马浚腾,吴海涛,卫仁杰,耿浩然,魏宗源,曹思婕,李世杰,董琛

• 1:苏州科技大学化学与生命科学学院
• 2:中国五洲工程设计集团有限公司

摘要(Abstract)：

全球能源问题愈发严峻，氢能源战略地位日益凸显。电解水制氢被认为是最有前景的获氢途径，但由于其析氢反应和析氧反应的反应动力学缓慢，导致实际生产中电解效率低且能耗高，故迫切需要开发高效且成本低廉的电催化剂。为此，以资源丰富的废弃榴莲壳为原料，在实现废弃生物质再利用的同时通过低温掺杂、高温碳化的方式制备了氮硫共掺杂榴莲壳衍生的生物质碳(NS-DC)。得益于氮、硫双杂原子的掺杂，碳材料导电能力与活性缺陷位点数量得到了良好平衡，使得NSDC的电催化性能得到明显提升。作为电解水析氧反应催化剂，NS-DC达到10 mA·cm~(-2)的电流密度仅需458 mV的较低过电位，塔菲尔斜率为92 mV·dec~(-1)，具有良好的电荷转移动力学，且具有优良的稳定性。NS-DC的成功制备不仅证实了废弃生物质资源化利用的可行性，也为双杂原子掺杂调控生物质碳基材料的结构与性能提供了新思路。

关键词(KeyWords)： 析氧反应;电解水;生物质碳;氮硫共掺杂;电催化剂

Abstract:

Keywords:

基金项目(Foundation): 江苏省基础研究计划自然科学基金青年项目(BK20230653);; 江苏省高等学校基础科学(自然科学)研究项目(22KJB530009)

作者(Author): 马浚腾,吴海涛,卫仁杰,耿浩然,魏宗源,曹思婕,李世杰,董琛

参考文献(References)：

• [1]MAIHAN R,UYSAL S Y. A brief overview of renewable hydrogen production:prospects and challenges[J]. International Journal of Engineering Applied Sciences and Technology,2022,7(9):21-28.
• [2]LI H, XIE H N, WANG X X, et al.(FeSe2+CoSe2)nanoparticles anchored on 3D porous ultrathin carbon nanosheets for highactivity oxygen evolution reaction[J]. ACS Applied Nano Materials,2023,6(11):9598-9607.
• [3]HOU Z Q, CUI C H, LI Y N, et al. Lattice-strain engineering for heterogenous electrocatalytic oxygen evolution reaction[J].Advanced Materials,2023,35(39):2209876.
• [4]LIU Y,LIU G,CHEN X Y,et al. Achieving negatively charged Pt single atoms on amorphous Ni(OH)2 nanosheets with promoted hydrogen absorption in hydrogen evolution[J]. Nano-Micro Letters,2024,16:202.
• [5]ZHENG X Z, SHI X Y, NING H H, et al. Tailoring a local acid-like microenvironment for efficient neutral hydrogen evolution[J].Nature Communications,2023,14:4209.
• [6]ZHU Y M, WANG J, KOKETSU T, et al. Iridium single atoms incorporated in Co3O4 efficiently catalyze the oxygen evolution in acidic conditions[J]. Nature Communications,2024,15:1395.
• [7]ZHANG Y D, WANG Y, SUN W, et al. Suppression of oxygen vacancies in rutile RuO2 via in situ exsolution for enhanced water electrocatalysis[J]. Advanced Materials Interfaces,2023,10(17):2300279.
• [8]XIE Y H,LUO F,YANG Z H. Acidic oxygen evolution reaction via lattice oxygen oxidation mechanism:progress and challenges[J].Energy Materials,2025,5:500026.
• [9]MITSUDOME T. Air-stable and highly active transition metal phosphide catalysts for reductive molecular transformations[J]. Catalysts,2024,14(3):193.
• [10]CHOI Y J,LEE J H,YOUN D H. A review of stoichiometric Nickel sulfide-based catalysts for hydrogen evolution reaction in alkaline media[J]. Molecules,2024,29:4975.
• [11]TUCI G, ROSSIN A, ZHANG X, et al. Exohedrally functionalized carbon-based networks as catalysts for electrochemical syntheses[J]. Current Opinion in Green and Sustainable Chemistry,2022,33:100579.
• [12]KAMARUZAMAN N A, KHAIRUL W M, SALEH N M, et al. Advancements in carbon-based transition metal compounds for enhanced hydrogen production via electrochemical water splitting[J]. International Journal of Electrochemical Science, 2024,19(9):100740.
• [13]CHEN P R, YE J S, WANG H, et al. Recent progress of transition metal carbides/nitrides for electrocatalytic water splitting[J].Journal of Alloys and Compounds,2021,883:160833.
• [14]LI X L, HE H, YU Y H, et al. Boosting oxygen evolution reaction by synergistically coupling amorphous high-entropy borate FeCoNiMnBOx with MXene[J]. Applied Surface Science,2024,645:158838.
• [15]刘法明，李国宁，马为洋，等.生物质碳基电解水催化剂定向构筑研究进展[J].洁净煤技术，2024,30(3):124-136.LIU F M,MA G N,MA W Y,et al. Research progress on the directed construction of biomass carbon-based electrocatalysts for water electrolysis[J]. Clean Coal Technology,2024,30(3):124-136.
• [16]WU H Y, ZHAO Q Q, JIANG S, et al. Research advances in doped carbon electrocatalysts derived from biomass[J]. Chemical Engineering Journal,2025,505:159694.
• [17]MISHRA R, SHU C M, ONG H C, et al. Progress and development of biochar as a catalyst for hydrogen production[J]. Journal of Cleaner Production,2024,477:143853.
• [18]YANG J T, TANG S B, MEI W J, et al. Valorising lignocellulosic biomass to high-performance electrocatalysts via anaerobic digestion pretreatment[J]. Biochar,2024,6(1):23.
• [19]ZHENG M, SHI K, ZHAO Y X, et al. The novel mushroom-like carbon nanotube top-supported FeNi alloy doped P material with ultra-high activity for OER/HER/ORR[J]. International Journal of Hydrogen Energy,2024,72:1077-1090.
• [20]RATH P C, PATRA J, HUANG H, et al. Carbonaceous anodes derived from sugarcane bagasse for sodium-ion batteries[J].ChemSusChem,2019,12(10):2302-2309.
• [21]CHEN Y, WU Y, LIAO Y, et al. Tuning carbonized wood fiber via sacrificial template-assisted hydrothermal synthesis for highperformance lithium/sodium-ion batteries[J]. Journal of Power Sources,2022,546:231993.
• [22]JIANG B,LI J X,LIU R,et al. Exclusively carbon-based self-supporting electrodes doped with different heteroatoms for overall water splitting in a wide pH range[J]. International Journal of Hydrogen Energy,2024,51(Part C):1314-1326.
• [23]LI Z J, YAO Y C, NIU Y, et al. Multi-heteroatom-doped hollow carbon tubes as robust electrocatalysts for the oxygen reduction reaction,oxygen and hydrogen evolution reaction[J]. Chemical Engineering Journal,2021,418:129321.
• [24]张永政，郭旭，宋欣月，等.过渡金属电解水催化剂的非金属掺杂研究进展[J].无机化学学报，2024,40(2):289-306.ZHANG Y Z, GUO X, SONG X Y, et al. Advances in non-metallic doping of transition metal electrocatalysts for overall water splitting[J]. Chinese Journal of Inorganic Chemistry,2024,40(2):289-306.
• [25]ZHANG C L, ZHENG K W, YE X Q, et al. Effects of nonmetallic heteroatoms doping on the catalytic performance of carbon materials[J]. Chemical Engineering Science,2025,304:120980.
• [26]ZHANG R,DU X H,LI S S,et al. Application of heteroatom doping strategy in electrolyzed water catalytic materials[J]. Journal of Electroanalytical Chemistry,2022,921:116679.
• [27]LANG M,WANG D M,YANG S B,et al. N-S vacancy sites on heteroatomic doping metal-free carbo-catalyst for efficient biomass hydrodeoxygenation[J]. Fuel,2024,366:131222.
• [28]KIM J,PARK J,LEE J,et al. Biomass-derived P,N self-doped hard carbon as bifunctional oxygen electrocatalyst and anode material for seawater batteries[J]. Advanced Functional Materials,2021,31(22):2010882.
• [29]QU J, WANG S H, ZHANG C R, et al. Active oxygen species mediate the iron-promoting electrocatalysis of oxygen evolution reaction on metal oxyhydroxides[J]. Nature Communications,2023,14:6826.
• [30]GAO Y P, CHEN R X, JIANG C H, et al. Tuning the microstructure of biomass-derived hard carbons by controlling the impurity removal process for enhanced Na ion storage performance[J]. Diamond and Related Materials,2024,148:111388.
• [31]YOSHIMOTO M, ITO K, OMOTE K. Local structure of amorphous carbon investigated by X-ray total scattering and RMC modeling[J]. Scientific Reports,2024,14:25298.
• [32]ZHAO P, SHEN B X, YANG M T, et al. Effect of nitrogen species on electrochemical properties of N-doped carbon nanotubes derived from co-pyrolysis of low-density polyethylene and melamine[J]. Journal of Energy Storage,2023,67:107569.
• [33]XIE W H, YAO X Y, LI H, et al. Biomass-based N-rich porous carbon materials for CO2 capture and in situ conversion[J].ChemSusChem,2022,15(18):e202201004.
• [34]LI S,WANG Y Y,SHI Y,et al. Nitrogen and sulfur co-doped biomass-derived porous carbon electrodes for ultra-high-performance all-aqueous thermally regenerative flow batteries[J]. The Journal of Physical Chemistry Letters,2024,15(26):6736-6742.
• [35]ZHENG D W, XV D K, LV X R, et al. High-efficiency acidic electrocatalytic hydrogen evolution enhanced by encapsulation of heterojunction CoP-MoP nanoparticles in a nitrogen-doped 3D nanocarbon framework[J]. Solar Energy Materials and Solar Cells,2024,269:112794.
• [36]HUANG Y Z,ZHANG C,WANG X Y,et al,Synergistic single-atom and clustered cobalt sites on N/S co-doped defect nano-carbon for efficient H2O2 electrosynthesis[J]. Nano-Micro Letters,2025,17:142.
• [37]NATH S S,CHANTHIRASEKARAN K,SATHIYA PRIYA S,et al. Boosting electrochemical behavior of Biomass-derived porous carbon via N, S, and N, S co-doping for enhanced supercapacitor Performance[J]. Diamond and Related Materials, 2025, 159:112850.
• [38]DOBELE G, VOLPERTS A, PLAVNIECE A, et al. Thermochemical activation of wood with NaOH, KOH and H3PO4 for the synthesis of nitrogen-doped nanoporous carbon for oxygen reduction reaction[J]. Molecules,2024,29(10):2238.
• [39]LI R L, TONG L J, JIANG Y T, et al. SnS2 nanoparticles embedded in sulfurized polyacrylonitrile composite fibers for highperformance potassium-ion batteries[J]. Interdisciplinary Materials,2024,3(1):150-159.
• [40]LI Z G, LI C L, CHEN J W, et al. Confined synthesis of MoS2 with rich co-doped edges for enhanced hydrogen evolution performance[J]. Journal of Energy Chemistry,2022,70:18-26.
• [41]LI H, LI Y, ZHANG L, CHEN Z, et al. Field-assisted electrocatalysts spark sulfur redox kinetics:From fundamentals to applications[J]. Interdisciplinary Materials,2023,2(3):390-415.
• [42]NALLAYAGARI A R,SGRECCIA E,PIZZOFERRATO R,et al. Tuneable properties of carbon quantum dots by different synthetic methods[J]. Journal of Nanostructure in Chemistry,2021,12:565-580.
• [43]KARUNAGARAN R,TRAN D,TUNG T T,et al. A unique synthesis of macroporous N-doped Carbon composite catalyst for oxygen reduction reaction[J]. Nanomaterials,2021,11(1):43.
• [44]LU F,ZHAN C Z,LIN H,et al. Carbon-based synergistic catalysis with transition metal dichalcogenides for electrocatalytic oxygen evolution/reduction[J]. Materials Chemistry and Physics,2024,317:129163.
• [45]CHEN Z J, YUN S N, WU L, et al. Waste-derived catalysts for water electrolysis:circular economy-driven sustainable green hydrogen energy[J]. Nano-Micro Letters,2023,15:4.
• [46]QU S,YUAN Y F,YANG X N,et al. Carbon defects in biochar facilitated nitrogen doping:The significant role of pyridinic nitrogen in peroxymonosulfate activation and ciprofloxacin Degradation[J]. Chemical Engineering Journal,2022,441:135864.
• [47]ZHONG X,WAN H,LIN Y,et al. N-doped bimetallic sulfides hollow spheres derived from metal-organic frameworks toward costefficient and high performance oxygen evolution Reaction[J]. Applied Surface Science,2022,591:153173.
• [48]TANG Y L, LI J N, LU Z Y, et al. MOF-derived CoSe2@NiFeOOH arrays for efficient oxygen evolution reaction[J].Nanomaterials,2023,13(19):2621.
• [49]FENG B M, CHEN J, YANG Y F, et al. Facile synthesis of nanosized spinel high entropy oxide(FeCoNiCrMn)3O4 for efficient oxygen evolution Reaction[J]. Journal of Materiomics,2024,10(4):919-927.
• [50]CHEN Y F,LI J H,LIU T T,et al. Constructing robust NiFe LDHs–NiFe alloy gradient hybrid bifunctional catalyst for overall water splitting:One-step electrodeposition and surface Reconstruction[J]. Rare Metals,2023,42(7):2272-2283.
• [51]WANG F,HUANG R W,HAN W C,et al. ZnO/ZnS heterostructure in N-doped porous carbon for anchoring–diffusion–conversion of polysulfides for high-performance lithium–sulfur Batteries[J]. Rare Metals,2024,43(8):3661-3676.
• [52]LU S S, SHI Y M, ZHOU W, et al. Dissolution of the heteroatom dopants and formation of ortho-ouinone moieties in the doped carbon materials during water electrooxidation[J]. Journal of the American Chemical Society,2022,144(7):3250-3258.
• [53]ZHANG X P, BI Y Y, WANG Y, et al. N, S co-doped graphene coupled with Ni2P/CoP-loaded carbon nanospheres:A novel catalyst for hydrogen evolution Reaction[J]. Materials Today Sustainability,2024,25:100677.
• [54]LIU Z,WANG M,HOU M,et al. Low-energy-consumption electrochemical CO2 reduction coupled with SO2 electrooxidation using bifunctional Ni-N-C Electrocatalysts[J]. Chemical Engineering Journal,2025,515:163706.
• [55]LI S J,MA Z M,FU M M,et al. Anion/cation-induced strong electronic polarization of N,Fe-CoS2 electrocatalyst to boost efficient oxygen Evolution[J]. Journal of Colloid and Interface Science,2024,654:1089-1097.