石墨烯是一种具有高度π键共轭相互作用的二维碳纳米材料，因其大的比表面积、出色的电荷载流子迁移率和高热/化学稳定性而被认为是最有前途的碳基材料，可在国民生活与生产的各个领域中广泛应用。作为变质程度最高的煤种，无烟煤的有机组分中含有丰富芳香碳环结构，可作为构成石墨烯的基本单元。基于无烟煤的这一特性，本论文以晋城无烟煤为原料，通过调变煤炭有机结构，采用自上而下的思路开发煤炭制备石墨烯的工艺路线，并对煤基石墨烯进行功能化修饰，考察其在氧还原反应（ORR）过程的催化性能。主要研究结果总结如下：

      （1）以廉价丰富的晋城煤作为碳源，经过粉碎、脱灰、高温石墨化及化学氧化等手段制备得到煤基氧化石墨烯（GO），进一步碳化得到煤基石墨烯（CGO）。以CGO和氮掺杂纳米结晶纤维素为原料，制备氮掺杂煤基石墨烯（NG），表征并测试其形貌、结构特征和ORR活性。研究表明：NG在碱性介质中具有比CGO催化剂更高的氧还原反应催化性能，同时保留了CGO优异的稳定性，在6 h后电流密度依旧保持在98.43%。

     （2）以GO为载体，将多巴胺包裹的ZIF-67核壳结构锚定在石墨烯表面，成功得到煤基石墨烯修饰的钴、氮共掺杂核壳碳基材料（Co-NDAC@CG）。采用SEM、TEM、Raman、XRD、BET、XPS等测试手段系统研究了复合材料Co-NDAC@CG的形貌和结构特征。研究表明：具有分级多孔结构和高表面积（439 m²·g^-1）等特点的Co-NDAC@CG显示出高的氧还原反应活性，在碱性介质中的半波电位和极限电流密度分别为0.84 V和4.73 mA·cm^-2，表现出优异的电化学性能。与商用的Pt/C催化剂相比，Co-NDAC@CG不仅具有良好的电化学稳定性，而且还具有优异的甲醇耐受性。

     （3）以无烟煤制备的GO为前驱体，制备得到钴、氮共掺杂碳纳米管（Co-N@CNT-CG）复合材料。采用SEM、TEM、Raman、XRD、BET、XPS等测试手段对合成的Co-N@CNT-CG结构和形貌进行表征。研究表明：所得到的Co-N@CNT-CG由许多石墨碳（包括碳纳米管）和大量的Co掺杂和N掺杂组成，具有较大的表面积（637 m²·g^-1）和良好的三维结构。进一步考察Co-N@CNT-CG材料的ORR性能可知，Co-N@CNT-CG在碱性电解质中表现出较好的ORR活性（E_1/2=0.85 V, j_k=6.21 mA·cm^-2），电化学稳定性和抗甲醇性得到进一步提高。

       Graphene is a two-dimensional carbon nanomaterial with highly conjugated π-bond interactions. It is considered the most promising carbon-based material due to its large specific surface area, excellent charge carrier mobility, and high thermal/chemical stability. Graphene materials can be applied in various fields in daily life and industrial processes. Anthracites, the most metamorphic coal species, contain many components with aromatic carbon ring structures, which can be used to construct a graphene framework. Based on the character mentioned above, Jincheng anthracite is used as a raw material to make coal-based graphene by adjusting the organic structure of the coal component. The relative process is also developed. Furthermore, the obtained coal-based graphene is functionalized and applied in oxygen reduction reaction (ORR) for catalytic proposes. The main research results are:

       (1) Jincheng coal, featured with low cost and easy obtaining, is used as a carbon source. Jincheng coal is processed by pulverization, grinding, acid leaching, and deashing to produce coal-based graphite. The obtained graphite is handled by the improved Hummers method with graphitization and high-temperature pyrolyzation to produce graphene (CGO). Nitrogen-doped coal-based graphene oxide (NG) was successfully prepared by pyrolysis of coal-based graphene oxide and nitrogen-doped nanocrystalline cellulose at a high temperature. The morphology, crystal structure, defects, nitrogen-based group, and ORR activity are tested. The results show that NG has higher catalytic performance for oxygen reduction reaction than CGO catalyst in alkaline medium. Nitrogen-doped coal-based graphene oxide retains the excellent stability of CGO, and the current density can be maintained to 98.43% after 6 h. The introduction of nitrogen groups significantly improved the ORR catalytic activity of the composite, but it is still inferior to commercialized Pt/C catalysts.

       (2) Core-shell structure ZIF-67 claded by dopamines was physically anchored to the GO surface to obtain the coal-based graphene embellished core-shell carbon-based material with Co-N doping (Co-NDAC@CG). The morphology and structure of the Co-NDAC@CG can be studied by the results from SEM, TEM, Raman, XRD, BET, and XPS. Coal-based GO exhibits a novel interconnected porous structure in the conductive network with a reasonable porous rate. Also, Co-NDAC@CG, featured with high specific surface area (439 m²·g^-1), showed high ORR activity. Co-NDAC@CG showed an excellent performance in half-wave potential and limiting current density in alkaline medium, with a value of E_1/2=0.84 V and j_k=4.73 mA·cm^-2 respectively. Compared with commercial Pt/C material, Co-NDAC@CG is better in electrochemical stability and methanol resistance.

       (3) With the graphene made from anthracite as the precursor, Co-N@CNT-CG was prepared by combining carambola-shaped MOFs (ZIF-8@ZIF-67). The structure and morphology of the synthesized Co-N@CNT-CG were characterized by SEM, TEM, Raman, XRD, BET, and XPS. The obtained Co-N@CNT-CG is composed of many graphite carbons (including carbon nanotubes) and a large amount of Co and N doping, with a large surface area (637 m²·g^-1) and an excellent three-dimensional structure. Co-N@CNT-CG exhibits excellent performance in terms of half-wave potential and finite current density in alkaline medium with a value of 0.85 V and 6.21 mA·cm^-2, respectively. Moreover, Co-N@CNT-CG exhibits good electrochemical stability and methanol tolerance compared with commercial Pt/C materials.

[1] Zhang Y, Jin B, Zou X, Zhao H. A clean coal utilization technology based on coal pyrolysis and chemical looping with oxygen uncoupling: Principle and experimental validation[J]. Energy, 2016; 98: 181-189.

[2] Huan X, Tang Y-G, Xu J-J, Lan C-Y, Wang S-Q. Structural characterization of graphenic material prepared from anthracites of different characteristics:A comparative analysis[J]. Fuel Processing Technology, 2019; 183: 8-18.

[3] Atria J V, Rusinko F, Schobert H H. Structural Ordering of Pennsylvania Anthracites on Heat Treatment to 2000-2900 oC[J]. Energy & Fuels, 2002; 16(6): 1343-1347.

[4] Wang S, Jiang S P. Prospects of fuel cell technologies[J]. National Science Review, 2017; 4(2):163-166.

[5] González D, Altin O, Eser S, Garcia A B. Temperature-programmed oxidation studies of carbon materials prepared from anthracites by high temperature treatment[J]. Materials Chemistry and Physics, 2007; 101(1): 137-141.

[6] Dave S H, Gong C, Robertson A W, Warner J H. Chemistry and Structure of Graphene Oxide via Direct Imaging[J]. ACS Nano, 2016; 10(8): 7515-7522.

[7] Zhao Y, Chai L, Yan X, Huang W, Fan T. Characteristics, properties, synthesis and advanced applications of 2D graphdiyne versus graphene[J]. Materials Chemistry Frontiers, 2022; 10: 1039-1046.

[8] Ghuge D, Shirode R, Abhay and Kadam J. Vilasrao, Graphene: A Comprehensive Review[J]. Current Drug Targets, 2017; 18(6): 724 - 733.

[9] Amiri A, Naraghi M, Ahmadi G, Soleymaniha M, Shanbedi M. A review on liquid-phase exfoliation for scalable production of pure graphene, wrinkled, crumpled and functionalized graphene and challenges[J]. FlatChem, 2018; 8: 40-71.

[10] Abdelkareem M A, Elsaid K, Wilberforce T, Kamil M, Sayed E T, Olabi A. Environmental aspects of fuel cells: A review[J]. Science of The Total Environment, 2021; 752: 141803.

[11] Stankovich S, Dikin D A, Piner R D, Kohlhaas K A, Kleinhammes A, Jia Y, Wu Y, Nguyen S T, Ruoff R S. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J]. Carbon, 2007; 45(7): 1558-1565.

[12] Zhou J, Xie Z, Liu R, Gao X, Li J, Xiong Y, Tong L, Zhang J, Liu Z. Synthesis of Ultrathin Graphdiyne Film Using a Surface Template[J]. ACS Applied Materials & Interfaces, 2019; 11(3): 2632-2637.

[13] Gao X, Ren H, Zhou J, Du R, Yin C, Liu R, Peng H, Tong L, Liu Z, Zhang J. Synthesis of Hierarchical Graphdiyne-Based Architecture for Efficient Solar Steam Generation[J]. Chemistry of Materials, 2017; 29(14): 5777-5781.

[14] Zhao L, Ward C R, French D, Graham I T, Dai S, Yang C, Xie P, Zhang S. Origin of a kaolinite-NH4-illite-pyrophyllite-chlorite assemblage in a marine-influenced anthracite and associated strata from the Jincheng Coalfield, Qinshui Basin, Northern China[J]. International Journal of Coal Geology, 2018; 185: 61-78.

[15] Nyathi M S, Clifford C B, Schobert H H. Characterization of graphitic materials prepared from different rank Pennsylvania anthracites[J]. Fuel, 2013; 114: 244-250.

[16] Liao K-H, Mittal A, Bose S, Leighton C, Mkhoyan K A, Macosko C W. Aqueous Only Route toward Graphene from Graphite Oxide[J]. ACS Nano, 2011; 5(2): 1253-1258.

[17] Zhou Q, Zhao Z, Zhang Y, Meng B, Zhou A, Qiu J. Graphene Sheets from Graphitized Anthracite Coal: Preparation, Decoration, and Application[J]. Energy & Fuels, 2012; 26(8): 5186-5192.

[18] Wang L, Zhu B, Cheng B, Zhang J, Zhang L, Yu J. In-situ preparation of TiO2/N doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO2 reduction performance[J]. Chinese Journal of Catalysis, 2021; 42(10): 1648-1658.

[19] Zhu H, Gan X, McCreary A, Lv R, Lin Z, Terrones M. Heteroatom doping of two-dimensional materials: From graphene to chalcogenides[J]. Nano Today, 2020; 30: 100829.

[20] Yang Y, Jiang X, Li Y, Jin W, Huang X. Construction of halogenated graphenes by halogenation of hydrogenated graphene[J]. Composites Communications, 2021; 25: 100771.

[21] Li G-L, Liu C-D, Chen S-M, Hao C, Cheng G-C, Xie Y-Y. Promotion of oxygen reduction performance by Fe3O4 nanoparticles support nitrogen-doped three dimensional meso/macroporous carbon based electrocatalyst[J]. International Journal of Hydrogen Energy, 2017; 42(7): 4133-4145.

[22] He W, Xue P, Du H, Xu L, Pang M, Gao X, Yu J, Zhang Z, Huang T. A facile method prepared nitrogen and boron doped carbon nano-tube based catalysts for oxygen reduction[J]. International Journal of Hydrogen Energy, 2017; 42(7): 4123-4132.

[23] Alaswad A, Baroutaji A, Achour H, Carton J, Al Makky A, Olabi A G. Developments in fuel cell technologies in the transport sector[J]. International Journal of Hydrogen Energy, 2016; 41(37): 16499-16508.

[24] Xu Q, Xia L, He Q, Guo Z, Ni M. Thermo-electrochemical modelling of high temperature methanol-fuelled solid oxide fuel cells[J]. Applied Energy, 2021; 291: 116832.

[25] Abdelkareem M A, Elsaid K, Wilberforce T, Kamil M, Sayed E T, Olabi A. Environmental aspects of fuel cells: A review[J]. Science of The Total Environment, 2021; 752: 141803.

[26] Lutz A E, Larson R S, Keller J O. Thermodynamic comparison of fuel cells to the Carnot cycle[J]. International Journal of Hydrogen Energy, 2002; 27(10): 1103-1111.

[27] Tommasi T, Lombardelli G. Energy sustainability of Microbial Fuel Cell (MFC): A case study[J]. Journal of Power Sources, 2017; 356: 438-447.

[28] Ferraren-De Cagalitan D D T, Abundo M L S. A review of biohydrogen production technology for application towards hydrogen fuel cells[J]. Renewable and Sustainable Energy Reviews, 2021; 151: 111413.

[29] Chatterjee S, Sengupta K, Mondal B, Dey S, Dey A. Factors Determining the Rate and Selectivity of 4e-/4H+ Electrocatalytic Reduction of Dioxygen by Iron Porphyrin Complexes[J]. Accounts of Chemical Research, 2017; 50(7): 1744-1753.

[30] Meng X, Ren H, Yang X, Tao T, Shao Z. Experimental study of key operating parameters effects on the characteristics of proton exchange membrane fuel cell with anode recirculation[J]. Energy Conversion and Management, 2022; 256: 115394.

[31] Thomas J M, Edwards P P, Dobson P J, Owen G P. Decarbonising energy: The developing international activity in hydrogen technologies and fuel cells[J]. Journal of Energy Chemistry, 2020; 51: 405-415.

[32] Li J, Sharma S, Liu X, Pan Y-T, Spendelow J S, Chi M, Jia Y, Zhang P, Cullen D A, Xi Z, Lin H, Yin Z, Shen B, Muzzio M, Yu C, Kim Y S, Peterson A A, More K L, Zhu H, Sun S. Hard-Magnet L10-CoPt Nanoparticles Advance Fuel Cell Catalysis[J]. Joule, 2019; 3(1): 124-135.

[33] Niu H-J, Chen H-Y, Wen G-L, Feng J-J, Zhang Q-L, Wang A-J. One-pot solvothermal synthesis of three-dimensional hollow PtCu alloyed dodecahedron nanoframes with excellent electrocatalytic performances for hydrogen evolution and oxygen reduction[J]. Journal of Colloid and Interface Science, 2019; 539: 525-532.

[34] Bu L, Shao Q, E B, Guo J, Yao J, Huang X. PtPb/PtNi Intermetallic Core/Atomic Layer Shell Octahedra for Efficient Oxygen Reduction Electrocatalysis[J]. Journal of the American Chemical Society, 2017; 139(28): 9576-9582.

[35] Bhalothia D, Chou J-P, Yan C, Hu A, Yang Y-T, Chen T-Y. Programming ORR Activity of Ni/NiOx@Pd Electrocatalysts via Controlling Depth of Surface-Decorated Atomic Pt Clusters[J]. ACS Omega, 2018; 3(8): 8733-8744.

[36] Li H, Ha T A, Jiang S, Pozo-Gonzalo C, Wang X, Fang J, Howlett P C, Wang X. N, F and S doped carbon nanofibers generated from electrospun polymerized ionic liquids for metal-free bifunctional oxygen electrocatalysis[J]. Electrochimica Acta, 2021; 377: 138089.

[37] Jiang H, Gu J, Zheng X, Liu M, Qiu X. Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER[J]. Energy Environ, 2019

[38] Ahamad T, Naushad M, Hassan Mousa R, Khalaf N, Alshehri S M. Synthesis and characterization cobalt phosphate embedded with N doped carbon for water splitting ORR and OER[J]. Journal of King Saud University-Science, 2020; 32(6): 2826-2830.

[39] Liu D, Li L, Xu H. Boosting ORR Catalytic Activity by Integrating Pyridine‐N Dopants, a High Degree of Graphitization, and Hierarchical Pores into a MOF‐Derived N‐Doped Carbon in a Tandem Synthesis[J]. Chemistry An Asian Journal, 2018; 18: 1318-1326.

[40] Gawande M B, Moores A, Varma R S. ACS Sustainable Chemistry & Engineering Virtual Special Issue on N-Doped Carbon Materials: Synthesis and Sustainable Applications[J]. ACS Sustainable Chemistry & Engineering, 2021; 9(11): 3975-3976.

[41] Kang B, Shi H, Wang F-F, Lee J Y. Importance of doping site of B, N, and O in tuning electronic structure of graphynes[J]. Carbon, 2016; 105: 156-162.

[42] Mousavi-Khoshdel S M, Jahanbakhsh-bonab P, Targholi E. Structural, electronic properties, and quantum capacitance of B, N and P-doped armchair carbon nanotubes[J]. Physics Letters A, 2016; 380(41): 3378-3383.

[43] Yu C, Fang H, Liu Z, Hu H, Meng X, Qiu J. Chemically grafting graphene oxide to B,N co-doped graphene via ionic liquid and their superior performance for triiodide reduction[J]. Nano Energy, 2016; 25: 184-192.

[44] Novodchuk I, Kayaharman M, Ausri I R, Karimi R, Tang X S, Goldthorpe I A, Abdel-Rahman E, Sanderson J, Bajcsy M, Yavuz M. An ultrasensitive heart-failure BNP biosensor using B/N co-doped graphene oxide gel FET[J]. Biosensors and Bioelectronics, 2021; 180: 113114.

[45] Novodchuk I, Kayaharman M, Ibrahim K, Al-Tuairqi S, Irannejad M, Abdel-Rahman E, Sanderson J, Bajcsy M, Yavuz M. B/N co-doped graphene oxide gel with extremely-high mobility and ION/IOFF for large-area field effect transistors[J]. Carbon, 2020; 158: 624-630.

[46] Li J-C, Qin X, Hou P-X, Cheng M, Shi C, Liu C, Cheng H-M, Shao M. Identification of active sites in nitrogen and sulfur co-doped carbon-based oxygen reduction catalysts[J]. Carbon, 2019; 147: 303-311.

[47] Yao S, Lyu D, Wei M, Chu B, Huang Y, Pan C, Zhang X, Tian Z Q, Shen P K. N, S, P co-doped graphene-like carbon nanosheets developed via in situ engineering strategy of carbon pz-orbitals for highly efficient oxygen redox reaction[J]. FlatChem, 2021; 27: 100250.

[48] Wang Y, Xu N, He R, Peng L, Cai D, Qiao J. Large-scale defect-engineering tailored tri-doped graphene as a metal-free bifunctional catalyst for superior electrocatalytic oxygen reaction in rechargeable Zn-air battery[J]. Applied Catalysis B: Environmental, 2021; 285: 119811.

[49] Ryabova A S, Bonnefont A, Simonov P A, Dintzer T, Ulhaq-Bouillet C, Bogdanova Y G, Tsirlina G A, Savinova E R. Further insights into the role of carbon in manganese oxide/carbon composites in the oxygen reduction reaction in alkaline media[J]. Electrochimica Acta, 2017; 246: 643-653.

[50] Daş E, Alkan Gürsel S, Bayrakçeken Yurtcan A. Pt-alloy decorated graphene as an efficient electrocatalyst for PEM fuel cell reactions[J]. The Journal of Supercritical Fluids, 2020; 165: 104962.

[51] Toh R J, Sofer Z, Pumera M. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table[J]. ChemPhysChem, 2015; 16: 3527-3531.

[52] Yang S, Du R, Yu Y, Zhang Z, Wang F. One-step electrodeposition of carbon quantum dots and transition metal ions for N-doped carbon coupled with NiFe oxide clusters: A high-performance electrocatalyst for oxygen evolution[J]. Nano Energy, 2020; 77: 105057.

[53] Zhang W, Sun S, Yang L, Lu C, He Y, Zhang C, Cai M, Yao Y, Zhang F, Zhuang X. Polymer nanosheets derived porous carbon nanosheets as high efficient electrocatalysts for oxygen reduction reaction[J]. Journal of Colloid and Interface Science, 2018; 516: 9-15.

[54] Chen J, Wei X, Zhang J, Luo Y, Chen Y, Wang G, Wang R. Titanium Nitride Hollow Spheres Consisting of TiN Nanosheets and Their Controllable Carbon-Nitrogen Active Sites as Efficient Electrocatalyst for Oxygen Reduction Reaction[J]. Industrial & Engineering Chemistry Research, 2019; 58(8): 2741-2748.

[55] Zhang H, Wang Z, Zhou J, Xie T, Zhou Z, Cao L, Gong X, Yang J. Strong anion exchange for improved NiCo2S4 oxygen reduction reaction via interlayer spacing manipulation[J]. International Journal of Hydrogen Energy, 2022; 47(21): 11224-11235.

[56] Fang W, Hu H, Jiang T, Li G, Wu M. N- and S-doped porous carbon decorated with in-situ synthesized Co-Ni bimetallic sulfides particles: A cathode catalyst of rechargeable Zn-air batteries[J]. Carbon, 2019; 146: 476-485.

[57] Zhu W, Pei Y, Douglin J C, Zhang J, Zhao H, Xue J, Wang Q, Li R, Qin Y, Yin Y, Dekel D R, Guiver M D. Multi-scale study on bifunctional Co/Fe-N-C cathode catalyst layers with high active site density for the oxygen reduction reaction[J]. Applied Catalysis B: Environmental, 2021; 299: 120656.

[58] Mo R, Zhang X, Chen Z, Huang S, Li Y, Liang L, Tian Z Q, Shen P K. Highly efficient PtCo nanoparticles on Co-N-C nanorods with hierarchical pore structure for oxygen reduction reaction[J]. International Journal of Hydrogen Energy, 2021; 46(29): 15991-16002.

[59] Hou Y, Zhao Z, Yu Z, Tang Y, Wang X, Qiu J. Two-dimensional graphene-like N, Co-codoped carbon nanosheets derived from ZIF-67 polyhedrons for efficient oxygen reduction reaction[J]. Chemical Communications, 2017; 53: 7840-7843.

[60] Zhang X, Huang X, Hu W, Huang Y. A metal-organic framework-derived Fe-N-C electrocatalyst with highly dispersed Fe-Nx towards oxygen reduction reaction[J]. International Journal of Hydrogen Energy, 2019; 44(50): 27379-27389.

[61] 张亚婷, 李可可, 刘国阳, 周安宁, 王露, 邱介山. 煤基石墨烯宏观体的制备及其在CO2光催化还原过程中的应用[J]. 新型炭材料, 2015; 30(06): 539-544.

[62] Zhou Q, Zhao Z, Zhang Y, Meng B, Zhou A, Qiu J. Graphene Sheets from Graphitized Anthracite Coal: Preparation, Decoration, and Application[J]. Energy & Fuels, 2012; 26(8): 5186-5192.

[63] Sridhar V, Kim H-J, Jung J-H, Lee C, Park S, Oh I-K. Defect-Engineered Three-Dimensional Graphene-Nanotube-Palladium Nanostructures with Ultrahigh Capacitance[J]. ACS Nano, 2012; 6(12): 10562-10570.

[64] Xing B, Zhang C, Cao Y, Huang G, Liu Q, Zhang C, Chen Z, Yi G, Chen L, Yu J. Preparation of synthetic graphite from bituminous coal as anode materials for high performance lithium-ion batteries[J]. Fuel Processing Technology, 2018; 172: 162-171.

[65] Xing B, Zeng H, Huang G, Zhang C, Yuan R, Cao Y, Chen Z, Yu J. Porous graphene prepared from anthracite as high performance anode materials for lithium-ion battery applications[J]. Journal of Alloys and Compounds, 2019; 779: 202-211.

[66] Savitskii D P. Preparation and characterization of colloidal dispersions of graphene-like structures from different ranks of coals[J]. Journal of Fuel Chemistry and Technology, 2017; 45(8): 897-907.

[67] Niu H-J, Zhang L, Feng J-J, Zhang Q-L, Huang H, Wang A-J. Graphene encapsulated cobalt nanoparticles embedded in porous nitrogen-doped graphitic carbon nanosheets as efficient electrocatalysts for oxygen reduction reaction[J]. Journal of Colloid and Interface Science, 2019; 552: 744-751.

[68] Peera S G, Sahu A K, Arunchander A, Bhat S D, Karthikeyan J, Murugan P. Nitrogen and fluorine co-doped graphite nanofibers as high durable oxygen reduction catalyst in acidic media for polymer electrolyte fuel cells[J]. Carbon, 2015; 93: 130-142.

[69] Cheng W, Zhao X, Su H. Lattice-strained metal-organic-framework arrays for bifunctional oxygen electrocatalysis[J]. Nat Energy, 2019; 4: 115-122.

[70] Peera S G, Sahu A K, Arunchander A, Bhat S D, Karthikeyan J, Murugan P. Nitrogen and fluorine co-doped graphite nanofibers as high durable oxygen reduction catalyst in acidic media for polymer electrolyte fuel cells[J]. Carbon, 2015; 93: 130-142.

[71] Geng Z, Cao Y, Chen W, Kong X, Liu Y, Yao T, Lin Y. Regulating the coordination environment of Co single atoms for achieving efficient electrocatalytic activity in CO2 reduction[J]. Applied Catalysis B: Environmental, 2019; 240: 234-240.

[72] Jiang S, Zhu C, Dong S. Cobalt and nitrogen-cofunctionalized graphene as a durable non-precious metal catalyst with enhanced ORR activity[J]. Journal of Materials Chemistry A, 2013; 1(11): 3593-3599.

[73] Wang K, Yang J, Liu W, Yang H, Yi W, Sun Y, Yang G. Self‑nitrogen-doped carbon materials derived from microalgae by lipid extraction pretreatment: Highly efficient catalyst for the oxygen reduction reaction[J]. Science of The Total Environment, 2022; 821: 153155.

[74] Ye H, Li L, Liu D, Fu Q, Zhang F, Dai P, Gu X, Zhao X. Sustained-Release Method for the Directed Synthesis of ZIF-Derived Ultrafine Co-N-C ORR Catalysts with Embedded Co Quantum Dots[J]. ACS Applied Materials & Interfaces, 2020; 12(52): 57847-57858.

[75] Ren S, Guo Y, Ma S, Mao Q, Wu D, Yang Y, Jing H, Song X, Hao C. Co3O4 nanoparticles assembled on polypyrrole/graphene oxide for electrochemical reduction of oxygen in alkaline media[J]. Chinese Journal of Catalysis, 2017; 38(7): 1281-1290.

[76] Zhou Q, Zhang Z, Cai J, Liu B, Zhang Y, Gong X, Sui X, Yu A, Zhao L, Wang Z, Chen Z. Template-guided synthesis of Co nanoparticles embedded in hollow nitrogen doped carbon tubes as a highly efficient catalyst for rechargeable Zn-air batteries[J]. Nano Energy, 2020; 71: 104592.

[77] Lai Q, Zheng L, Liang Y, He J, Zhao J, Chen J. Metal-Organic-Framework DerivedFe-N/C Electrocatalyst with Five-Coordinated Fe-Nx Sites for Advanced Oxygen Reduction in Acid Media[J]. ACS Catalysis, 2017; 7(3): 1655-1663.

[78] Xia D, Tang F, Yao X, Wei Y, Cui Y, Dou M, Gan L, Kang F. Seeded growth of branched iron-nitrogen-doped carbon nanotubes as a high performance and durable non-precious fuel cell cathode[J]. Carbon, 2020; 162: 300-307.

[79] Niu Y, Teng X, Wang J, Liu Y, Guo L, Song W, Chen Z. Space-Confined Strategy to Fe7C3 Nanoparticles Wrapped in Porous Fe-/N-Doped Carbon Nanosheets for Efficient Oxygen Electrocatalysis[J]. ACS Sustainable Chemistry & Engineering, 2019; 7(15): 13576-13583.

[80] Zhu Z, Chen C, Cai M, Cai Y, Ju H, Hu S, Zhang M. Porous Co-N-C ORR catalysts of high performance synthesized with ZIF-67 templates[J]. Materials Research Bulletin, 2019; 114: 161-169.

[81] Wang T, He Y, Liu Y, Guo F, Li X, Chen H, Li H, Lin Z. A ZIF-triggered rapid polymerization of dopamine renders Co/N-codoped cage-in-cage porous carbon for highly efficient oxygen reduction and evolution[J]. Nano Energy, 2021; 79: 105487

[82] Mehri M, Mousavi-Khoshdel S M, Molaei M. First-principle calculations study of pristine, S-, O-, and P-doped g-C3N4 as ORR catalysts for Li-O2 batteries[J]. Chemical Physics Letters, 2021; 775: 138614.

[83] Zhang J, Song L, Zhao C, Yin X, Zhao Y. Co, N co-doped porous carbons as high-performance oxygen reduction electrocatalysts[J]. New Carbon Materials, 2021; 36(1): 209-218.

[84] Gu D, Ma R, Zhou Y, Wang F, Yan K, Liu Q, Wang J. Synthesis of Nitrogen-Doped Porous Carbon Spheres with Improved Porosity toward the Electrocatalytic Oxygen Reduction[J]. ACS Sustainable Chemistry & Engineering, 2017; 5(11): 11105-11116.

[85] Liu Y, Li Z, Wang L, Zhang L, Niu X. Tunable Fe/N co-doped 3D porous graphene with high density Fe-Nx sites as the efficient bifunctional oxygen electrocatalyst for Zn-air batteries[J]. International Journal of Hydrogen Energy, 2021; 46(74): 36811-36823.

[86] Zhang Y, Wang P, Yang J, Li K, Long X, Li M, Zhang K, Qiu J. Fabrication of core-shell nanohybrid derived from iron-based metal-organic framework grappled on nitrogen-doped graphene for oxygen reduction reaction[J]. Chemical Engineering Journal, 2020; 401: 126001.

[87] Shi C, Liu Y, Qi R, Li J, Zhu J, Yu R, Li S, Hong X, Wu J, Xi S, Zhou L, Mai L. Hierarchical N-doped carbon spheres anchored with cobalt nanocrystals and single atoms for oxygen reduction reaction[J]. Nano Energy, 2021; 87: 106153.

[88] Cai J-J, Zhou Q-Y, Gong X-F, Liu B, Zhang Y-L, Dai Y-K, Gu D-M, Zhao L, Sui X-L, Wang Z-B. Metal-free amino acid glycine-derived nitrogen-doped carbon aerogel with superhigh surface area for highly efficient Zn-Air batteries[J]. Carbon, 2020; 167: 75-84.

[89] Fu K, Wang Y, Mao L, Yang X, Jin J, Yang S, Li G. Strongly coupled Co, N co-doped carbon nanotubes/graphene-like carbon nanosheets as efficient oxygen reduction electrocatalysts for primary Zinc-air battery[J]. Chemical Engineering Journal, 2018; 351: 94-102.

[90] Guo X, Zheng S, Luo Y, Pang H. Synthesis of confining cobalt nanoparticles within SiOx/nitrogen-doped carbon framework derived from sustainable bamboo leaves as oxygen electrocatalysts for rechargeable Zn-air batteries[J]. Chemical Engineering Journal, 2020; 401: 126005.

[91] Liu H, Liu Z-h, Zhang J-q, Zhi L-j, Wu M-b. Boron and nitrogen co-doped carbon dots for boosting electrocatalytic oxygen reduction[J]. New Carbon Materials, 2021; 36(3): 585-593.

[92] Zhang Y, Wang P, Yang J, Lu S, Li K, Liu G, Duan Y, Qiu J. Decorating ZIF-67-derived cobalt-nitrogen doped carbon nanocapsules on 3D carbon frameworks for efficient oxygen reduction and oxygen evolution[J]. Carbon, 2021; 177: 344-356.

[93] Wu M-X, Wang Y, Zhou G, Liu X. Core-Shell MOFs@MOFs: Diverse Designability and Enhanced Selectivity[J]. ACS Applied Materials & Interfaces, 2020; 12(49): 54285-54305.

[94] Panchariya D K, Rai R K, Anil Kumar E, Singh S K. Core-Shell Zeolitic Imidazolate Frameworks for Enhanced Hydrogen Storage[J]. ACS Omega, 2018; 3(1): 167-175.

[95] Meng J, Niu C, Xu L, Li J, Liu X, Wang X, Wu Y, Xu X, Chen W, Li Q, Zhu Z, Zhao D, Mai L. General Oriented Formation of Carbon Nanotubes from Metal–Organic Frameworks[J]. Journal of the American Chemical Society, 2017; 139(24): 8212-8221.

[96] Mi J-L, Liang J-H, Yang L-P, Wu B, Liu L. Effect of Zn on Size Control and Oxygen Reduction Reaction Activity of Co Nanoparticles Supported on N-Doped Carbon Nanotubes[J]. Chemistry of Materials, 2019; 31(21): 8864-8874.

[97] Zhang J, Zhang J, He F, Chen Y, Zhu J, Wang D. Defect and Doping Co-engineered Non-Metal Nanocarbon ORR Electrocatalyst[J]. Nano-Micro Letters, 2020, 65; 42-43.

[98] Wang H, Abruña H D. IrPdRu/C as H2 Oxidation Catalysts for Alkaline Fuel Cells[J]. Journal of the American Chemical Society, 2017; 139(20): 6807-6810.