews, 2009, 38(5): 1450–1459

111 Yi J D , Xie R , Xie Z L , Chai G L , Liu T F , Chen R P , Huang Y B , Cao R . Highly selective CO₂ electroreduction to CH₄ by in situ generated Cu₂O single-type sites on a conductive MOF: stabilizing key intermediates with hydrogen bonding. Angewandte Chemie, 2020, 132(52): 23849–23856

112 Liu Y , Li S , Dai L , Li J , Lv J , Zhu Z , Yin A , Li P , Wang B . The synthesis of hexaazatrinaphthylene-based 2D conjugated copper metal-organic framework for highly selective and stable electroreduction of CO₂ to methane. Angewandte Chemie, 2021, 133(30): 16545–16551

113 Li J , Huang H , Xue W , Sun K , Song X , Wu C , Nie L , Li Y , Liu C , Pan Y . . Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO₂ photoreduction to CH₄. Nature Catalysis, 2021, 4(8): 719–729

114 Tian Y , Zhu C , Yan L , Zhao J , Su Z . Two-dimensional π-conjugated metal bis(dithiolene) nanosheets as promising electrocatalysts for carbon dioxide reduction: a computational study. Journal of Materials Chemistry A, 2019, 7(25): 15341–15346

115 Xing G , Cheng L , Li K , Gao Y , Tang H , Wang Y , Wu Z . Efficient electroreduction of CO₂ by single-atom catalysts two-dimensional metal hexahydroxybenzene frameworks: a theoretical study. Applied Surface Science, 2021, 550: 149389

116 Cove H , Toroz D , Di Tommaso D . The effect of the oxidation state of the metal center in metalloporphyrins on the electrocatalytic CO₂-to-CO conversion: a density functional theory study. Molecular Catalysis, 2020, 498: 111248

117 Zou L , Sa R , Lv H , Zhong H , Wang R . Recent advances on metalloporphyrin-based materials for visible-light-driven CO₂ reduction. ChemSusChem, 2020, 13(23): 6124–6140

118 Zhang R , Warren J J . Recent developments in metalloporphyrin electrocatalysts for reduction of small molecules: strategies for managing electron and proton transfer reactions. ChemSusChem, 2021, 14(1): 293–302

119 Kumar S , Wani M Y , Arranja C T , e Silva J A , Avula B , Sobral A J F N . Porphyrins as nanoreactors in the carbon dioxide capture and conversion: a review. Journal of Materials Chemistry A, 2015, 3(39): 19615–19637

120 Gotico P , Halime Z , Aukauloo A . Recent advances in metalloporphyrin-based catalyst design towards carbon dioxide reduction: from bio-inspired second coordination sphere modifications to hierarchical architectures. Dalton Transactions, 2020, 49(8): 2381–2396

121 Szkaradek K , Buzar K , Pidko E A , Szyja B M . Supported Ru metalloporphyrins for electrocatalytic CO₂ conversion. ChemCatChem, 2018, 10(8): 1814–1820

122 Gao W Y , Tsai C Y , Wojtas L , Thiounn T , Lin C C , Ma S . Interpenetrating metal-metalloporphyrin framework for selective CO₂ uptake and chemical transformation of CO₂. Inorganic Chemistry, 2016, 55(15): 7291–7294

123 Ifraemov R , Mukhopadhyay S , Hod I . Photo-assisted electrochemical CO₂ reduction to CH₄ using a Co-porphyrin-based metal-organic framework. Solar RRL, 2023, 7(5): 2201068

124 Wang C , Liu X M , Zhang M , Geng Y , Zhao L , Li Y G , Su Z M . Two-dimensional cobaltporphyrin-based cobalt-organic framework as an efficient photocatalyst for CO₂ reduction reaction: a computational study. ACS Sustainable Chemistry & Engineering, 2019, 7(16): 14102–14110

125 Wang X , Maeda K , Thomas A , Takanabe K , Xin G , Carlsson J M , Domen K , Antonietti M . A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nature Materials, 2009, 8(1): 76–80

126 Masih D , Ma Y , Rohani S . Graphitic C₃N₄ based noble-metal-free photocatalyst systems: a review. Applied Catalysis B: Environmental, 2017, 206: 556–588

127 Wen J , Xie J , Chen X , Li X . A review on g-C₃N₄-based photocatalysts. Applied Surface Science, 2017, 391: 72–123

128 Fu J , Yu J , Jiang C , Cheng B . g-C₃N₄-based heterostructured photocatalysts. Advanced Energy Materials, 2018, 8(3): 1701503

129 Ismael M . A review on graphitic carbon nitride (g-C₃N₄) based nanocomposites: synthesis, categories, and their application in photocatalysis. Journal of Alloys and Compounds, 2020, 846: 156446

130 Liu R , Chen Z , Yao Y , Li Y , Cheema W A , Wang D , Zhu S . Recent advancements in g-C₃N₄-based photocatalysts for photocatalytic CO₂ reduction: a mini review. RSC Advances, 2020, 10(49): 29408–29418

131 Ghosh U , Majumdar A , Pal A . Photocatalytic CO₂ reduction over g-C₃N₄ based heterostructures: recent progress and prospects. Journal of Environmental Chemical Engineering, 2021, 9(1): 104631

132 Ao C , Feng B , Qian S , Wang L , Zhao W , Zhai Y , Zhang L . Theoretical study of transition metals supported on g-C₃N₄ as electrochemical catalysts for CO₂ reduction to CH₃OH and CH₄. Journal of CO₂ Utilization, 2020, 36: 116–123

133 Sun N , Zhu Y , Li M , Zhang J , Qin J , Li Y , Wang C . Thermal coupled photocatalysis over Pt/g-C₃N₄ for selectively reducing CO₂ to CH₄ via cooperation of the electronic metal-support interaction effect and the oxidation state of Pt. Applied Catalysis B: Environmental, 2021, 298: 120565

134 Li H , Gao Y , Xiong Z , Liao C , Shih K . Enhanced selective photocatalytic reduction of CO₂ to CH₄ over plasmonic Au modified g-C₃N₄ photocatalyst under UV-vis light irradiation. Applied Surface Science, 2018, 439: 552–559

135 Guo C , Zhang T , Deng X , Liang X , Guo W , Lu X , Wu C M L . Electrochemical CO₂ reduction to C1 products on single nickel/cobalt/iron-doped graphitic carbon nitride: a DFT study. ChemSusChem, 2019, 12(23): 5126–5132

136 Wu T , Sun M , Huang B . Graphdiyne based catalysts for energy applications. Materials Chemistry Frontiers, 2021, 5(20): 7369–7383

137 Gao X , Liu H , Wang D , Zhang J . Graphdiyne: synthesis, properties, and applications. Chemical Society Reviews, 2019, 48(3): 908–936

138 Song B , Chen M , Zeng G , Gong J , Shen M , Xiong W , Zhou C , Tang X , Yang Y , Wang W . Using graphdiyne (GDY) as a catalyst support for enhanced performance in organic pollutant degradation and hydrogen production: a review. Journal of Hazardous Materials, 2020, 398: 122957

139 Wu S , Ji Y , Wang L , Wu X , Xu H . Selective CO₂-to-CH₄ photoconversion in aqueous solutions catalyzed by atomically dispersed copper sites anchored on ultrathin graphdiyne oxide nanosheets. Solar RRL, 2021, 5(7): 2100200

140 Zhao J , Chen Z , Zhao J . Metal-free graphdiyne doped with sp-hybridized boron and nitrogen atoms at acetylenic sites for high-efficiency electroreduction of CO₂ to CH₄ and C₂H₄. Journal of Materials Chemistry A, 2019, 7(8): 4026–4035

141 Feng Z , Tang Y , Ma Y , Li Y , Dai Y , Ding H , Su G , Dai X . Theoretical investigation of CO₂ electroreduction on N(B)-doped graphdiyne mononlayer supported single copper atom. Applied Surface Science, 2021, 538: 148145

142 Zhang W , Chao Y , Zhang W , Zhou J , Lv F , Wang K , Lin F , Luo H , Li J , Tong M , Wang E , Guo S . Emerging dual-atomic-site catalysts for efficient energy catalysis. Advanced Materials, 2021, 33(36): 2102576

143 Ying Y , Luo X , Qiao J , Huang H . “More is different:” synergistic effect and structural engineering in double-atom catalysts. Advanced Functional Materials, 2021, 31(3): 2007423

144 Zhang J , Huang Q A , Wang J , Wang J , Zhang J , Zhao Y . Supported dual-atom catalysts: preparation, characterization, and potential applications. Chinese Journal of Catalysis, 2020, 41(5): 783–798

145 Lin L , Li H , Yan C , Li H , Si R , Li M , Xiao J , Wang G , Bao X . Synergistic catalysis over iron-nitrogen sites anchored with cobalt phthalocyanine for efficient CO₂ electroreduction. Advanced Materials, 2019, 31(41): 1903470

146 Pei J , Wang T , Sui R , Zhang X , Zhou D , Qin F , Zhao X , Liu Q , Yan W , Dong J . . N-Bridged Co–N–Ni: new bimetallic sites for promoting electrochemical CO₂ reduction. Energy & Environmental Science, 2021, 14(5): 3019–3028

147 Jiao J , Yuan Q , Tan M , Han X , Gao M , Zhang C , Yang X , Shi Z , Ma Y , Xiao H . . Constructing asymmetric double-atomic sites for synergistic catalysis of electrochemical CO₂ reduction. Nature Communications, 2023, 14(1): 6164

148 Yang J , Liu X , Yuan H , Sun J , Li L , Goh K E J , Yu Z G , Xue J , Wang J , Zhang Y W . Beyond single-atom catalysts: exploration of Cu dimer and trimer for CO₂ reduction to methane. Applied Catalysis A: General, 2022, 642: 118708

149 Liu H , Huang Q , An W , Wang Y , Men Y , Liu S . Dual-atom active sites embedded in two-dimensional C₂N for efficient CO₂ electroreduction: a computational study. Journal of Energy Chemistry, 2021, 61: 507–516

150 Huang B , Wu Y , Luo Y , Zhou N . Double atom-anchored defective boron nitride catalyst for efficient electroreduction of CO₂ to CH₄: a first principles study. Chemical Physics Letters, 2020, 756: 137852

151 Kim C , Dionigi F , Beermann V , Wang X , Möller T , Strasser P . Alloy nanocatalysts for the electrochemical oxygen reduction (ORR) and the direct electrochemical carbon dioxide reduction reaction (CO₂RR). Advanced Materials, 2019, 31(31): 1805617

152 Liu J , Zhang T , Waterhouse G I . Complex alloy nanostructures as advanced catalysts for oxygen electrocatalysis: from materials design to applications. Journal of Materials Chemistry A, 2020, 8(44): 23142–23161

153 Da Y , Jiang R , Tian Z , Han X , Chen W , Hu W . The applications of single-atom alloys in electrocatalysis: progress and challenges. SmartMat, 2023, 4(1): e1136

154 Greeley J , Mavrikakis M . Near-surface alloys for hydrogen fuel cell applications. Catalysis Today, 2006, 111(1–2): 52–58

155 Huynh H L , Tucho W M , Yu X , Yu Z . Synthetic natural gas production from CO₂ and renewable H₂: towards large-scale production of Ni-Fe alloy catalysts for commercialization. Journal of Cleaner Production, 2020, 264: 121720

156 Zhao Z , Lu G . Computational screening of near-surface alloys for CO₂ electroreduction. ACS Catalysis, 2018, 8(5): 3885–3894

157 Mohan O , Xu R , Mushrif S H . Novel nickel-based single-atom alloy catalyst for CO₂ conversion reactions: computational screening and reaction mechanism analysis. Journal of Physical Chemistry C, 2021, 125(7): 4041–4055

158 Nasalevich M , Van der Veen M , Kapteijn F , Gascon J . Metal-organic frameworks as heterogeneous photocatalysts: advantages and challenges. CrystEngComm, 2014, 16(23): 4919–4926

159 Mahmood A , Guo W , Tabassum H , Zou R . Metal-organic framework-based nanomaterials for electrocatalysis. Advanced Energy Materials, 2016, 6(17): 1600423

160 Guo C C , Chu M F , Liu Q , Liu Y , Guo D C , Liu X Q . Effective catalysis of simple metalloporphyrins for cyclohexane oxidation with air in the absence of additives and solvents. Applied Catalysis A: General, 2003, 246(2): 303–309

161 Yu H , Xue Y , Li Y . Graphdiyne and its assembly architectures: synthesis, functionalization, and applications. Advanced Materials, 2019, 31(42): 1803101

162 Giannakakis G , Flytzani-Stephanopoulos M , Sykes E C H . Single-atom alloys as a reductionist approach to the rational design of heterogeneous catalysts. Accounts of Chemical Research, 2019, 52(1): 237–247

163 Zafeiratos S , Piccinin S , Teschner D . Alloys in catalysis: phase separation and surface segregation phenomena in response to the reactive environment. Catalysis Science & Technology, 2012, 2(9): 1787–1801

164 Chen B W , Xu L , Mavrikakis M . Computational methods in heterogeneous catalysis. Chemical Reviews, 2021, 121(2): 1007–1048

165 Sun Z , Yin H , Liu K , Cheng S , Li G K , Kawi S , Zhao H , Jia G , Yin Z . Machine learning accelerated calculation and design of electrocatalysts for CO₂ reduction. SmartMat, 2022, 3(1): 68–83

166 Mou L H , Han T , Smith P E , Sharman E , Jiang J . Machine learning descriptors for data-driven catalysis study. Advanced Science, 2023, 10(22): 2301020

167 Guo Y , He X , Su Y , Dai Y , Xie M , Yang S , Chen J , Wang K , Zhou D , Wang C . Machine-learning-guided discovery and optimization of additives in preparing Cu catalysts for CO₂ reduction. Journal of the American Chemical Society, 2021, 143(15): 5755–5762

168 Chen A , Zhang X , Chen L , Yao S , Zhou Z . A machine learning model on simple features for CO₂ reduction electrocatalysts. Journal of Physical Chemistry C, 2020, 124(41): 22471–22478