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Kuderedzwa kwecarbon dioxide kuita formic acid nemagetsi inzira inovimbisa yekuvandudza kushandiswa kwecarbon dioxide uye ine mukana wekushandiswa senzvimbo yekuchengetedza hydrogen. Mubasa iri, dhizaini yekubatanidza electrode ye zero-gap membrane yakagadzirwa kuti igadzire zvakananga formic acid kubva kucarbon dioxide. Kufambira mberi kukuru kwetekinoroji i membrane ye cation yakaboorwa, iyo, kana ikashandiswa mu forward bias bipolar membrane configuration, inobvumira formic acid yakagadzirwa pa membrane interface kuti ifambiswe kuburikidza ne anodic flow field mu concentrations dzakaderera se 0.25 M. Pasina zvimwe zvikamu zve sandwich pakati pe anode ne cathode, pfungwa iyi inovavarira kushandisa zvinhu zviripo zvebhatiri nemagadzirirwo akajairika muma fuel cells ne hydrogen electrolysis, zvichibvumira shanduko nekukurumidza kuenda ku scale-up uye kushambadzira. Mu 25 cm2 cell, perforated cation exchange membrane configuration inopa >75% Faraday efficiency ye formic acid pa <2 V uye 300 mA/cm2. Chinonyanya kukosha, bvunzo yekugadzikana kwemaawa makumi mashanu nemashanu pa200 mA/cm2 yakaratidza stable Faraday efficiency uye cell voltage. Ongororo yezvehupfumi netekinoroji inoshandiswa kuratidza nzira dzekuwana kuenzana kwemitengo nenzira dziripo dzekugadzira formic acid.
Kuderedzwa kwecarbon dioxide kuita formic acid nemagetsi uchishandisa magetsi anodzokororwa kwakaratidzwa kuderedza mari yekugadzira kusvika ku75%1 zvichienzaniswa nenzira dzechinyakare dzinoshandisa mafuta ekare. Sezvinoratidzwa mumabhuku2,3, formic acid ine mashandisirwo akasiyana-siyana, kubva munzira inoshanda uye isingadhuri yekuchengetedza nekutakura hydrogen kuenda kunzvimbo yekudya yeindasitiri yemakemikari4,5 kana indasitiri yebiomass6. Formic acid yakatoonekwa senzvimbo yekudya yekushandurwa kuita organic jet fuel intermediates uchishandisa metabolic engineering7,8. Nekuvandudzwa kweformic acid economics1,9, mabasa akati wandei ekutsvagisa akatarisana nekuvandudza catalyst selectivity10,11,12,13,14,15,16. Zvisinei, kuedza kwakawanda kuri kuramba kuchitarisa pamasero madiki eH kana masero emvura anoshanda pahuwandu hwakaderera hwemagetsi (<50 mA/cm2). Kuti kuderedza mitengo, kuwana kutengeserana uye kuwedzera kupinda kwemusika kunotevera, kuderedzwa kwe electrochemical carbon dioxide (CO2R) kunofanirwa kuitwa pahuwandu hwemagetsi akawandisa (≥200 mA/cm2) uye Faraday efficiency (FE)17 ukuwo kuwedzera kushandiswa kwezvinhu uye kushandisa zvikamu zvebhatiri kubva kuTechnology fuel cells uye water electrolysis zvinobvumira michina yeCO2R kushandisa mukana wehupfumi hwechikero18. Pamusoro pezvo, kuwedzera kushandiswa kwekugadzira uye kudzivirira kuwedzera kugadzirwa, formic acid inofanira kushandiswa sechigadzirwa chekupedzisira pane kugadzira munyu19.
Munzira iyi, kuedza kwakaitwa munguva pfupi yapfuura kugadzira michina yeCO2R formate/formic acid based gas diffusion electrode (GDE) inoshanda mumaindasitiri. Ongororo yakazara yakaitwa naFernandez-Caso et al.20 inopfupikisa magadzirirwo ese emasero emagetsi ekuderedza CO2 kuita formic acid/formate nguva dzose. Kazhinji, magadzirirwo ese aripo anogona kukamurwa kuita zvikamu zvitatu zvikuru: 1. Flow-through catholytes19,21,22,23,24,25,26,27, 2. Single membrane (cation exchange membrane (CEM)28 kana anion exchange membrane (AEM)29 uye 3. Sandwich configuration15,30,31,32. Zvikamu zvakapfava zvemagadzirirwo aya zvinoratidzwa muMufananidzo 1a. Pakugadziriswa kweflow ye catholyte, electrolyte chamber inogadzirwa pakati pe membrane ne cathode yeGDE. Flow-through catholyte inoshandiswa kugadzira ion channels mu cathode layer ye catalyst33, kunyangwe kudiwa kwayo kwekudzora formate selectivity kuri kukakavadzana34. Zvisinei, magadzirirwo aya akashandiswa naChen et al. Vachishandisa SnO2 cathode pane carbon substrate ine 1.27 mm thick catholyte layer, kusvika 90% FE 35 pa 500 mA/cm2 kwakawanikwa. Kubatanidzwa kwe thick catholyte layer uye reverse-biased bipolar membrane (BPM) inoderedza ion transfer inopa voltage yekushanda ye6 V uye kushanda zvakanaka kwesimba kwe15%. Kuti vawedzere kushanda zvakanaka kwesimba, Li et al., vachishandisa single CEM configuration, vakawana FE 29 ye93.3% pa ​​fractional current density ye51.7 mA/cm2. Diaz-Sainz et al.28 vakashandisa filter press ine single CEM membrane pa current density ye45 mA/cm2. Zvisinei, nzira dzese dzakagadzira formate pane chigadzirwa chaidiwa, formic acid. Kuwedzera kune zvimwe zvinodiwa pakugadzirisa, muma CEM configurations, mafomati akadai seKCOOH anogona kuungana nekukurumidza mumunda weGDE uye flow, zvichikonzera kurambidzwa kwekutakura uye kutadza kwemasero pakupedzisira.
Kuenzanisa kwezvitatu zvinonyanya kuzivikanwa zveCO2R kune magadzirirwo emidziyo yekushandura formate/formic acid uye magadzirirwo akatsanangurwa muchidzidzo chino. b Kuenzanisa kwehuwandu hwehuwandu hwemagetsi neformate/formic acid ye catholyte configurations, magadzirirwo esandwich, magadzirirwo eCEM imwe chete mumabhuku (anoratidzwa muSupplementary Table S1) nebasa redu. Mavanga akavhurika anoratidza kugadzirwa kweformate solution, uye mavanga akasimba anoratidza kugadzirwa kweformic acid. *Kugadziriswa kunoratidzwa uchishandisa hydrogen pa anode. c Zero-gap MEA configuration uchishandisa composite bipolar membrane ine perforated cation exchange layer inoshanda mu forward bias mode.
Kuti vadzivise kuumbwa kwemaforme, Proietto nevamwe 32 vakashandisa nzira yekusvina isina kupatsanurwa iyo mvura yakabviswa inopinda nepakati pe interlayer. Sisitimu iyi inogona kusvika >70% CE muhuwandu hwe current density hwe50–80 mA/cm2. Saizvozvowo, Yang nevamwe 14 vakakurudzira kushandiswa kwe solid electrolyte interlayer pakati peCEM neAEM kukurudzira kuumbwa kwe formic acid. Yang nevamwe 31,36 vakawana 91.3% FE mu 5 cm2 cell pa 200 mA/cm2, zvichigadzira 6.35 wt% formic acid solution. Xia nevamwe 32 Vachishandisa nzira yakafanana, 83% shanduko ye carbon dioxide (CO2) kuita formic acid FE yakawanikwa pa 200 mA/cm2, uye kusimba kwesisitimu kwakaedzwa kwemaawa zana nemaminitsi makumi matatu. Kunyangwe mhedzisiro midiki ichivimbisa, kuwedzera kwemutengo uye kuomarara kwema "porous ion exchange resins" kunoita kuti zviome kukwidza ma "interlayer configurations" kune masisitimu makuru (semuenzaniso, 1000 cm2).
Kuti tifunge nezvemhedzisiro yemagadzirirwo akasiyana, takaronga kugadzirwa kweformate/formic acid pa kWh yemasisitimu ese ambotaurwa uye takaaronga muMufananidzo 1b. Zviri pachena pano kuti chero sisitimu ine catholyte kana interlayer ichasvika pakushanda kwayo pa low current densities uye ichaderera pa high current densities, uko muganho we ohmic ungasarudza voltage yemasero. Uyezve, kunyangwe CEM configuration isingashandise simba ichipa molar formic acid yakakwira pa kWh, munyu wakawanda unogona kukonzera kudzikira kwekushanda nekukurumidza pa high current densities.
Kuti tideredze mamiriro ekukundikana akambotaurwa, takagadzira membrane electrode assembly (MEA) ine composite forward biased BPM ine perforated cation exchange membrane (PCEM). Magadzirirwo acho anoratidzwa muMufananidzo 1c. Hydrogen (H2) inopinzwa muanode kuti igadzire maproton kuburikidza nehydrogen oxidation reaction (HOR). PCEM layer inopinzwa muBPM system kuti ibvumire ma ion anogadzirwa pa cathode kuti apfuure neAEM, pamwe chete nemaproton kuti agadzire formic acid paBPM interface uye interstitial pores yeCEM, uye yobva yabuda neGDE anode uye flow field. . Tichishandisa configuration iyi, takawana >75% FE ye formic acid pa <2 V uye 300 mA/cm2 yenzvimbo ye 25 cm2 cell. Chinonyanya kukosha ndechekuti, dhizaini inoshandisa zvikamu zvinowanikwa mumusika uye hardware architectures ye fuel cell uye water electrolysis plants, zvichibvumira nguva yekukurumidzira kukura. Catholyte configurations ine catholyte flow chambers izvo zvinogona kukonzera kusagadzikana kwekumanikidzwa pakati pegasi ne liquid phases, kunyanya muma configuration makuru e cell. Kune zvivakwa zvesandwich zvine maburi emvura anoyerera, zvinodikanwa kushanda nesimba kukuru kuti pave nepakati pemaburi emvura kuti paderedzwe kudonha kwesimba uye kuunganidzwa kwecarbon dioxide mukati mepakati pemaburi. Zvese izvi zvinogona kukonzera kukanganiswa kwekutaurirana kwemasero. Zvakaomawo kugadzira maburi matete ane maburi akareruka pamwero mukuru. Kusiyana neizvi, gadziriro itsva inodiwa igadziriro yeMEA isina zero-gap isina flow chamber kana intermediate layer. Zvichienzaniswa nemamwe masero emagetsi aripo, gadziriro iyi yakasiyana nekuti inobvumira kugadzirwa kwakananga kweformic acid mugadziriro inokwenenzverwa, isingashandise simba zvakanyanya, uye isina zero-gap.
Kudzvinyirira kushanduka kwehydrogen, kuedza kukuru kwekuderedza CO2 kwakashandisa MEA neAEM membrane configurations pamwe chete ne high molar concentration electrolytes (semuenzaniso, 1-10 M KOH) kugadzira alkaline conditions pa cathode (sezvakaratidzwa muMufananidzo 2a). Mukugadzirisa uku, formate ions dzakaumbwa pa cathode dzinopfuura nepa membrane semhando dzakachajwa zvisina kunaka, ipapo KCOOH inoumbwa uye inobuda mu system kuburikidza ne anodic KOH stream. Kunyangwe formate FE ne cell voltage zvaive zvakanaka pakutanga sezvakaratidzwa muMufananidzo 2b, kuyedzwa kwekugadzikana kwakaita kuti FE iderere neanenge 30% mumaawa gumi chete (Mufananidzo S1a–c). Zvinofanira kucherechedzwa kuti kushandiswa kwe 1 M KOH anolyte kwakakosha kuderedza anodic overvoltage mu alkaline oxygen evolution reaction (OER) systems37 uye kuwana ion accessibility mukati me cathode catalyst bed33. Kana huwandu hweanolyte hwadzikiswa kusvika pa0.1 M KOH, magetsi ese ari maviri uye oxidation ye formic acid (kurasikirwa kwe formic acid) zvinowedzera (Mufananidzo S1d), zvichiratidza kutengesa zero-sum. Dhigirii re oxidation yeformate rakaongororwa uchishandisa huwandu hwese hwemasasi; kuti uwane rumwe ruzivo, ona chikamu che "Methods". Kushanda uchishandisa MEA uye single CEM membrane configurations kwakadzidzwawo, uye mhedzisiro yacho inoratidzwa muMufananidzo S1f,g. FE formate yakaunganidzwa kubva ku cathode yaive >60% pa200 mA/cm2 pakutanga kwebvunzo, asi yakakurumidza kuora mukati memaawa maviri nekuda kwekuunganidzwa kwe cathode salt kwakambotaurwa (Mufananidzo S11).
Chimiro che zero-gap MEA ine CO2R pa cathode, hydrogen oxidation reaction (HOR) kana OER pa anode, uye imwe AEM membrane iri pakati. b FE ne cell voltage yegadziriro iyi ine 1 M KOH ne OER inoyerera pa anode. Error bars dzinomiririra standard deviation yezvikamu zvitatu zvakasiyana. mu FE ne system cell voltage ine H2 ne HOR pa anode. Mavara akasiyana anoshandiswa kusiyanisa kugadzirwa kweformate ne formic acid. d Chimiro che Schematic diagram ye MEA ine BPM yakachinjirwa mberi pakati. FE ne battery voltage ichienzaniswa nenguva pa 200 mA/cm2 uchishandisa gadziriro iyi. f Mufananidzo we cross-sectional we forward-biased BPM MEA mushure mebvunzo pfupi.
Kuti igadzire formic acid, hydrogen inoendeswa kune Pt-on-carbon (Pt/C) catalyst pa anode. Sezvakaratidzwa muMufananidzo 2d, BPM inogadzira mapurotoni pa anode yakamboongororwa kuti iwane formic acid production. BPM tuning unit yakakundikana mushure memaminitsi makumi mana ekushanda pa 200 mA/cm2 current, pamwe chete ne voltage surge inodarika 5 V (Mufananidzo 2e). Mushure mekuyedza, delamination yakajeka yakaonekwa pa CEM/AEM interface. Kunze kweformate, maanion akadai se carbonate, bicarbonate uye hydroxide anogonawo kupfuura nepaAEM membrane uye oita nemaprotoni pa CEM/AEM interface kugadzira CO2 gas nemvura yemvura, zvichikonzera BPM delamination (Mufananidzo 2f) uye , zvichizopedzisira zvaita kuti cell failure isashande.
Zvichibva pakushanda uye kukundikana kwemaitiro ekugadzirisa ari pamusoro apa, dhizaini itsva yeMEA inokurudzirwa sezvakaratidzwa muMufananidzo 1c uye yakatsanangurwa muMufananidzo 3a38. Pano, PCEM layer inopa nzira yekufamba kwe formic acid nemaanion kubva kuCEM/AEM interface, nokudaro ichideredza kuunganidzwa kwechinhu ichi. Panguva imwe chete, nzira yePCEM interstitial inotungamira formic acid mu diffusion medium uye flow field, ichideredza mukana we formic acid oxidation. Mhedzisiro ye polarization inoshandisa AEMs dzine ukobvu hwe 80, 40 uye 25 mm inoratidzwa muMufananidzo 3b. Sezvakatarisirwa, kunyangwe voltage yesero ichiwedzera nekuwedzera kweAEM ukobvu, kushandisa AEM yakakora kunodzivirira back diffusion ye formic acid, nokudaro zvichiwedzera cathode pH uye kuderedza kugadzirwa kweH2 (Mufananidzo 3c–e).
Mufananidzo wechimiro cheMEA chine AEM neCEM yakaboorwa uye nzira dzakasiyana dzekutakura formic acid. b Voltage yemasero pahuwandu hwakasiyana hwemagetsi uye ukobvu hwakasiyana hweAEM. muEE pahuwandu hwakasiyana hwemagetsi nehukobvu hweAEM hwe80 μm (d) 40 μm, e) 25 μm. Mitsetse yekukanganisa inomiririra kutsauka kwakajairwa kwakayerwa kubva kumasampuli matatu akasiyana. f Mhedzisiro yekufananidza yehuwandu hweformic acid uye pH kukosha paCEM/AEM interface pahukobvu hwakasiyana hweAEM. f PC uye pH mu cathode layer ye catalyst ine ukobvu hwakasiyana hweAEM film. g Kugoverwa kwezvikamu zviviri kwehuwandu hweformic acid neCEM/AEM interface uye kuboorwa.
Mufananidzo S2 unoratidza kugoverwa kwehuwandu hweasidhi yefomu uye pH muhukobvu hweMEA uchishandisa Poisson-Nernst-Planck finite element modeling. Hazvishamisi kuti huwandu hwakanyanya hweasidhi yefomu, 0.23 mol/L, hunoonekwa paCEM/AEM interface, sezvo formic acid inoumbwa pahukobvu uhwu. Kuwanda kweasidhi yefomu kuburikidza neAEM kunoderera nekukurumidza sezvo ukobvu hweAEM huchiwedzera, zvichiratidza kuramba kukuru kuchinjirwa kwemasero uye kuyerera kushoma kweasidhi yefomu nekuda kwekupararira kwemashure. Mifananidzo 3 f na g inoratidza pH uye formic acid values ​​​​mubed catalyst inokonzerwa nekupararira kwemashure uye kupararira kwehuwandu hweasidhi yefomu, zvichiteerana. Kana AEM membrane yakatetepa, huwandu hweasidhi yefomu pedyo necathode hunokwira, uye pH yecathode inova acidic. Nokudaro, kunyangwe AEM membranes yakakora ichikonzera kurasikirwa kwakanyanya kwe ohmic, zvakakosha kudzivirira kupararira kweasidhi yefomu kuenda ku cathode uye kuwedzera kuchena kwakanyanya kweFE formic acid system. Pakupedzisira, kuwedzera ukobvu hweAEM kusvika 80 μm kwakaita kuti FE >75% ye formic acid pa <2 V uye 300 mA/cm2 yenzvimbo yesero ye25 cm2.
Kuti kuyedze kugadzikana kwechimiro ichi chakavakirwa paPECM, simba rebhatiri rakachengetwa pa200 mA/cm2 kwemaawa makumi mashanu nemashanu. Mhedzisiro yese inoratidzwa muMufananidzo 4, nemhedzisiro yemaawa matatu ekutanga yakaratidzwa muMufananidzo S3. Pakushandisa Pt/C anodic catalyst, voltage yemasero yakawedzera zvakanyanya mukati memaminitsi makumi matatu ekutanga (Mufananidzo S3a). Nenguva yakareba, voltage yemasero yakaramba yakafanana, zvichipa mwero wekuora kwe0.6 mV/h (Mufananidzo 4a). Pakutanga kwebvunzo, PV ye formic acid yakaunganidzwa pa anode yaive 76.5% uye PV yehydrogen yakaunganidzwa pa cathode yaive 19.2%. Mushure meawa yekutanga yebvunzo, hydrogen FE yakaderera kusvika pa13.8%, zvichiratidza kuvandudzika kweformate selectivity. Zvisinei, mwero wekuoxidation we formic acid musystem wakaderera kusvika 62.7% muawa imwe chete, uye mwero wekuoxidation we anodic formic acid wakawedzera kubva painenge zero pakutanga kwebvunzo kusvika 17.0%. Mushure mezvo, FE yeH2, CO, formic acid uye mwero wekuoxidation we formic acid wakaramba wakasimba panguva yekuyedza. Kuwedzera kwe formic acid oxidation mukati meawa yekutanga kunogona kunge kuri nekuda kwekuunganidzwa kwe formic acid paPCEM/AEM interface. Sezvo huwandu hwe formic acid huchiwedzera, haingobudi nepaburi re membrane chete, asiwo inopararira kuburikidza neFEM pachayo uye inopinda muPt/C anode layer. Sezvo formic acid iri mvura pa60°C, kuunganidzwa kwayo kunogona kukonzera matambudziko ekutapurirana kwehuwandu uye kukonzera oxidation inosarudzwa kupfuura hydrogen.
a Sero voltage vs nguva (200 mA/cm2, 60 °C). Chinyorwa chiri mukati chinoratidza mufananidzo we optical microscope wechikamu cheMEA chine EM yakaboorwa. Scale bar: 300 µm. b Kuchena kwePE uye formic acid sekushanda kwenguva pa200 mA/cm2 uchishandisa Pt/C anode.
Maumbirwo emasampuli pakutanga kwekuyedzwa (BOT) panguva yekugadzirira uye pakupera kwekuyedzwa (EOT) mushure memaawa makumi mashanu nemashanu ekuyedzwa kwekugadzikana akatsanangurwa achishandisa nano-X-ray computed tomography (nano-CT), sezvakaratidzwa muMufananidzo 5 a. Muenzaniso weEOT une saizi yakakura ye catalyst particle ine dhayamita ye1207 nm zvichienzaniswa ne930 nm yeBOT. Mifananidzo yeHigh-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) uye mhedzisiro ye energy-dispersive X-ray spectroscopy (EDS) inoratidzwa muMufananidzo 5b. Kunyange hazvo BOT catalyst layer iine akawanda ema catalyst particles madiki pamwe nemamwe ma agglomerates makuru, muchikamu cheEOT catalyst layer inogona kukamurwa kuita nzvimbo mbiri dzakasiyana: imwe ine ma solid particles akakura zvakanyanya uye imwe ine ma porous regions akawanda. Huwandu hwema porous particles. Mufananidzo weEDS unoratidza kuti ma solid particles makuru akapfuma muBi, pamwe metallic Bi, uye ma porous regions akapfuma mu oxygen. Kana sero richishanda pa200 mA/cm2, simba re cathode risingashande zvakanaka richakonzera kudzikira kweBi2O3, sezvinoratidzwa nemhedzisiro ye in situ X-ray absorption spectroscopy yakakurukurwa pazasi. Mhedzisiro ye HAADF-STEM ne EDS mapping inoratidza kuti Bi2O3 inopinda muchirongwa chekudzikisa, zvichiita kuti varasikirwe neokisijeni uye vaungane kuita zvidimbu zvesimbi zvakakura. Mapatani eX-ray diffraction ema BOT ne EOT cathodes anosimbisa dudziro yedata re EDS (Mufananidzo 5c): crystalline Bi2O3 chete ndiyo yakaonekwa mu BOT cathode, uye crystalline bimetal yakawanikwa mu EOT cathode. Kuti tinzwisise mhedzisiro ye cathode potential pa oxidation state ye Bi2O3 cathode catalyst, tembiricha yakasiyana kubva pa open circuit potential (+0.3 V vs RHE) kusvika -1.5 V (vs RHE). Zvinoonekwa kuti chikamu cheBi2O3 chinotanga kudzikiswa pa -0.85 V zvichienzaniswa neRHE, uye kudzikira kwesimba remutsara muchena munzvimbo yemucheto we spectrum kunoratidza kuti metallic Bi inodzikiswa kusvika 90% yeRHE pa -1.1. V ichipesana neRHE (Mufananidzo 5d). Pasinei nemaitiro acho, sarudzo yese yeformeti pa cathode haina kuchinja, sezvinoonekwa kubva kuH2 neCOFE uye formic acid formation, pasinei nekuchinja kukuru mu cathode morphology, catalyst oxidation state, uye microcrystalline structure.
a Chimiro chechikamu chetatu che catalyst layer uye kugoverwa kwezvikamu zve catalyst zvinowanikwa uchishandisa nano-X-ray CT. Scale bar: 10 µm. b Pamusoro 2: Mifananidzo yeHAADF-STEM yema cathode layers eBOT neEOT catalysts. Scale bar: 1 µm. Pasi 2: Mifananidzo yakakura yeHADF-STEM neEDX ye cathode layer yeEOT catalyst. Scale bar: 100 nm. c Mapatani eX-ray diffraction eBOT neEOT cathode samples. d In situ X-ray absorption spectra yeBi2O3 electrode mu 0.1 M KOH sebasa re potential (0.8 V kusvika -1.5 V vs. RHE).
Kuti tizive kuti ndeapi mikana iripo yekuvandudza mashandiro esimba nekudzivirira formic acid oxidation, H2 reference electrode yakashandiswa kuona mupiro wekurasikirwa kwevoltage39. Pahuwandu hwemagetsi huri pasi pe500 mA/cm2, cathode potential inoramba iri pasi pe -1.25 V. Anodic potential yakakamurwa kuita zvikamu zviviri zvikuru: exchange current density HOR uye theoretical overvoltage HOR 40 yakafanotaurwa neBulter-Volmer equation yakayerwa kare, uye chikamu chasara chinokonzerwa neoxidation formic acid. Nekuda kwe reaction kinetics inononoka zvikuru kana ichienzaniswa neHOR41, mwero mudiki we formic acid oxidation reaction pa anode unogona kukonzera kuwedzera kukuru kweanodic potential. Mhedzisiro yacho inoratidza kuti kudziviswa kwakakwana kwe formic acid anodic oxidation kunogona kubvisa overvoltage inosvika 500 mV.
Kuti tiedze fungidziro iyi, mwero wekuyerera kwemvura yakabviswa ion (DI) panzvimbo inopinzwa anode wakasiyana-siyana kuderedza kuwanda kwe effluent formic acid. Mifananidzo 6b na c inoratidza FE, kuwanda kwe formic acid, uye cell voltage sebasa re DI flux pa anode pa 200 mA/cm2. Sezvo mwero wekuyerera kwemvura yakabviswa ion wakawedzera kubva pa 3.3 mL/min kusvika pa 25 mL/min, kuwanda kwe formic acid pa anode kwakaderera kubva pa 0.27 mol/L kusvika pa 0.08 mol/L. Mukuenzanisa, uchishandisa chimiro chesandwich chakakurudzirwa naXia et al. 30, kuwanda kwe formic acid kwe 1.8 mol/L kwakawanikwa pa 200 mA/cm2. Kuderedza kuwanda kunovandudza FE yese ye formic acid uye kunoderedza FE ye H2 sezvo cathode pH ichiwedzera alkaline nekuda kwekudzikira kwekupararira kwe formic acid kumashure. Kudzikira kwehuwandu hweasidhi yeforamu pahuwandu hweDI hwakabvisawo zvachose oxidation yeforamu, zvichikonzera huwandu hwemagetsi esero ari pasi pe1.7 V pa200 mA/cm2. Kupisa kwebhatiri kunokanganisawo mashandiro ese, uye mhedzisiro yacho inoratidzwa muMufananidzo S10. Zvisinei, magadzirirwo akavakirwa paPCEM anogona kuvandudza zvakanyanya kushanda kwesimba mukudzivirira oxidation yeforamu, kungave kuburikidza nekushandisa anodic catalysts ine hydrogen selectivity yakagadziridzwa kune formic acid kana kuburikidza nekushanda kwemudziyo.
a Kuputsika kwemagetsi emasero uchishandisa electrode yeH2 reference cell inoshanda pa60 °C, anode yePt/C uye 80 µm AEM. b Kuwanda kweFE uye formic acid kunounganidzwa pa200 mA/cm2 uchishandisa mwero wakasiyana wekuyerera kwemvura inobviswa ion. c Kana anode ikaunganidza formic acid muhuwandu hwakasiyana, voltage yemasero i200 mA/cm2. Error bars inomiririra kutsauka kwakajairwa kwezviyero zvitatu zvakasiyana. d Mutengo wekutengesa wakaderera unopatsanurwa nekushanda pamitengo yakasiyana-siyana yekuyerera kwemvura inobviswa ion uchishandisa mitengo yemagetsi yeindasitiri yenyika yeUS$0.068/kWh uye US$4.5/kg hydrogen. (*: Mamiriro ekunze e oxidation e formic acid pa anode anofungidzirwa kuva 10 M FA, avhareji yemutengo wemagetsi eindasitiri yenyika i $0.068/kWh, uye hydrogen i $4.5/kg. **: Mamiriro ekunze e oxidation i anofungidzirwa kuti i formic acid. Kuwanda kweFA pa anode i 1.3 M anode, mutengo wemagetsi wemangwana unotarisirwa i $0.03/kWh, uye mutsetse une dotted unomiririra mutengo wemusika we 85 wt% FA.
Ongororo yezvehupfumi (TEA) yakaitwa kuti pave nemutengo wekutengesa wemafuta pasi pemamiriro akasiyana-siyana ekushanda, sezvakaratidzwa muMufananidzo 5d. Nzira nedata rekare reTEA zvinogona kuwanikwa muSI. Kana huwandu hweLC mu anode exhaust hwakakwira, pasinei ne voltage yakakwira yemasero, mutengo wese we fuel assembly unodzikira nekuda kwekuderedzwa kwemutengo wekuparadzanisa. Kana anodic oxidation ye formic acid inogona kuderedzwa kuburikidza ne catalyst development kana electrode technology, kusanganiswa kwe voltage yakaderera yemasero (1.66 V) uye huwandu hwakakwira hwe FA mu effluent (10 M) zvaizoderedza mutengo we electrochemical FA production kusvika pa 0.74 US dollars/kg (zvichienderana nemagetsi). mutengo) $0.068/kWh uye $4.5/kg hydrogen42. Uyezve, kana zvabatanidzwa nemutengo wemangwana wemagetsi anogona kushandiswazve we $0.03/kWh uye hydrogen ye $2.3/kg, chinangwa cheFA wastewater chinoderedzwa kusvika pa 1.3 miriyoni, zvichikonzera mutengo wekupedzisira wekugadzira i US$0.66/kg43. Izvi zvinoenzaniswa nemitengo yemusika iripo. Saka, kuedza mune ramangwana kwakatarisana nezvinhu zvemagetsi nemaumbirwo zvinogona kuderedza anodization uku zvichibvumira kushanda pama voltage emasero akaderera kugadzira huwandu hweLC hwakakwira.
Muchidimbu, takadzidza zvimiro zvakawanda zveMEA zve zero-gap zvekuderedza CO2 kuita formic acid uye takapa chimiro chine composite forward-biased bipolar membrane inosanganisira perforated cation exchange membrane (PECM) kuti zvibatsire membrane mass transfer interface yeformic acid inobuda. . Kugadziriswa uku kunogadzira >96% formic acid pahuwandu hunosvika 0.25 M (pa anode DI flow rate ye3.3 mL/min). Pa DI flow rates yakakwira (25 mL/min), kurongeka uku kwakapa current density ye >80% FE ye200 mA/cm2 pa 1.7 V tichishandisa 25 cm2 cell area. Pa 25 cm2 anodic DI rates (10 mL/min), kurongeka kwePECM kwakachengetedza voltage yakagadzikana uye high formic acid FE levels kwemaawa makumi mashanu nemashanu ekuyedza pa 200 mA/cm2. Kugadzikana kwakanyanya uye kusarudza kunowanikwa nema catalysts anowanikwa mukutengeserana uye polymeric membrane materials zvinogona kuwedzerwa nekubatanidza nema optimized electrocatalysts. Basa rinotevera richatarisa pakugadzirisa mamiriro ekushanda, anode catalyst selectivity, uye chimiro cheMEA kuderedza formic acid oxidation, zvichikonzera kubuda kwemvura yakawanda pamagetsi emasero akaderera. Nzira iri nyore yekushandisa carbon dioxide ye formic acid yakaratidzwa pano inobvisa kudiwa kwemakamuri e anolyte ne catholyte, zvikamu zvesandwich, nezvinhu zvakakosha, nokudaro zvichiwedzera kushanda zvakanaka kwesimba remasero uye kuderedza kuoma kwesystem, zvichiita kuti zvive nyore kuwedzera. Kugadziriswa kwacho kunopa puratifomu yekuvandudza mune ramangwana zvirimwa zveCO2 zvinobudirira mune zvehunyanzvi uye zvemari.
Kunze kwekunge zvataurwa neimwe nzira, zvinhu zvese zvemhando yemakemikari uye zvinonyungudutsa zvakashandiswa sezvakagamuchirwa. Bismuth oxide catalyst (Bi2O3, 80 nm) yakatengwa kubva kuUS Research Nanomaterials, Inc. Polymer powder (AP1-CNN8-00-X) yakapihwa neIONOMR. Omnisolv® brand N-propanol (nPA) uye ultrapure water water (18.2 Ω, Milli–Q® Advantage A10 water purification system) zvakatengwa kubva kuMillipore Sigma. Methanol neacetone zvakabvumidzwa neACS zvinotengwa kubva kuVWR Chemicals BDH® neFisher Chemical, zvichiteerana. Polymer powder yakasanganiswa nemusanganiswa weacetone nemethanol muchiyero che1:1 nehuremu kuti pave nekupararira kwepolymer ine huwandu hwe6.5 wt.%. Gadzirira inki yecatalytic nekusanganisa 20g Bi2O3, ultrapure water, nPA uye ionomer dispersion mubhodhoro re30ml. Musanganiswa wacho waiva ne30 wt.% catalyst, chiyero chehukuru hweionomer kune catalyst che0.02 uye chiyero chehukuru hwealcohol nemvura che2:3 (40 wt.% nPA). Usati wasanganisa, 70g yeGlen Mills 5mm zirconia grinding material yakawedzerwa kumusanganiswa. Samples dzakaiswa paFisherbrand™ digital bottle roller pa80 rpm kwemaawa makumi maviri nematanhatu. Rega inki igare kwemaminitsi makumi maviri usati waisa. Inki yeBi2O3 yakaiswa paQualtech automatic applicator (QPI-AFA6800) uchishandisa 1/2″ x 16″ laboratory wirewound refill (RD Specialties - 60 mil diameter) pa22°C. 5 mL yeinki catalytic yakaiswa pa7.5 x 8 inch Sigraacet 39 BB carbon gas diffusion carrier (fuel cell storage) nekuisa tsvimbo paavhareji yakatarwa ye55 mm/sec. Tumira maerekitirodhi aya akaputirwa muovheni woomesa pa80 °C. Maitiro ekuputira tsvimbo nemifananidzo yeGDE coating zvinoratidzwa muMifananidzo S4a uye b. Chishandiso cheX-ray fluorescence (XRF) (Fischerscope® XDV-SDD, Fischer-Technolgy Inc. USA) chakasimbisa kuti GDE loading yakaputirwa yaive 3.0 mg Bi2O3/cm2.
Pakuumbwa kwe membrane ine anion exchange membrane (AEM) neCEM yakaboorwa. Nafion NC700 (Chemours, USA) ine ukobvu hwe 15 µm yakashandiswa se CEM layer. Anodic catalyst yakapfapfaidzwa zvakananga pa FEM ne ionomer kune carbon ratio ye 0.83 uye nzvimbo yekufukidza ye 25 cm2. Platinum yakatsigirwa ine nzvimbo yakakura yepamusoro (50 wt.% Pt/C, TEC 10E50E, TANAKA precious metal) ine mutoro we 0.25 mg Pt/cm2 yakashandiswa se anode catalyst. Nafion D2020 (Ion Power, USA) yakashandiswa se anode layer ye anode ye catalyst. CEM perforation inoitwa nekucheka mitsara yakafanana pa CEM film panguva dze 3mm. Tsanangudzo yemaitiro ekuboorwa inoratidzwa muMifananidzo S12b na c. Uchishandisa X-ray computed tomography, zvakasimbiswa kuti mukana wekuboorwa kwemasero waiva 32.6 μm, sezvakaratidzwa muMufananidzo S12d na e. Panguva yekuungana kwemasero, membrane yeCEM yakaboorwa necatalyst yakaiswa papepa reToray re 25 cm2 (5 wt% PTFE yakarapwa, Fuel Cell Store, USA). Kamudzira keAEM (PiperION, Versogen, USA) kane ukobvu hwe 25, 40 kana 80 μm kakaiswa pamusoro peCEM uye ipapo paGDE cathode. Kamudzira keAEM kakachekwa kuita zvidimbu zve 7.5 × 7.5 cm kuti kavhare nzvimbo yese yekuyerera kwemvura uye kakanyikwa husiku hwese mu 1 M potassium hydroxide solution isati yaungana. Anode ne cathode zvese zvinoshandisa PTFE spacers dzakakora zvakakwana kuti dzisvike pakumanikidzwa kweGDE kwakanaka kwe 18%. Tsanangudzo yemaitiro ekubatanidza mabhatiri inoratidzwa muMufananidzo S12a.
Munguva yekuedza, sero rakaunganidzwa rakachengetwa pa60 °C (30, 60, uye 80 °C kuti pave nezvidzidzo zvekushandiswa kwetembiricha) ne0.8 L/min yehydrogen gasi yakapihwa kune anode uye 2 L/min yecarbon dioxide yakapihwa kune cathode. Mhepo dzinoyerera dzeanodic necathodic dzakanyoroveswa pa100% hunyoro uye 259 kPa absolute cathodic pressure. Munguva yekushanda, cathode gas stream yakasanganiswa ne1 M KOH solution pachiyero che2 mL/min kukurudzira kushandiswa kwe cathode catalyst bed uye ionic conduction. Sanganisa rwizi rwegasi reanode nemvura yakabviswa ionized pachiyero che10 ml/min kubvisa formic acid pa anode. Ruzivo rwezvinopinzwa nezvinobuda mumudziyo zvinoratidzwa muMufananidzo S5. Cathode exhaust gas ine CO2 uye inogadzira CO2 neH2. Utsi hwemvura hunobviswa kuburikidza ne condenser (low temperature heat exchanger pa2°C). Gasi rasara richaunganidzwa kuti riongorore nguva yegasi. Kuyerera kweanode kuchapfuurawo nemuchina we condenser kuti uparadzanise mvura kubva mugasi. Mvura yakasviba ichaunganidzwa mumabhodhoro akachena uye ichaongororwa uchishandisa liquid chronometry kuti uverenge formic acid inogadzirwa. Miedzo ye electrochemical yakaitwa uchishandisa Garmy potentiostat (nhamba yekutarisa 30K, Gamry, USA). Vasati vayera polarization curve, sero rakagadziriswa ka4 kubva pa0 kusvika 250 mA/cm2 vachishandisa linear voltammetry ine scan rate ye2.5 mA/cm2. Polarization curves dzakawanikwa mu galvanostatic mode nesero rakachengetwa pa current density kwemaminitsi mana vasati vatora cathode gas ne anolyte liquid.
Tinoshandisa hydrogen reference electrode muMEA kupatsanura cathode neanodic potentials. Maumbirwo e electrode reference anoratidzwa muMufananidzo S6a. Nafion membrane (Nafion 211, IonPower, USA) yakashandiswa se ionic bridge kubatanidza MEA membrane ne reference electrode. Mugumo mumwe weNafion strip wakabatana ne 1 cm2 gas diffusion electrode (GDE) yakazadzwa ne 0.25 mg Pt/cm2 (50 wt% Pt/C, TEC10E50E, TANAKA Precious Metals) yakaputirwa pa 29BC carbon paper (Fuel Cell Store, USA). ). Special polyetheretherketone (PEEK) hardware inoshandiswa kuvhara gasi uye kuona kuti GDE neNafion strips zvinobatana zvakanaka, uye kubatanidza reference electrode ne fuel cell hardware. Mumwe mugumo weNafion strip wakabatana ne extruding edge ye CEM battery. Mufananidzo S6b unoratidza cross section ye reference electrode yakabatana ne MEA.
Mushure mekunge gasi rinobuda mumhepo rapfuura nemuchina we condenser uye gas-liquid separator, sampuro dzegasi dzinotorwa kubva mu cathode. Gasi rakaunganidzwa rakaongororwa katatu uchishandisa 4900 Micro GC (10 μm molecular sieve, Agilent). Sampuro dzakaunganidzwa mumabhegi e sample gas sample ane inert multi-layer aluminium foil gas sample bags Supel™ (Sigma-Aldrich) kwenguva yakatarwa (masekondi makumi matatu) uye dzakaiswa nemaoko mu microgas chromatograph mukati memaawa maviri ekutora. Tembiricha ye injection yakaiswa pa110°C. Carbon monoxide (CO) ne hydrogen (H2) zvakaparadzaniswa pa column ye MS5A ine pressurized (28 psi) 10 m uchishandisa argon (Matheson Gas-Matheson Purity) segasi rinotakura. Kubatana uku kunowanikwa uchishandisa Thermal Conductivity Detector (TCD) yakavakwa mukati. GC chromatograms uye CO ne H2 calibration curves zvinoratidzwa muMufananidzo S7. Sampuli dzemvura dzinonzi liquid formic acid dzakaunganidzwa kubva muanode kwenguva yakatarwa (masekonzi 120) uye dzakasefa uchishandisa 0.22 μm PTFE syringe filter mumabhodhoro e2 mL. Zvigadzirwa zvemvura mumabhodhoro zvakaongororwa uchishandisa Agilent 1260 Infinity II bioinert high-performance liquid chromatography (HPLC) system, umo 20 μl yesample yakapinzwa kuburikidza ne autosampler (G5668A) ine mobile phase ye 4 mM sulfuric acid (H2SO4). ) pa flow rate ye 0.6 ml/min (quaternary pump G5654A). Zvigadzirwa zvakaparadzaniswa pa (35°C, column oven G7116A) Aminex HPX-87H 300 × 7.8 mm (Bio-Rad) yakatangira ne Micro-Guard Cation H guard column. Formic acid yakaonekwa uchishandisa diode array detector (DAD). pa wavelength ye 210 nm uye bandwidth ye 4 nm. HPL chromatogram uye formic acid standard calibration curve zvinoratidzwa muMufananidzo S7.
Zvigadzirwa zvegasi (CO neH2) FE zvinoverengerwa uchishandisa equation inotevera, uye huwandu hwese hwemamoles egasi hunoverengerwa uchishandisa equation yegasi yakakodzera:
Pakati pavo: \({n}_{i}\): huwandu hwemaerekitironi mu electrochemical reaction. \(F\): Faraday's constant. \({C}_{i}\): HPLC liquid product concentration. \(V\): vhoriyamu yemvura yakaunganidzwa munguva yakatarwa t. \(j\): current density. \(A\): Geometric area ye electrode (25 cm2). \(t\): sampling time period. \(P\): absolute pressure. \({x}_{i}\): Mole percent yegesi inotsanangurwa neGC. \(R\): gas constant. \(T\): tembiricha.
Kuwanda kwema "anodic cations" kwakayerwa uchishandisa inductively coupled plasma atomic emission spectroscopy (ICP-OES). Ma "cations" anogona kupinda mu "anode" anosanganisira Ti, Pt, Bi na K. Kunze kweK, mamwe ma "cations" ese aive pasi pe "detection limit". Ma "ions" mu "solution" anosiya "anode" ichibatana nema "protons" kana mamwe ma "cations". Saka, kuchena kwe "formic acid" kunogona kuverengerwa se
Kugadzirwa kweFormate/FA kunomiririra huwandu hweFA hunogadzirwa pa kWh yemagetsi anoshandiswa uchishandisa MEA configuration chaiyo, mu mol/kWh. Inoverengerwa zvichibva pahuwandu hwemazuva ano, voltage yemasero uye kushanda zvakanaka kweFaraday pasi pemamiriro chaiwo ekushanda.
Verenga huwandu hwe formic acid yakasanganiswa pa anode zvichibva pahuwandu hwe ...
Takashandisa GC kuyera huwandu hwe formic acid, hydrogen, uye CO zvakaunganidzwa neHPLC. Zvinofanira kucherechedzwa kuti yakawanda ye formic acid yakaunganidzwa kubva ku anode tichishandisa setup inoratidzwa muSupplementary Figure S5. Huwandu hweformate hwakaunganidzwa kubva mu cathode chamber hauna kukosha, hunenge huviri hukuru hwakaderera, uye hunosvika pasi pe0.5% yehuwandu hwese hwe SC.
Modhi yekufambisa inoenderera mberi yakashandiswa pano yakavakirwa pabasa rekare pamasisitimu akafanana34. Sisitimu yakabatana yePoisson-Nerst-Planck (PNP) equations inoshandiswa kuona huwandu hwemvura uye electrostatic potential muzvikamu zvemagetsi uye ionically conducting. Ongororo yakadzama ye equations dziri pasi uye model geometry inopiwa muSI.
Sisitimu iyi inosarudza huwandu hwezvinhu zvisere zvine mvura (\({{{{{\rm{C}}}}}}}{{{{{\rm{O}}}}}}}}_{2 \left ({{{{{\rm{aq}}}}}}}\right)}\), \({{{{{\rm{H}}}}}}}}}^{+ }\ ), \ ({{{{\rm{O}}}}}}{{{{{\rm{H}}}}}}^{-}\), \({{{ {{ \rm{HCO}}}}}}}_{3}^{-}\), \({{{{\rm{CO}}}}}}_{3}^{ 2-} \ ),\ ({{{{\rm{HCOOH}}}}}}}\), \({{{{{\rm{HCOO}}}}}}}}}^{- }\) uye \({{{ {{\rm{K}}}}}}}^{+}\)), electrostatic potential mu ionic conducting phase (\({\phi }_{I}\ )) uye anodic uye cathodic electron conductivity. Electrostatic potentials muzvikamu (\({\phi }_{A}\) uye \({\phi }_{C}\) zvichiteerana). Pane kudaro, hapana local electrical neutral kana charge distribution functions dzinoitwa, nzvimbo ye space charge inogadziriswa zvakananga uchishandisa Poisson's equation; Iyi nzira inotibvumira kutevedzera zvakananga Donnan repulsion effects paCEM|AEM, CEM|Pore, uye AEM|Pore interfaces. Pamusoro pezvo, porous electrode theory (PET) inoshandiswa kutsanangura charge transport mu anodic uye cathodic layers ye catalyst. Sekuziva kwevanyori, basa iri rinomiririra kushandiswa kwekutanga kwePET mumasisitimu ane nzvimbo dzakawanda dzekuchaja.
Samples dzeGDE BOT neEOT cathode dzakaedzwa pachishandiswa Zeiss Xradia 800 Ultra ine 8.0 keV X-ray source, absorption uye wide field modes, uye image fusion1. Mifananidzo 901 yakaunganidzwa kubva -90° kusvika 90° nenguva yekuona 50 seconds. Kugadziriswa patsva kwakaitwa pachishandiswa back projection filter ine voxel size ye64 nm. Kuongorora kupatsanurwa kwezvikamu uye particle size distribution kwakaitwa pachishandiswa kodhi yakanyorwa zvakananga.
Kushandiswa kwemaerekitironi nemicroscope kunosanganisira kuisa maMEA ekuedzwa mu epoxy resin mukugadzirira kupatsanurwa kwakatetepa nebanga redhaimani. Chikamu cheMEA yega yega chakachekwa kusvika paukobvu hwe50 kusvika 75 nm. Talos F200X transmission electron microscope (Thermo Fisher Scientific) yakashandiswa pakuongorora transmission electron microscopy (STEM) uye energy-dispersive X-ray spectroscopy (EDS). Maikorosikopu iyi ine EDS Super-X system ine ma detector mana asina mahwindo eSDD uye inoshanda pa200 kV.
Mapatani eX-ray diffraction ePowder X-ray (PXRD) akawanikwa paBruker Advance D8 powder X-ray diffractometer ine Ni-filtered Cu Kα radiation inoshanda pa40 kV uye 40 mA. Range yekuskena iri kubva pa10° kusvika 60°, saizi yedanho i0.005°, uye kumhanya kwekuwana data imasekondi 1 padanho rega rega.
RAS spectrum iri kumucheto kweBi2O3 Bi L3 catalyst yakayerwa sebasa re potential uchishandisa cell yakagadzirwa kumba. Inki yeBi2O3 catalytic ionomer yakagadzirwa uchishandisa 26.1 mg Bi2O3 yakasanganiswa ne 156.3 μL ionomer solution (6.68%) uye yakabviswa ne 1 M KOH, mvura (157 μL) uye isopropyl alcohol (104 μL) kuti iwane inki yeionomer. Catalyst coefficient ndeye 0.4. Inki yakaiswa pamapepa e graphene munzvimbo dzakaita rectangular (10×4 mm) kusvika Bi2O3 catalyst loading yasvika 0.5 mg/cm2. Rimwe pepa re graphene rakaputirwa neKapton kuti iparadzanise nzvimbo idzi kubva ku electrolyte. Pepa re graphene rakaputirwa ne catalyst rakaiswa pakati pe PTFE mbiri uye rakabatanidzwa ku cell body (PEEK) ne screws, Mufananidzo S8. Hg/HgO (1 M NaOH) rakashandiswa se reference electrode, uye carbon paper rakashandiswa se counter electrode. Hg/HgO reference electrode yakayerwa uchishandisa waya yeplatinum yakanyudzwa muhydrogen-saturated 0.1 M KOH kuti ishandure ma potentials ese akayerwa kuita reversible hydrogen electrode (RHE) scale. XRD spectra dzakawanikwa nekutarisa potential yeBi2O3/graphene sheet working electrode yakanyudzwa mu0.1 M KOH, ichipisa kusvika 30 °C. Electrolyte inotenderera mubhatiri, electrolyte inlet iri pasi pesero uye outlet iri pamusoro kuti ive nechokwadi chekuti electrolyte inosangana ne catalyst layer kana mabubbles aumbwa. CH Instruments 760e potentiostat yakashandiswa kudzora potential ye electrode inoshanda. Potential sequence yaive open circuit potential: -100, -200, -300, -400, -500, -800, -850, -900, -1000, -1100, -1500 uye +700 mV zvichienderana neRHE. Ma potentials ese e iR akagadziriswa.
Bi L3 edge (~13424 eV yeBi metal) X-ray absorption fine structure (XAFS) spectroscopy yakaitwa pa channel 10-ID, Advanced Photon Source (APS), Argonne National Fluorescence Laboratory. National Model Measurement Laboratory. Monochromator yeTwo-crystal Si(111) yakatonhodzwa ne liquid nitrogen yakashandiswa kugadzirisa simba reX-ray, uye girazi rakaputirwa nerhodium rakashandiswa kuderedza harmonic content. Simba reScan rakasiyana kubva pa13200 kusvika 14400 eV, uye fluorescence yakayerwa uchishandisa 5 × 5 silicon PIN diode array isina ma filters kana Soller slits. Zero crossing energy ye second derivative inoyerwa pa13271.90 eV kuburikidza neL2 edge yePt foil. Nekuda kweukobvu hwe electrochemical cell, zvaisakwanisika kuyera panguva imwe chete spectrum ye reference standard. Saka, shanduko yakaverengerwa ye scan-to-scan mu incident X-ray energy i ±0.015 eV zvichibva pakuyerwa kwakadzokororwa mukati mekuyedzwa. Ukobvu hweBi2O3 layer hunotungamira kune imwe nhanho yekuzvinyudza kwe fluorescence; ma electrodes anochengetedza tarisiro yakatarwa maererano ne incident beam uye detector, zvichiita kuti ma scan ese aite seakafanana. Near-field XAFS spectrum yakashandiswa kuona mamiriro e oxidation uye chemical form ye bismuth nekuenzanisa neXANES region yeBi neBi2O3 standards uchishandisa linear combination fitting algorithm yeAthena software (version 0.9.26). ne code IFEFFIT 44.
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