氢氧根交换膜燃料电池(HEMFCs)技术快速发展,碱性介质中用于催化阴极氧还原反应(ORR)的非贵金属电催化剂已有广泛研究。但HEMFCs存在的一个巨大挑战是阳极氢氧化反应(HOR)相对缓慢的动力学,因此需要较高负载量的Pt基阳极电催化剂才能实现较高的性能,这制约了HEMFCs的发展。由于Pt价格昂贵、地球储量有限,开发非Pt阳极HOR电催化剂被认为是减少Pt用量和降低燃料电池生产成本的可行途径。这里从电催化剂的异质结构、支撑效应、金属合金等方面,总结了近3年来非Pt贵金属(Ru、Rh、Pd、Ir)基HOR电催化剂的最新研究进展,归纳了相应的电催化性能,并阐明了其HOR机理。最新报道的非Pt HOR电催化剂可以降低阳极电催化剂的成本,并具有与商业Pt/C媲美的活性与稳定性。最后,基于目前对非Pt贵金属电催化剂结构特征分析,进一步对HOR研究的未来发展方向做出了展望。
Hydroxide exchange membrane fuel cells (HEMFCs) technology is rapidly developing and non-precious metal electrocatalysts for catalyzing cathodic oxygen reduction reaction (ORR) in alkaline media have been extensively investigated.However,a major challenge for HEMFCs is the relatively slow kinetics of the anodic hydrogen oxidation reaction (HOR),which limits the development of HEMFC,thus requiring high loadings of Pt-based anode electrocatalysts to achieve high performance.Due to the high price of Pt and limited earth reserves,the development of non-Pt anode HOR electrocatalysts is considered a viable way to reduce the amount of Pt usage and lower the cost of fuel cell production.Here,we reviewed the latest research progress of non-Pt precious metal (Ru,Rh,Pd,Ir)-based HOR electrocatalysts in the past three years in terms of their heterogeneous structure,support effects and metal alloys,summarized the corresponding electrocatalytic performance,and elucidated their HOR mechanisms.The recently reported non-Pt HOR electrocatalysts could reduce the cost of anode electrocatalysts and had activity and stability comparable to that of commercial Pt/C.Finally,based on the current structural characterization of non-Pt precious metal electrocatalysts,an outlook on the future development of HOR research was further provided.
[1] Gallagher J.Tracking hydrogen projects[J].Nature Energy,2023,8(2):107-108.
[2] Höfer T,Madlner R.Locational (in) efficiency of renewable energy feed-in into the electricity grid:a spatial regression analysis[J].The Energy Journal,2021,42(1):171-195.
[3] nci M,Büyük M,Demir M H,et al.A review and research on fuel cell electric vehicles:topologies,power electronic converters,energy management methods,technical challenges,marketing and future aspects[J].Renewable and Sustainable Energy Reviews,2021,137:110648.
[4] Zhao R P,Yue X,Li Q H,et al.Recent advances in electrocatalysts for alkaline hydrogen oxidation reaction[J].Small,2021,17(47):2100391.
[5] Zhao T W,Wang Y,Karuturi S,et al.Design and operando/in situ characterization of precious-metal-free electrocatalysts for alkaline water splitting[J].Carbon Energy,2020,2(4):582-613.
[6] Chao T T,Hu Y M,Hong X,et al.Design of noble metal electrocatalysts on an atomic level[J].ChemElectroChem,2019,6(2):289-303.
[7] 马腾,张万益,贾德龙.新铂资源现状与需求趋势[J].矿产保护与利用,2019,39(5):90-97.
[8] Tang M H,Zhang S M,Chen S L.Pt utilization in proton exchange membrane fuel cells:structure impacting factors and mechanistic insights[J].Chemical Society Reviews,2022,51(4):1529-1546.
[9] Zheng J,Sheng W C,Zhuang Z B,et al.Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy[J].Science Advances,2016,2(3):e1501602.
[10] Du N Y,Roy C,Peach R,et al.Anion-exchange membrane water electrolyzers[J].Chemical Reviews,2022,122(13):11830-11895.
[11] Mosallaei H,Hadadzadeh H,Foelske A,et al.[Ru(tmphen)3]2[Fe(CN)6] and [Ru(phen)3][Fe(CN)5(NO)] complexes and formation of a heterostructured RuO2-Fe2O3 nanocomposite as an efficient alkaline HER and OER electrocatalyst[J].Dalton Transactions,2022,51(16):6314-6331.
[12] Zhang X B,Xia L X,Zhao G Q,et al.Fast and durable alkaline hydrogen oxidation reaction at the electron-deficient ruthenium-ruthenium oxide interface[J].Advanced Materials,2023,35(9):2208821.
[13] Su L X,Jin Y M,Gong D,et al.The role of discrepant reactive intermediates on Ru-Ru2P heterostructure for pH-universal hydrogen oxidation reaction[J].Angewandte Chemie International Edition,2023,62(2):e202215585.
[14] Zhang H,Wang J,Qin F Q,et al.V-doped Ni3N/Ni heterostructure with engineered interfaces as a bifunctional hydrogen electrocatalyst in alkaline solution:simultaneously improving water dissociation and hydrogen adsorption[J].Nano Research,2021,14(10):3489-3496.
[15] Zhang B H,Zhao G Q,Zhang B X,et al.Lattice-confined Ir clusters on Pd nanosheets with charge redistribution for the hydrogen oxidation reaction under alkaline conditions[J].Advanced Materials,2021,33(43):2105400.
[16] Liu D Q,Luo Z X,Zhang B X,et al.Tailoring interfacial charge transfer of epitaxially grown Ir clusters for boosting hydrogen oxidation reaction[J].Advanced Energy Materials,2023,13(1):2202913.
[17] Su L X,Zhao Y M,Jin Y M,et al.Identifying the role of hydroxyl binding energy in a non-monotonous behavior of Pd-Pd4S for hydrogen oxidation reaction[J].Advanced Functional Materials,2022,32(27):2113047.
[18] Zhou Y Y,Xie Z Y,Jiang J X,et al.Lattice-confined Ru clusters with high CO tolerance and activity for the hydrogen oxidation reaction[J].Nature Catalysis,2020,3(5):454-462.
[19] Cui A L,Ren P W,Bai Y,et al.Nanoparticle size effect of Pt and TiO2 anatase/rutile phases “volcano-type” curve for HOR electrocatalytic activity at Pt/TiO2-CNx nanocatalysts[J].Applied Surface Science,2022,584:152644.
[20] Zhang Y,Li G,Zhao Z L,et al.Atomically isolated Rh sites within highly branched Rh2Sb nanostructures enhance bifunctional hydrogen electrocatalysis[J].Advanced Materials,2021,33(43):2105049.
[21] Zeng L M,Peng H Q,Liu W,et al.Extraordinary activity of mesoporous carbon supported Ru toward the hydrogen oxidation reaction in alkaline media[J].Journal of Power Sources,2020,461:228147.
[22] Liu H X,Fu J T,Li H Y,et al.Single palladium site in ordered porous heteroatom-doped carbon for high-performance alkaline hydrogen oxidation[J].Applied Catalysis B:Environmental,2022,306:121029.
[23] Ji X F,Chen P,Liu Y J,et al.N-Doped carbon as a promoted substrate for Ir nanoclusters toward hydrogen oxidation in alkaline electrolytes[J].Inorganic Chemistry,2022,61(35):14187-14194.
[24] Yuan L,Boukhvalov D W,Lv C C,et al.TiO2-enhanced in situ electrochemical activation of Co3O4 for the alkaline hydrogen evolution reaction[J].Journal of Materials Chemistry A,2022,10(26):13769-13779.
[25] Yao N,Meng R,Wu F,et al.Oxygen-vacancy-induced CeO2/Co4N heterostructures toward enhanced pH-universal hydrogen evolution reactions[J].Applied Catalysis B:Environmental,2020,277:119282.
[26] Jiang J X,Tao S C,He Q,et al.Interphase-oxidized ruthenium metal with half-filled d-orbitals for hydrogen oxidation in an alkaline solution[J].Journal of Materials Chemistry A,2020,8,10168-10174.
[27] Ralbag N,Davydova E S,Mann-Lahav M,et al.Ceria entrapped palladium novel composites for hydrogen oxidation reaction in alkaline medium[J].Journal of The Electrochemical Society,2020,167(5):054514.
[28] Pagliaro M V,Wen C L,Sa B S,et al.Improving alkaline hydrogen oxidation activity of palladium through interactions with transition-metal oxides[J].ACS Catalysis,2022,12(17):10894-10904.
[29] Cruz-Reyes I,Trujillo-Navarrete B,García-Tapia K,et al.Pd/MnO2 as a bifunctional electrocatalyst for potential application in alkaline fuel cells[J].Fuel,2020,279:118470.
[30] Luo H,Wang K,Lin F X,et al.Amorphous MoOx with high oxophilicity interfaced with PtMo alloy nanoparticles boosts anti-CO hydrogen electrocatalysis[J].Advanced Materials,2023:2211854.
[31] Su L X,Fan X R,Jin Y M,et al.Hydroxyl-binding energy-induced kinetic gap narrowing between acidic and alkaline hydrogen oxidation reaction on intermetallic Ru3Sn7 catalyst[J].Small,2023:2207603.
[32] Dong Y T,Sun Q T,Zhan C H,et al.Lattice and surface engineering of ruthenium nanostructures for enhanced hydrogen oxidation catalysis[J].Advanced Functional Materials,2023,33(5):2210328.
[33] Yuan Q,Yang Y,Gong S P,et al.RuNi alloy nanoparticles encapsulated in oxygen-doped carbon as bifunctional catalyst towards hydrogen electrocatalysis[J].Chinese Journal of Chemistry,2021,39(12):3455-3461.
[34] Li Y B,Yang C Y,Ge C X,et al.Electronic modulation of Ru nanosheet by d-d orbital coupling for enhanced hydrogen oxidation reaction in alkaline electrolytes[J].Small,2022,18(29):2202404.
[35] Tran D S,Park H,Kim H,et al.Electrodeposited NiRh alloy as an efficient low-precious metal catalyst for alkaline hydrogen oxidation reaction[J].International Journal of Energy Research,2021,45(4):5325-5336.
[36] Kwon I S,Kwak I H,Zewdie G Mu,et al.MoSe2-VSe2-NbSe2 ternary alloy nanosheets to boost electrocatalytic hydrogen evolution reaction[J].Advanced Materials,2022,34(41):2205524.
[37] Yao H X,Wang X K,Li K,et al.Strong electronic coupling between ruthenium single atoms and ultrafine nanoclusters enables economical and effective hydrogen production[J].Applied Catalysis B:Environmental,2022,312:121378.
[38] Shen T,Wang S,Zhao T H,et al.Recent advances of single-atom-alloy for energy electrocatalysis[J].Advanced Energy Materials,2022,12(39):2201823.
[39] Mao J J,He C T,Pei J J,et al.Isolated Ni atoms dispersed on Ru nanosheets:high-performance electrocatalysts toward hydrogen oxidation reaction[J].Nano Letters,2020,20(5):3442-3448.
基金资助
国家自然科学基金(22262018)
PDF
