面向大电流密度电解水的碳基催化剂研究进展.pdf

Cite this:NewCarbonMaterials,2024,39(1):1-16DOI:10.1016/S1872-5805(24)60831-0Carbon-based electrocatalysts for water splitting athigh-current-densities:A reviewCHENYu-xiang1,2,*,ZHAOXiu-hui3,DONGPeng2,ZHANGYing-jie2,ZOUYu-qin4,*,WANGShuang-yin4（1.Faculty of Material Science and Engineering,Kunming University of Science and Technology,Kunming 650093,China;2.National and Local Joint Engineering Laboratory for Lithium-ion Batteries and Materials Preparation Technology,Key Laboratory of Advanced BatteryMaterials of Yunnan Province,Kunming University of Science and Technology,Kunming 650093,China;3.College of Aerospace Science and Engineering,National University of Defense Technology,Changsha 410073,China;4.State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,Advanced Catalytic Engineering Re-search Center of the Ministry of Education,Hunan University,Changsha 410082,China）Abstract：Electrocatalyticwatersplittingisapromisingstrategytogeneratehydrogenusingrenewableenergyundermildcondi-tions.Carbon-basedmaterialshaveattractedattentioninelectrocatalyticwatersplittingbecauseoftheirdistinctivefeaturessuchashighspecificarea,highelectronmobilityandabundantnaturalresources.Hydrogenproducedbyindustrialelectrocatalyticwatersplittinginalargequantityrequireselectrocatalysisatalowoverpotentialatalargecurrentdensity.Substantialeffortsfocusedonfundamentalresearchhavebeenmade,whilemuchlessattentionhasbeenpaidtothehigh-current-densitytest.Therearemanydis-tinctdifferencesinelectrocatalysistosplitwaterusinglowandhighcurrentdensitiessuchasthebubblephenomenon,localenviron-mentaroundactivesites,andstability.Recentresearchprogressoncarbon-basedelectrocatalystsforwatersplittingatlowandhighcurrentdensitiesissummarized,significantchallengesandprospectsforcarbon-basedelectrocatalystsarediscussed,andpromisingstrategiesareproposed.Key words:Electrocatalyticwatersplitting；Carbon-basedmaterial；Bubble；Highcurrentdensity；Decouple1IntroductionHydrogen emerges global wide applications inpetroleumrefining,industrialproductionofammoniaandmethanol,fuelcells,andmetallurgicalindustry12.Comparedwithsteamreformingofmethanolandcoalgasification that produce hydrogen,electrochemicalwatersplittinghasvariousadvantages3,suchashighpurity carbon-free hydrogen,use of renewablesources,nontoxic reagent and scale flexibility46.Typically,hydrogen evolution reaction(HER)andoxygenevolutionreaction(OER)arethetwostepsinelectrocatalyticwatersplitting7.OERrequires4elec-tronsduringtheprocess,while2electronsareneededinHER8.Besides,alargerthanthethermodynamicpotentialshouldberequiredinelectrolysisduetotheintrinsicbarriers9.Reducingtheoverpotentialanden-hancingthestabilityisofenormouseconomicbenefittorealizeindustrialapplications1011.Infundamental laboratory research at low cur-rentdensities12,thechargestateofcarbon-basedcata-lysts can be easily regulated through engineeringstructuredefects,heteroatomengineering,heterojunc-tionengineering,andstructureregulation13.Forex-ample,defective carbon materials and carbon-basednoble/non-noblemetalmaterialsarepotentialsubsti-tutesfornoblemetalcatalystsduetotheirmultiplesu-periorities14,suchasexcellentelectronicconductiv-ity,high surface area,excellent resistance to corro-sion,lowcostandstructuralflexibility.Breakingthesp2carbonlatticewithelectroneutralitycanleadtoune-venchargedistributioninthecarbonmatrixthatserveasnewelectrocatalyticactivesites.Aseriesofdefect-ivecarbonelectrocatalystsexhibitingsuperiorHERorReceived date：2023-10-16；Revised date：2023-11-29Corresponding author：CHENYu-xiang,Professor.E-mail:;ZOUYu-qin,Professor.E-mail:yuqin_Author introduction：CHENYu-xiang,Professor.E-mail:Homepage:http:/ carbon-based catalysts are able to achievemore excellent electrocatalytic performance by themodificationwithmetalspecies.Besides,thechargetransferbetweenthecarbonhostandmetalormetalcompounds can regulate the electronic structure ofeachcomponent1516.Owingtothemodificationbymetalspecies,carbon-basedcatalystscanachievein-creasedelectrocatalyticperformance.Theinterconnectionofthechargetransferpathoncarbon-basedmaterialsandtheelectrocatalyticwa-ter splitting behavior have been reviewed previ-ously12.Although great progress in advanced elec-trocatalysts under laboratory conditions has beenachieved1719,thelaboratoryresearchisusuallycar-riedoutindilutesolutionatalowcurrentdensity20.Actually,theoptimizedelectrocatalysts,exhibitinganexcellentHERandOERperformanceatalowcurrentdensityusually,donotdisplayanexpectedperform-ance at a high current density21.Because currentdensitygreatlyimpactstheelectrontransferatthein-terfaceof electrocatalyst-electrolyte and electrocata-lyst-support22.Forexample,MoS2/Mo2Ccatalystde-livers a commonplace electrocatalytic performancecomparedwithPtatalowcurrentdensity.Incontrast,MoS2/Mo2Ccatalystrequiresmuchloweroverpoten-tials to realize high current densities(191 mV 500mAcm2)thancommercialPtfoil(567mV500mAcm2)22.Theabovetremendousperformancedifferences demonstrate that the anode and cathodeprocesses of water splitting become complicated atlargecurrentdensities2329.Thedifferenceintestingcurrentdensityleadstoasignificantdiscrepancyinelectrocatalystdesignandelectrodedesign30.Inageneraltest,anelectrocata-lystmixedwithNafionisusuallyloadedonaglasscarbon substrate to form a thin film.The thin filmconfigurationusuallyemployslowloadinglevelsoflessthan1mgcm2,asaresultwellmasstransferandfluent release of generated hydrogen and oxygenbubblescanberealizedwhenthecurrentdensityislow(0.05 VRHEHydrogen evolutionProduct:H2Potential:1.23 VRHEOrganic oxidationProduct:chemicalsOnset potential:1 VRHECurrent density0.20.40.6Potential(vs.RHE)/VCell voltagePlatformchemicalsValue-addedchemicalsProduct/useFuranic polyesterinterleukin inhibitorOOOOOOOOHOOHHMFCAH2OHOHFuroic acidFurfuralHMFElectrooxidationOrganic synthesismedicinesperfumesfuroate esters0.81.01.21.41.6(b)Cathode reactionBiomassfeedstocksStarchCelluloseHemicelluloseFig.7Waterelectrolysissystemswithvariousanodereactions107.(a)Comparisonofvariousanodereactionsforwaterelectrolysis.(b)Electrochemistry-in-volvedconversionpathfrombiomassfeedstockintovalue-addedchemicals.Reproducedwithpermission10新型炭材料（中英文）第39卷electrocatalyticcatalystduetotheinterfaceforce,es-peciallyathighcurrentdensities,leadingtoreducedaccessiblesolid-liquidinterfacecontactareaandlim-itedmassandelectrontransfer.Rationalengineering,nano-microstructureandchemicalcoatingtocreateuniquesuperaerophobicfeaturesatthecatalystsur-facearefavorablyusedtoenhancetheHERperform-anceathighcurrentdensities118,whichleadstoalowinterfacial adhesion on the interface of electrolyte-catalyst,enhancesthereleaseofgeneratedhydrogenbubblesfromtheelectrocatalystelectrodesurfaceandrealizestheincreasedexposureextentofelectrocata-lyticactivesitestothesurroundingelectrolyte79.Stability is another key concern for evaluatingtheelectrocatalystperformance,includingmechanicalandchemicalstabilities.Inthebinderandbinder-freesystems,themechanicalstabilityisgreatlyinfluencedbytheadhesionstrengthamongthesupport,theelec-trocatalystsandthebubble119.Thechemicalstabilityisgreatlyaffectedbytheresistancetocorrosionofthesupportandtheelectrocatalystinaliquidmediumun-deroxidation120,corrosionandreduction121.Besides,conventionalcarbon-basedsupportsandcarbon-basedcatalystsarepronetopassivationordissolutionunderanoxidative environment,especially at high poten-tials.Exploringadvancedbinderandsurfacechemic-al modification method is vital for the powder-sup-portsystemelectrocatalyticelectrodeinelectrochem-icalwatersplitting122.HERandOERarebothinterfacialsensitivereac-tions.Theinterfacialmicroenvironmentisinvolvedintheelectrocatalyticprocess123.Thefastdecreasedre-actantconcentrationneartheelectrocatalystsmayde-pressthestabilityunderhighcurrentdensities.Sub-stantialconventionalstrategieshavebeenmadetoen-hancethekineticsoftheHERandOER.However,theseattemptscannotchangethefeatureofthelowconcentrationofprotonsinanon-acidicmedium124.Hence,generatingalocalacidicenvironmentbyafa-vorableelectrodesysteminnon-acidicmediaismoreeffectiveforenhancingtheelectrocatalyticperform-anceofthesamecatalyst125.Engineeringrationalandmultifunctionalcocatalystsincarbon-basedmaterialseffectivelysolvestheabovepoints126.Todate,substantialattemptshavebeencontrib-uted to develop new and advanced solid polymermembranes.Benefitingfromtheadvantagesofanionorprotonsolidexchangemembrane,waterelectrolys-iscanbecarriedoutathugepressuredifferences.Inrecent years,substantial works have been done onelectrocatalyticwatersplitting,butmostofthemfo-cusedonincreasingtheefficiencyofHERandOERthemselves.However,theefficientformationofoxy-genandhydrogenisoflittleuseunlessgeneratedoxy-genandhydrogencanbekeptseparatetotally.Anditisstillchallengingtorealizetheadequateseparationof oxygen and hydrogen upon electrolysis127.De-couplingHERandOERofferasolutiontoavoidthesechallengesbygeneratingoxygenandhydrogenindif-ferentelectrochemicalcells128atdifferenttimesandatdifferentrates129.Muchmoreattentionshouldbepaidtoshorteningthegapbetweenindustrialapplica-tionandfundamentalresearch.Apartfromtheaboveissues,continuedattentionisworthtobepaidtoothervitalconcernstoincreasetheactivityandstabilityofcarbon-basedmaterialsforelectrocatalyticwatersplitting130,suchastheelectro-lyte131132,environmentconditionsincludingthepres-sure133andtemperature134135,flowcell136andheatmanagement137138.AcknowledgementsThisworkwassupportedbyChinaPostdoctoralScienceFoundation(2020M672471).References Chen M,Kitiphatpiboon N,Feng C,et al.Recent progress intransition-metal-oxide-basedelectrocatalystsfortheoxygenevolution reaction in natural seawater splitting:A criticalReviewJ.eScience，2023，3（2）：100111.1Ye K,Chai Z,Gu J,et al.BiOI BiVO4 photoanodes withsignificantlyimprovedsolarwatersplittingcapability:p-njunctionto expand 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