目前有关电催化剂应用的诸多研究领域,特别是商业领域,仍然由贵金属及其氧化物占据,但因其存在高成本和易中毒的壁垒而迫使科研人员把研究目光转向钨基电催化材料。氧化钨在制备条件得到有效控制的前提下可实现晶型结构及钨元素价态的多变,因此易于参加多种电化学反应,可实现对特定电化学反应的有效催化。回顾了不同晶相结构氧化钨基电极材料和不同异质结构钨基电极材料的制备方法、结构优势及其对各类电化学反应的优越催化性能,并从电极材料的制备和结构入手深入分析了文中所涉及电极材料优越催化性能的本质原因。以氧化钨及钨基电极材料的优越电催化性能为主线,辅以对电极材料的制备方法和特殊结构的分析,深入探讨了此类电催化材料的优势和发展方向,并总结本领域近5年的科研成果,为此类研究方向的深入开展提供了一定的借鉴经验。
In recent years,intense research areas related to the development and applications of electrocatalysis,especially in the commercial field,are still dominated by the noble metals and their oxides.However,the high cost and toxicity limit their large-scale applications,and tungsten-based electrocatalytic materials have attracted more and more attention.Tungsten oxide can achieve versatility in crystalline structure and tungsten elemental valence state under effectively controlled preparation conditions,and thus can easily participate in a variety of electrochemical reactions and achieve effective catalysis for specific electrochemical reactions.This paper reviewed the latest advances in the preparation methods,structural advantages and superior catalytic performance of tungsten oxide-based electrode materials with different crystalline structures and tungsten-based electrode materials with different heterogeneous structures for various electrochemical reactions.In terms of the structure modulation and preparation,the essential reasons for the superior catalytic performance of the related electrode materials were analyzed in depth.Taking tungsten oxide and tungsten-based electrode materials' excellent electrocatalytic performance as the main focus,complemented by the analysis of electrode material preparation methods and special structures,the advantages and development directions of such electrocatalytic materials were deeply explored.Furthermore,recent scientific research achievements in this field in the past five years were summarized,providing some valuable reference experience for the further development of research.
[1] Wagner F T,Lakshmanan B,Mathias M F.Electrochemistry and the future of the automobile[J].The Journal of Physical Chemistry Letters,2010,1(14):2204-2219.
[2] Gewirth A A,Varnell J A,Diascro A M.Nonprecious metal catalysts for oxygen reduction in heterogeneous aqueous systems[J].Chemical Reviews,2018,118(5):2313-2339.
[3] 李伟斌,郭文林,姚根有,等.质子交换膜燃料电池阴极催化剂研究进展[J].化工新型材料,2021,49(S1):296-300.
[4] Bhargava A,Chen C Y,Dhaka Kl,et al.Mn cations control electronic transport in spinel CoxMn3-xO4 nanoparticles[J].Chemistry of Materials,2019,31:4228-4233.
[5] Chen X Y,Yang J,Gao Y F,et al.Effect of transition metals on the oxygen reduction reaction activity at metal-N3/C active sites[J].ChemElectroChem,2021,8:1-15.
[6] Tian H,Cui X Z,Shi J I,et al.Emerging electrocatalysts for PEMFCs applications:tungsten oxide as an example[J].Chemical Engineering Journal,2021,421:129430.
[7] Kim G Y,Yoon K R,Shin K Y,et al.Black tungsten oxide nanofiber as a robust support for metal catalysts:high catalyst loading for electrochemical oxygen reduction[J].Small,2021,17(47):e2103755.
[8] 黄龙,徐海超,荆碧,等.质子交换膜燃料电池铂基催化剂研究进展[J].电化学,2022,28(1):16-32.
[9] Lu Y Z,Jiang Y Y,Gao X H,et al.Strongly coupled Pd nanotetrahedron/tungsten oxide nanosheet hybrids with enhanced catalytic activity and stability as oxygen reduction electrocatalysts[J].Journal of the American Chemical Society,2014,136:11687.
[10] Jiang B Z,Sun H,Yuan T,et al.Framework-derived tungsten single-atom catalyst for oxygen reduction reaction[J].Energy Fuels,2021,35:8173-8180.
[11] 何小龙,龚元林,陈姝敏.金属有机骨架材料的制备及其在光催化领域的应用进展[J].化工新型材料,2022,50(S1):156-160,167.
[12] Yang Q X,He L J,Ke C Y,et al.Design of Fe-Nx/tungsten carbide for efficient electrocatalyst oxygen reduction in acidic media[J].Israel Journal of Chemistry,2021,61:1-9.
[13] Chen Z G,Gong W B,Cong S,et al.Eutectoid-structured WC/W2C heterostructures:a new platform for long-term alkaline hydrogen evolution reaction at low overpotentials[J].Nano Energy,2020,68:104335.
[14] Hou Y,Zhuang X D,Feng X I,et al.Recent advances in earth-abundant heterogeneous electrocatalysts for photoelectrochemical water splitting[J].Small Methods,2017,1:1700090.
[15] Zhang J,Zhang Q Y,Feng X I.Support and interface effects in water-splitting electrocatalysts[J].Advanced Materials,2019,31:1808167.
[16] Sun S C,Jiang H,Chen Z Y,et al.Bifunctional WC-supported RuO2 nanoparticles for robust water splitting in acidic media[J].Angewandte Chemie International Edition,2022,61(21):e202202519.
[17] Wang D I,Li H P,Du N,et al.Single platinum atoms immobilized on monolayer tungsten trioxide nanosheets as an efficient electrocatalyst for hydrogen evolution reaction[J].Advanced Functional Materials,2021,31:2009770.
[18] Li P S,Duan X X,Kuang Y,et al.Iridium in tungsten trioxide matrix as an tfficient Bi-functional electrocatalyst for overall water splitting in acidic media[J].Small,2021,17:2102078.
[19] Maslana K,Wenelska K,Biegun M,et al.High catalytic performance of tungsten disulphide rodes in oxygen evolution reactions in alkaline solutions[J].Applied Catalysis B:Environmental,2020,266:118575.
[20] Malavekar D B,Lokhande V C,Patil D J,et al.Amorphous nickel tungstate films prepared by SILAR method for electrocatalytic oxygen evolution reaction[J].Journal of Colloid and Interface Science,2022,609:734-745.
[21] Cho H D,Iianchezhiyan P,Kumar G M,et al.Highly carbonized tungsten trioxide thin films and their enhanced oxygen evolution related electrocatalytic functions[J].Journal of Materials Research and Technology,2021,12:2216-2223.
[22] 宋乃建,郭明媛,南皓雄,等.过渡金属基催化剂用于氧析出反应的研究进展[J].储能科学与技术,2021,10(6):1906-1917.
[23] Diao J X,Qiu Y,Liu S Q,et al.Interfacial engineering of W2N/WC heterostructures derived from solid-state synthesis:a highly efficient trifunctional electrocatalyst for ORR,OER,and HER[J].Advanced Materials,2020,32:1905679.
[24] Balaji R,Nguyen T T,Harish K,et al.Modulating heterointerfaces of tungsten incorporated CoSe/Co3O4 as a highly efficient electrocatalyst for overall water splitting[J].Journal of Materials Chemistry A,2022,10:3782-3792.
[25] 申雪然,冯彩虹,代政,等.电解海水制氢的研究进展[J].化工新型材料,2021,49(12):55-60.
[26] Zheng T T,Sang W,He Z H,et al.Conductive tungsten oxide nanosheets for highly efficient hydrogen evolution[J].Nano Letters,2017,17:7968-7973.
[27] Xi G C,Ye J H,Ma Q,et al.In situ growth of metal particles on 3D urchin-like WO3 nanostructures[J].Journal of the American Chemical Society,2012,134:6508-6511.
[28] Wang F G,Valentin C D,Pacchioni G,et al.Semiconductor-to-metal transition in WO3-x:nature of the oxygen vacancy[J].Physical Review B,2011,84:073103.
[29] Lu J J,Qian G F,Luo L,et al.Contributions of oxygen vacancies to the hydrogen evolution catalytic activity of tungsten oxides[J].International Journal of Hydrogen Energy,2021,46:676-682.
[30] 赵林艳,席晓丽,樊佑书,等.纳米氧化钨的水热/溶剂热法制备及应用的综述[J].材料导报,2019,33(19):3203-3209.
[31] He X,Wang X Y,Sun B N,et al.Synthesis of three-dimensional hierarchical furball-like tungsten trioxide microspheres for high performance supercapacitor electrodes[J].RSC Advances,2020,10(23):13437-13441.
[32] Zhang X P,Jin G Y,Wang D,et al.Crystallographic phase and morphology dependent hydrothermal synthesis of tungsten oxide for robust hydrogen evolution reaction[J].Journal of Alloys and Compounds,2021,875:160054.
[33] Zhu W X,Ren M R,Hu N,et al.Traditional NiCo2S4 phase with porous nanosheets array topology on carbon cloth:a flexible,versatile and fabulous electrocatalyst for overall water and urea electrolysis[J].ACS Sustainable Chemistry and Engineering,2018,6:5011-5020.
[34] Mohamed M,Salama T M,Hegazy M A,et al.Synthesis of hexagonal WO3 nanocrystals with various morphologies and their enhanced electrocatalytic activities toward hydrogen evolution[J].International Journal of Hydrogen Energy,2019,44:4724-4736.
[35] Sarma P V,Vineesh T V,Kumar R,et al.Nanostructured tungsten oxysulfide as an efficient electrocatalyst for hydrogen evolution reaction[J].ACS Catalysis,2020,10:6753-6762.
[36] Voiry D,Yamaguchi H Y,Li J,et al.Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution[J].Nature Materials,2013,12:850-855.
[37] Anis S F,Lalia B S,Mostafa A O,et al.Electrospun nickel-tungsten oxide composite fibers as active electrocatalysts for hydrogen evolution reaction[J].Journal of Materials Science,2017,52:7269-7281.
[38] Nguyen T A,Jun T S,Rashid M,et al.Synthesis of mesoporous tungsten oxide nanofibers using the electrospinning method[J].Materials Letters,2011,65:2823-2825.
[39] Li D X,Xu Y,Lu Y I,et al.Defect-rich engineering of Ni-incorporated tungsten oxides micro-flowers on carbon cloth:a binder-free electrode for highly efficient hydrogen evolution reaction[J].Journal of Power Sources,2022,520:230862.
[40] Tian H,Cui X Z,Zeng L M,et al.Oxygen vacancy-assisted hydrogen evolution reaction of the Pt/WO3 electrocatalyst[J].Journal of Materials Chemistry A,2019,7:6285-6293.
[41] Xu K K,Fu X I,Li H,et al.A novel composite of network-like tungsten phosphide nanostructures grown on carbon fibers with enhanced electrocatalytic hydrogen evolution efficiency[J].Applied Surface Science,2018,456:230-237.
[42] Jiang S Y,Lu J J,Yu G T,et al.Carbon-encapsulated WOx hybrids as efficient catalysts for hydrogen evolution[J].Advanced Materials,2018,30:1705979.
[43] Cui Y L S,Tan X,Xiao K F,et al.Tungsten oxide/carbide surface heterojunction catalyst with high hydrogen evolution activity[J].ACS Energy Letters,2020,5:3560-3568.
[44] Sun T M,Zhong W T,Zhang M K,et al.A low-cost 2D WO3/Ni3S2 heterojunction for highly stable hydrogen evolution[J].Materials Chemistry Frontiers,2021,5:8248-8254.
基金资助
国家自然科学基金(52163029)
PDF
