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Kugabanya dioxyde de carbone muri aside formike mu buryo bw'amashanyarazi ni uburyo bwiza bwo kunoza ikoreshwa rya dioxyde de carbone kandi bushobora gukoreshwa nk'uburyo bwo kubika hydrogen. Muri iki gikorwa, hakozwe imiterere y'iteraniro rya zero-gap electrode assemblée kugira ngo hakorwe electrochemical synthesis ya aside formike iva muri dioxyde de carbone. Iterambere ry'ingenzi mu ikoranabuhanga ni membrane ya cation isohotse, iyo ikoreshejwe mu buryo bwa bipolar membrane, yemerera aside formike ikorewe ku murongo wa membrane kwimurwa binyuze mu murima wa anode mu bipimo biri hasi nka 0.25 M. Hatabayeho ibindi bice bya sandwich hagati ya anode na cathode, igitekerezo kigamije gukoresha ibikoresho bya bateri n'imiterere bisanzwe mu turemangingo twa lisansi na electrolysis ya hydrogen, bigatuma habaho ihinduka ryihuse mu kwagura no gucuruzwa. Mu turemangingo twa cm2 25, imiterere ya membrane ya cation isohotse itanga >75% by'ubushobozi bwa Faraday kuri aside formike kuri <2 V na 300 mA/cm2. Icy'ingenzi kurushaho, ikizamini cyo guhagarara kw'amasaha 55 kuri 200 mA/cm2 cyagaragaje ubushobozi buhamye bwa Faraday n'imbaraga z'uturemangingo. Isesengura ry’ikoranabuhanga n’ubukungu rikoreshwa mu kwerekana uburyo bwo kugera ku buringanire bw’ibiciro n’uburyo bugezweho bwo gukora aside formike.
Kugabanya dioxyde de carbone kuva kuri aside formike hakoreshejwe amashanyarazi ashobora kuvugururwa byagaragaye ko bigabanya ikiguzi cy’umusaruro kugeza kuri 75% ugereranije n’uburyo gakondo bushingiye kuri peteroli. Nk’uko byagaragajwe mu nyandiko2,3, aside formike ifite uburyo bwinshi bwo kuyikoresha, kuva ku buryo bwiza kandi buhendutse bwo kubika no gutwara hydrogen mu nganda zikora imiti4,5 cyangwa inganda zikora biomass6. Aside formike yanagaragaye nk’inyongeramusaruro yo guhindurwamo ibyuma biramba bikoresha ikoranabuhanga rya metabolisme7,8. Hamwe n’iterambere ry’ubukungu bwa aside formike1,9, ubushakashatsi bwinshi bwibanze ku kunoza uburyo bwo guhitamo catalyst10,11,12,13,14,15,16. Ariko, imbaraga nyinshi zikomeje kwibanda ku tunyangingo duto twa H cyangwa utunyangingo tw’amazi dukora ku bucucike buke bw’amashanyarazi (<50 mA/cm2). Kugira ngo bigabanye ibiciro, bigere ku bucuruzi no kongera uburyo isoko rishyirwa mu bikorwa nyuma yaho, kugabanya amashanyarazi ya karubone dioxyde (CO2R) bigomba gukorwa ku bucucike bw'amashanyarazi buri hejuru (≥200 mA/cm2) na Faraday efficiency (FE)17 mu gihe kongera ikoreshwa ry'ibikoresho no gukoresha ibice bya bateri biva mu turemangingo twa lisansi tw'ikoranabuhanga na electrolysis y'amazi bituma ibikoresho bya CO2R bibyaza umusaruro ubukungu bw'ibipimo18. Byongeye kandi, kugira ngo byongere akamaro k'umusaruro no kwirinda kongerwaho uburyo bwo gutunganya ibintu, aside formike igomba gukoreshwa nk'umusaruro wa nyuma aho gukoreshwa nk'umunyu wa foromate19.
Muri uru rwego, hakozwe ingamba ziherutse zo guteza imbere ibikoresho bya CO2R formate/forme based gas diffusion electrode (GDE) bifitanye isano n’inganda. Isuzuma ryimbitse ryakozwe na Fernandez-Caso et al.20 rigaragaza muri make imiterere yose y’uturemangingo tw’amashanyarazi kugira ngo CO2 ikomeze kugabanuka kugeza kuri aside formic/formate. Muri rusange, imiterere yose ihari ishobora kugabanywamo ibice bitatu by'ingenzi: 1. Catholytes zinyura mu mazi19,21,22,23,24,25,26,27, 2. Uruhu rw'umurambararo rumwe (uruhererekane rw'ihindagurika ry'amazi (CEM)28 cyangwa uruhererekane rw'ihindagurika ry'amazi (AEM)29 na 3. Imiterere ya Sandwich15,30,31,32. Ibice byoroheje by'iyi miterere bigaragazwa ku Ishusho ya 1a. Ku miterere y'ihindagurika ry'amazi, hakorwa icyumba cya electrolyte hagati y'uruhererekane na cathode ya GDE. Catholyte inyura mu mazi ikoreshwa mu gukora imiyoboro ya ion mu urwego rwa cathode rwa catalyst33, nubwo bikenewe kugenzura guhitamo formate bigibwaho impaka34. Ariko, iyi miterere yakoreshejwe na Chen et al. Hakoreshejwe cathode ya SnO2 ku gice cya karuboni gifite urwego rwa catholyte rufite ubugari bwa mm 1.27, kugeza kuri 90% FE 35 kuri 500 mA/cm2 byagezweho. Guhuza urwego rwa catholyte rufite ubugari na membrane ya bipolar membrane (BPM) igabanya ihererekanya rya iyoni itanga voltage y'imikorere ya 6 V n'ingufu za 15%. Kugira ngo Li et al., bakoresheje imiterere imwe ya CEM, bageze kuri FE 29 ya 93.3% ku bucucike bw'umuyoboro wa fractional wa 51.7 mA/cm2. Diaz-Sainz et al.28 bakoresheje filter press hamwe na membrane imwe ya CEM ku bucucike bw'umuyoboro wa 45 mA/cm2. Ariko, uburyo bwose bwakozwe na aside formic aho kuba ibicuruzwa byakunzwe. Uretse ibindi bisabwa mu gutunganya, muri configurations za CEM, imiterere nka KCOOH ishobora kwirundanya vuba mu murima wa GDE no mu ruziga rw'amazi, bigatera imbogamizi zo gutwara no gucika intege kw'uturemangingo.
Kugereranya CO2R eshatu zigaragara cyane n'imiterere y'ibikoresho bihindura aside forma/formic hamwe n'imiterere yatanzwe muri ubu bushakashatsi. b Kugereranya umusaruro w'aside forma na forma/formic yose ku miterere ya catholyte, imiterere ya sandwich, imiterere ya CEM imwe mu nyandiko (yerekanywe mu Imbonerahamwe y'Inyongera S1) n'umurimo wacu. Ibimenyetso bifunguye bigaragaza umusaruro wa formate, naho ibimenyetso bikomeye bigaragaza umusaruro wa aside forma. *Imiterere yerekanwe hakoreshejwe hydrogen kuri anode. c Imiterere ya MEA y'icyuho ntarengwa ikoresheje membrane ya bipolar ivanze ifite urwego rwo guhinduza cation rufite imyobo ikora mu buryo bwa forward bias.
Kugira ngo hirindwe ko habaho ihinduka ry’imiterere y’ingirabuzimafatizo, Proietto n’abandi 32 bakoresheje uburyo bwo gukurura amazi adafite iy’ingirabuzimafatizo aho amazi yavuye mu ruganda anyura mu rundi ruhande. Ubu buryo bushobora kugera kuri >70% CE mu rugero rw’ubucucike buri hagati ya 50–80 mA/cm2. Mu buryo nk’ubwo, Yang n’abandi 14 batanze igitekerezo cyo gukoresha urwego rw’amashanyarazi hagati ya CEM na AEM kugira ngo bateze imbere ikorwa rya aside formike. Yang n’abandi 31,36 bageze kuri 91.3% FE mu karemangingo ka 5 cm2 kuri 200 mA/cm2, bigatuma habaho umuti wa aside formike wa 6.35 wt%. Xia n’abandi. Bakoresheje uburyo nk’ubwo, 83% bya dioxyde de carbone (CO2) muri aside formike FE byagezweho kuri 200 mA/cm2, kandi kuramba kwa sisitemu kwapimwe amasaha 100 n’iminota 30. Nubwo ibisubizo bito bitanga icyizere, igiciro cyiyongera n'ubukana bw'imiyoboro y'amazi ihinduranya iy'i ...
Kugira ngo turebe ingaruka z’imiterere itandukanye, twashyize ku rutonde umusaruro wa aside formate/formic kuri kWh kuri sisitemu zose zavuzwe haruguru maze tubishushanya ku Ishusho ya 1b. Biragaragara hano ko sisitemu iyo ari yo yose irimo catholyte cyangwa interlayer izagera ku musaruro wayo ku bucucike bw’umuyoboro w’amashanyarazi buri hasi kandi ikagabanuka ku bucucike bw’umuyoboro w’amashanyarazi buri hejuru, aho umupaka wa ohmic ushobora kugena voltage y’uturemangingo. Byongeye kandi, nubwo imiterere ya CEM ikoresha ingufu nke itanga umusaruro wa aside forma ya molar iri hejuru kuri kWh, kwiyongera k’umunyu bishobora gutuma habaho kwangirika kw’imikorere vuba ku bucucike bw’umuyoboro w’amashanyarazi buri hejuru.
Kugira ngo tugabanye uburyo bwo gucika intege bwavuzwe mbere, twakoze igikoresho cya membrane electrode assemblée (MEA) kirimo BPM ihuza imbere hamwe na membrane ya cation (PCEM) ifite perforated cation exchange membrane). Imiterere igaragara ku Ishusho ya 1c. Hydrogen (H2) yinjizwa muri anode kugira ngo ikore proton binyuze muri hydrogen oxidation reaction (HOR). Urwego rwa PCEM rwinjizwa muri sisitemu ya BPM kugira ngo itume ifomate ikorwa kuri cathode inyura muri AEM, ihuzwa na protons kugira ngo ikore aside formic kuri BPM interface na interstitial pores za CEM, hanyuma isohoka muri GDE anode na flow field. . Dukoresheje iyi configuration, twageze kuri >75% bya aside formic kuri <2 V na 300 mA/cm2 ku gace ka 25 cm2 ka selile. Icy'ingenzi kurushaho, igishushanyo gikoresha ibice bigurishwa n'imiterere y'ibikoresho bya selile za lisansi n'amazi, bigatuma habaho igihe cyihuse cyo kwaguka. Imiterere ya Catholyte irimo campholyte flow chambers ishobora gutera ubusumbane bw'umuvuduko hagati ya gaze na liquid phases, cyane cyane mu miterere minini ya selile. Ku nyubako za sandwich zifite ibice by'amazi bitonyanga, hakenewe imbaraga nyinshi kugira ngo hakorwe neza urwego rw'amazi rutonyanga kugira ngo hagabanuke kugabanuka k'umuvuduko no kwibumbira muri dioxyde de carbone muri urwo rwego rw'amazi. Ibi byombi bishobora gutuma itumanaho rya terefone rihungabana. Biragoye kandi gukora ibice by'amazi bito bito bihagaze ku rugero runini. Mu buryo bunyuranye, imiterere mishya yatanzwe ni imiterere ya MEA idafite icyuho kidakubiyemo icyumba cy'amazi cyangwa urwego rw'amazi rudakoresha icyuho. Ugereranyije n'izindi selile zisanzweho za electrochemical, imiterere yatanzwe ni yihariye kuko yemerera gukora aside formike mu buryo butaziguye mu buryo bushobora kwaguka, bukoresha ingufu nke kandi butakoresha icyuho kidakoresha icyuho.
Kugira ngo hakorwe ihindagurika rya hydrogen, ingamba nini zo kugabanya CO2 zakoresheje imiterere ya MEA na AEM membrane hamwe na electrolytes nyinshi zo mu bwoko bwa molar (urugero, 1-10 M KOH) kugira ngo habeho imiterere ya alkaline kuri cathode (nk'uko bigaragara ku Ishusho ya 2a). Muri izi imiterere, i-formate iyoni zakorewe kuri cathode zinyura muri membrane nk'ubwoko bwa electrode mbi, hanyuma KCOOH iraremwa ikava muri sisitemu inyuze mu muyoboro wa KOH wa anodic. Nubwo formate FE na voltage ya selile byari byiza mbere nkuko bigaragara ku Ishusho ya 2b, isuzuma ry'ubudahangarwa ryatumye FE igabanukaho hafi 30% mu masaha 10 gusa (Ishusho ya S1a–c). Tugomba kumenya ko ikoreshwa rya 1 M KOH anolyte ari ingenzi kugira ngo tugabanye volteji nyinshi za anodic muri sisitemu ya alkaline oxygen evolution reaction (OER)37 no kugera ku bushobozi bwo kugera kuri iyoni muri cathode catalyst bed33. Iyo igipimo cya anolyte cyagabanutse kikagera kuri 0.1 M KOH, voltage y'uturemangingo na oxidation ya aside formike (igabanuka rya aside formike) biriyongera (Ishusho S1d), bigaragaza ubucuruzi bwa zeru-sum. Igipimo cya oxidation ya formatike cyapimwe hakoreshejwe ingano rusange y'uburemere; kugira ngo ubone ibisobanuro birambuye, reba igice cya "Uburyo". Imikorere hakoreshejwe MEA na configuration ya membrane ya CEM imwe nayo yizwe, kandi ibisubizo bigaragara ku Ishusho S1f, g. FE formate yakusanyijwe muri cathode yari >60% kuri 200 mA/cm2 mu ntangiriro y'ikizamini, ariko yangiritse vuba mu masaha abiri bitewe no kwibumbira mu munyu wa cathode twavuze mbere (Ishusho S11).
Igishushanyo cya MEA ifite zero-gap MEA ifite CO2R kuri cathode, reaction ya hydrogen oxidation (HOR) cyangwa OER kuri anode, n'urukiramende rumwe rwa AEM ruri hagati. b FE na voltage ya selile kuri iyi configuration hamwe na 1 M KOH na OER binyura kuri anode. Uduce tw'amakosa tugaragaza ihinduka risanzwe ry'ibipimo bitatu bitandukanye. muri FE na voltage ya selile ya sisitemu hamwe na H2 na HOR kuri anode. Amabara atandukanye arakoreshwa mu gutandukanya ikorwa rya formate na aside formic. d Igishushanyo cya MEA hamwe na BPM cyimuriwe imbere hagati. Voltage ya FE na bateri ugereranyije n'igihe kuri 200 mA/cm2 hakoreshejwe iyi configuration. f Ishusho y'igice cya BPM MEA ishingiye imbere nyuma y'ikizamini gito.
Kugira ngo hakorwe aside formike, hidrojeni igezwa kuri katalyst ya Pt-on-carbon (Pt/C) kuri anode. Nkuko bigaragara ku Ishusho ya 2d, protoni zikora BPM zishingiye imbere kuri anode zakoreweho ubushakashatsi mbere kugira ngo haboneke aside formike. Igice cyo gupima BPM cyananiwe nyuma y'iminota 40 gikoreshwa ku muvuduko wa 200 mA/cm2, hamwe n'izamuka ry'amashanyarazi rirenze 5 V (Ishusho ya 2e). Nyuma yo gupima, hagaragaye delamination igaragara ku rubuga rwa CEM/AEM. Uretse formate, anions nka karubone, bicarbonate na hydroxide nazo zishobora kunyura muri membrane ya AEM zikavugana na protoni ku rubuga rwa CEM/AEM kugira ngo zikore gaze ya CO2 n'amazi y'amazi, bigatera delamination ya BPM (Ishusho ya 2f) na , amaherezo bigatera gutsindwa kwa selile.
Hashingiwe ku mikorere n'uburyo bwo gutsindwa kw'imiterere yavuzwe haruguru, hatanzwe imiterere mishya ya MEA nk'uko bigaragara ku Ishusho ya 1c kandi birambuye ku Ishusho ya 3a38. Aha, urwego rwa PCEM rutanga inzira yo kwimuka kwa aside formike na anions biva kuri CEM/AEM, bityo bigabanye ukwiyongera kw'ikintu. Muri icyo gihe, inzira ya PCEM iyobora aside formike mu gice cyo gukwirakwiza no mu murima w'amazi, bigagabanya amahirwe yo gutwika aside formike. Ibisubizo bya polarization hakoreshejwe AEM zifite ubunini bwa mm 80, 40 na 25 bigaragazwa ku Ishusho ya 3b. Nkuko byitezwe, nubwo voltage rusange y'uturemangingo yiyongera uko ubunini bwa AEM bwiyongera, gukoresha AEM ikomeye birinda gukwirakwira kwa aside formike inyuma, bityo byongera pH ya cathode kandi bigagabanya umusaruro wa H2 (Ishusho ya 3c–e).
Ishusho y'imiterere ya MEA ifite AEM na CEM ifite imyobo hamwe n'inzira zitandukanye zo gutwara aside formike. b Umuvuduko w'uturemangingo ku bucucike butandukanye bw'umuyoboro w'amashanyarazi n'ubucucike butandukanye bwa AEM. muri EE ku bucucike butandukanye bw'umuyoboro w'amashanyarazi hamwe n'ubucucike bwa AEM bwa 80 μm (d) 40 μm, e) 25 μm. Uduce tw'amakosa tugaragaza ihindagurika risanzwe ripimwe mu ngero eshatu zitandukanye. f Ibisubizo byo kwigana igipimo cya aside formike n'agaciro ka pH ku kimenyetso cya CEM/AEM ku bucucike butandukanye bwa AEM. f PC na pH mu urwego rwa cathode rwa catalyst hamwe n'ubucucike butandukanye bwa filime ya AEM. g Ikwirakwizwa ry'ibipimo bya aside formike mu buryo bubiri hamwe n'ikimenyetso cya CEM/AEM hamwe n'imyobo.
Ishusho S2 igaragaza ikwirakwizwa ry’icyiciro cya aside formike na pH mu bunini bwa MEA hakoreshejwe uburyo bwa Poisson-Nernst-Planck finite element modeling. Ntibitangaje ko icyiciro kinini cya aside formike, 0.23 mol/L, kigaragara ku rubuga rwa CEM/AEM, kubera ko aside formike ikorwa kuri uru rubuga. Icyiciro cya aside formike binyuze muri AEM kigabanuka vuba uko ubunini bwa AEM bwiyongera, bigaragaza ko ubushobozi bwo kwihanganira ihererekanya ry’ibintu byinshi n’ihindagurika rike rya aside formike bitewe no gukwirakwira kw’inyuma. Ishusho ya 3 f na g igaragaza agaciro ka pH na aside formike mu gice cy’ingufu cya cathode giterwa no gukwirakwira kw’inyuma n’ikwirakwizwa ry’icyiciro cya aside formike mu buryo bubiri. Uko membrane ya AEM igenda iba nto, ni ko icyiciro cya aside formike hafi ya cathode kiba kinini, kandi pH ya cathode iba aside. Kubwibyo, nubwo membrane nini ya AEM itera igihombo kinini cya ohmic, ni ingenzi mu gukumira gukwirakwira kw’inyuma kwa aside formike kuri cathode no kongerera ubuziranenge bwinshi bwa sisitemu ya aside formike ya FE. Amaherezo, kongera ubunini bwa AEM kugeza kuri 80 μm byatumye FE igera kuri 75% kuri aside formike kuri <2 V na 300 mA/cm2 ku gace k'uturemangingo ka 25 cm2.
Kugira ngo hamenyekane uburyo iyi miterere ishingiye kuri PECM ihagaze neza, umuvuduko wa batiri wagumye kuri 200 mA/cm2 mu gihe cy'amasaha 55. Ibisubizo rusange bigaragara ku Ishusho ya 4, hamwe n'ibyavuye mu masaha 3 ya mbere bigaragara ku Ishusho ya S3. Mu gihe cyo gukoresha catalyst ya anodic ya Pt/C, voltage ya selile yariyongereye cyane mu minota 30 ya mbere (Ishusho ya S3a). Mu gihe kirekire, voltage ya selile yagumye hafi nta yindi, bitanga igipimo cyo kwangirika cya 0.6 mV/h (Ishusho ya 4a). Mu ntangiriro y'ikizamini, PV ya aside formic yakusanyijwe kuri anode yari 76.5% naho PV ya hydrogen yakusanyijwe kuri cathode yari 19.2%. Nyuma y'isaha ya mbere y'ikizamini, hydrogen FE yagabanutse igera kuri 13.8%, bigaragaza ko habayeho impinduka nziza mu guhitamo formate. Ariko, igipimo cyo gushonga kwa aside formike muri sisitemu cyagabanutse kigera kuri 62.7% mu isaha imwe, kandi igipimo cyo gushonga kwa aside formike formike cyariyongereye kuva hafi ya zeru mu ntangiriro y'ikizamini kigera kuri 17.0%. Nyuma yaho, FE ya H2, CO, aside formike n'igipimo cyo gushonga kwa aside formike formike byakomeje kumera neza mu gihe cy'igerageza. Ukwiyongera kwa aside formike mu isaha ya mbere bishobora guterwa no kwibumbira kwa aside formike ku rubuga rwa PCEM/AEM. Uko igipimo cya aside formike cyiyongera, ntabwo isohoka gusa mu gutobora kwa membrane, ahubwo inakwirakwira muri FEM ubwayo ikinjira mu cyiciro cya anode ya Pt/C. Kubera ko aside formike ari amazi kuri 60°C, kwibumbira kwayo bishobora guteza ibibazo byo kohereza ibintu byinshi kandi bigatera gushonga kurusha hydrogen.
Umuvuduko w'ingirabuzimafatizo ugereranije n'igihe (200 mA/cm2, 60 °C). Ishusho y'imbere igaragaza ishusho ya mikorosikopi y'urumuri rw'igice cya MEA gifite EM ifite icyuho. Umurongo w'igipimo: 300 µm. b Ubuziranenge bwa PE na aside formike nk'uko igihe kigenda kuri 200 mA/cm2 hakoreshejwe anode ya Pt/C.
Imiterere y'ibipimo mu ntangiriro z'igerageza (BOT) mu gihe cyo gutegura no mu mpera z'igerageza (EOT) nyuma y'amasaha 55 y'igerageza ry'ubudahangarwa yagaragajwe hakoreshejwe nano-X-ray computed tomography (nano-CT), nk'uko bigaragara ku Ishusho ya 5 a. Icyitegererezo cya EOT gifite ingano nini ya katalyst ifite umurambararo wa 1207 nm ugereranije na 930 nm kuri BOT. Amashusho ya mikroskopi ya electron scanning dark-field scanning (HAADF-STEM) hamwe n'ibisubizo bya X-ray dispersive energy-dispersive (EDS) bigaragara ku Ishusho ya 5b. Nubwo urwego rwa katalyst rwa BOT rurimo uduce twinshi duto twa katalyst ndetse n'utundi duce duto, mu cyiciro cya EOT urwego rwa katalyst rushobora kugabanywamo uturere tubiri dutandukanye: kamwe gafite uduce duto cyane n'utundi gafite uduce twinshi. Umubare w'uduce duto. Ishusho ya EDS igaragaza ko uduce duto duto dukungahaye kuri Bi, birashoboka ko ari icyuma cya Bi, kandi uturere dufite utundi duce dukungahaye kuri ogisijeni. Iyo aka karemangingo gakoreshejwe kuri 200 mA/cm2, ubushobozi bubi bwa cathode buzatuma Bi2O3 igabanuka, nk'uko bigaragazwa n'ibisubizo bya X-ray absorption spectroscopy bivugwa hano hepfo. Ibisubizo bya HAADF-STEM na EDS mapping bigaragaza ko Bi2O3 inyura mu nzira yo kugabanya, bigatuma itakaza ogisijeni maze igakora uduce duto tw'icyuma. Imiterere ya X-ray diffraction ya cathodes za BOT na EOT yemeza ibisobanuro by'amakuru ya EDS (Ishusho ya 5c): Bi2O3 crystalline ni yo yabonetse muri cathode ya BOT, naho bimetal crystalline yabonetse muri cathode ya EOT. Kugira ngo dusobanukirwe ingaruka za cathode potential ku miterere ya oxidation ya cathode catalyst ya Bi2O3, ubushyuhe bwaratandukanye kuva kuri open circuit potential (+0.3 V vs RHE) kugeza kuri -1.5 V (vs RHE). Byagaragaye ko igice cya Bi2O3 gitangira kugabanuka kuri -0.85 V ugereranije na RHE, kandi kugabanuka k'ubukana bw'umurongo wera mu gace k'inkombe z'umubumbe w'urumuri bigaragaza ko Bi y'icyuma yagabanutseho 90% bya RHE kuri -1.1. V ugereranije na RHE (Ishusho ya 5d). Uko imikorere yaba iri kose, uburyo bwo guhitamo muri rusange formate kuri cathode ntabwo buhinduka, nk'uko byagaragajwe na H2 na CO FE hamwe no gushyiraho aside formike, nubwo hari impinduka zikomeye mu miterere ya cathode, imiterere ya catalyst oxidation, n'imiterere ya microcrystalline.
Imiterere y'urwego rwa katalojiya ifite imiterere itatu n'ikwirakwizwa ry'uduce twa katalojiya twabonetse hakoreshejwe nano-X-ray CT. Umurongo w'igipimo: 10 µm. b Hejuru 2: Amashusho ya HAADF-STEM y'imiterere ya katojiya ya BOT na katalojiya za EOT. Umurongo w'igipimo: 1 µm. Hasi 2: Amashusho ya HADF-STEM na EDX yagutse y'urwego rwa katojiya rwa katalojiya ya EOT. Umurongo w'igipimo: 100 nm. c Imiterere ya diffraction ya X-ray y'ingero za katojiya za BOT na EOT. d Imbere muri X-ray absorption spectra ya electrode ya Bi2O3 muri 0.1 M KOH nk'uko ubushobozi buhagaze (0.8 V kugeza -1.5 V vs. RHE).
Kugira ngo hamenyekane neza amahirwe ahari yo kunoza imikorere myiza y'ingufu binyuze mu kubuza ogisijeni ya aside formike, electrode y'icyitegererezo cya H2 yakoreshejwe kugira ngo hamenyekane uruhare rw'igabanuka ry'amashanyarazi39. Ku bucucike bw'amashanyarazi buri munsi ya 500 mA/cm2, ubushobozi bwa cathode buguma munsi ya -1.25 V. Ubushobozi bwa anodic bugabanyijemo ibice bibiri by'ingenzi: ubucucike bw'amashanyarazi HOR na overvoltage ya theoretical HOR 40 yahanuwe n'ikigereranyo cya Bulter-Volmer cyapimwe mbere, naho igice gisigaye giterwa na ogisijeni formike. Bitewe n'uburyo bwo gukora buhoro cyane ugereranije na HOR41, igipimo gito cya ogisijeni formike reaction kuri anode gishobora gutuma habaho kwiyongera gukomeye kwa anodic potential. Ibisubizo bigaragaza ko guhagarika burundu ogisijeni formike formike bishobora gukuraho overvoltage ya hafi 500 mV.
Kugira ngo hagenzurwe iki gipimo, umuvuduko w'amazi yavuye mu kirere (DI) ku gice cy'amazi cya anode warahindutse kugira ngo ugabanye umuvuduko w'aside formic yamenetse. Ishusho ya 6b na c yerekana FE, umuvuduko w'aside formic, na voltage y'uturemangingo nk'uko bigendekera DI flux kuri anode kuri 200 mA/cm2. Uko umuvuduko w'amazi yavuye mu kirere wazamukaga kuva kuri 3.3 mL/min kugera kuri 25 mL/min, umuvuduko w'aside formic kuri anode waragabanutse kuva kuri 0.27 mol/L kugera kuri 0.08 mol/L. Mu kugereranya, hakoreshejwe imiterere ya sandwich yatanzwe na Xia et al. 30, umuvuduko w'aside formic wa 1.8 mol/L wabonetse kuri 200 mA/cm2. Kugabanya umuvuduko w'aside formic byazamuye FE muri rusange kandi bigabanya FE ya H2 kuko pH ya cathode iba alkaline cyane bitewe no kugabanuka k'umugongo wa aside formic. Kugabanuka k'umubare w'aside formike ku muvuduko ntarengwa wa DI byanakuyeho ogisijeni ya formike, bigatuma ingufu zose z'uturemangingo ziri munsi ya 1.7 V kuri 200 mA/cm2. Ubushyuhe bwa batiri nabwo bugira ingaruka ku mikorere rusange, kandi ibisubizo bigaragara ku Ishusho ya S10. Ariko, imiterere ishingiye kuri PCEM ishobora kunoza cyane imikorere y'ingufu mu gukumira ogisijeni ya formike, haba hakoreshejwe catalysts za anodike zifite uburyo bwo guhitamo neza hydrogen kuri aside formike cyangwa binyuze mu mikorere y'igikoresho.
a Gusenyuka k'umuvuduko w'uturemangingo hakoreshejwe electrode ya H2 reference cell ikora kuri 60 °C, anode ya Pt/C na 80 µm AEM. b FE na aside formic ikusanyirijwe kuri 200 mA/cm2 hakoreshejwe uburyo butandukanye bwo gutembera kw'amazi ya anode deionized. c Iyo anode ikusanyije aside formic mu buryo butandukanye, voltage ya selile ni 200 mA/cm2. Uduce tw'amakosa tugaragaza ihinduka ry'ibipimo bitatu bitandukanye. d Igiciro gito cyo kugurisha gihabanye n'imikorere ku buryo butandukanye bwo gutembera kw'amazi ya deionized hakoreshejwe ibiciro by'amashanyarazi by'inganda bya US$ 0.068/kWh na hydrogen ya US$ 4.5/kg. (*: Imiterere y’ingufu nkeya ya aside formike kuri anode ifatwa nk'ingana na 10 M FA, igiciro cy’ingufu z’inganda ku rwego rw’igihugu ni $0.068/kWh, naho hydrogen ni $4.5/kg. **: Imiterere y’ingufu nkeya ni aside formike ifatwa nk'ingufu. Igipimo cya FA kuri anode ni 1.3 M anode, igiciro cy’amashanyarazi cyitezwe mu gihe kizaza ni $0.03/kWh, kandi umurongo w’utudomo ugaragaza igiciro cy’isoko cya 85 wt% FA.
Isesengura ry’ikoranabuhanga n’ubukungu (TEA) ryakozwe kugira ngo haboneke igiciro gito cyo kugurisha cy’ibikoresho bya lisansi mu buryo butandukanye bw’imikorere, nk’uko bigaragara ku Ishusho ya 5d. Uburyo n’amakuru y’inyuma ya TEA biboneka muri SI. Iyo ingano ya LC mu ibyuka bya anode iri hejuru, nubwo amashanyarazi ari menshi, ikiguzi rusange cy’ibikora bya lisansi kiragabanuka bitewe no kugabanuka kw’ikiguzi cyo gutandukanya. Niba oxidation ya aside formike ya anode ishobora kugabanuka binyuze mu iterambere rya catalyst cyangwa ikoranabuhanga rya electrode, guhuza voltage ntoya y’uturemangingo (1.66 V) n’ingano nini ya FA mu myanda (10 M) byagabanya ikiguzi cyo gukora electrochemical FA kikagera ku madolari 0.74 y’Amerika / kg (hashingiwe ku mashanyarazi). igiciro) $0.068/kWh na $4.5/kg hidrojeni42. Byongeye kandi, iyo bihujwe n’ikiguzi cy’amashanyarazi ashobora kongera gukoreshwa cya $0.03/kWh na hidrojeni ya $2.3/kg, intego y’amazi mabi ya FA igabanuka ikagera kuri miliyoni 1.3, bigatuma ikiguzi cya nyuma cy’umusaruro kiba US$0.66/kg43. Ibi bigereranywa n'ibiciro biri ku isoko. Bityo, imbaraga zizaza zibanda ku bikoresho bya electrode n'imiterere yazo zishobora kugabanya cyane uburyo bwo gusohora amashanyarazi mu gihe zituma imikorere ku muvuduko muto w'uturemangingo irushaho kuba myiza.
Muri make, twize imiterere myinshi ya MEA idafite icyuho cyo kugabanya CO2 ikaba aside formike, tunatanga igitekerezo cy’imiterere irimo membrane ya bipolar ihuza imbere harimo na membrane ya cation exchange cation (PECM) kugira ngo yorohereze uburyo bwo kohereza aside formike ivamo. Iyi imiterere ikora aside formike >96% ku gipimo cya 0.25 M (ku gipimo cya anode DI cya 3.3 mL/min). Ku gipimo cyo hejuru cya DI flow (25 mL/min), iyi imiterere yatanze ubucucike bwa >80% FE bwa 200 mA/cm2 kuri 1.7 V dukoresheje agace ka 25 cm2. Ku gipimo cyo hagati cya anodic DI (10 mL/min), imiterere ya PECM yagumanye voltage ihamye n’urwego rwo hejuru rwa aside formike FE mu gihe cy’amasaha 55 yo gupima kuri 200 mA/cm2. Gutuza no guhitamo bigerwaho na catalysts ziboneka ku isoko n’ibikoresho bya polymeric membrane bishobora kongerwa kurushaho binyuze mu kubihuza na electrocatalysts nziza. Imirimo ikurikira izibanda ku guhindura imiterere y'imikorere, guhitamo anode catalyst, n'imiterere ya MEA kugira ngo bigabanye oxidation ya aside formike, bigatuma imyanda yiyongera cyane ku muvuduko muto w'uturemangingo. Uburyo bworoshye bwo gukoresha dioxyde de carbone kuri aside formike bwagaragajwe hano bukuraho gukenera ibyumba bya anolyte na catholyte, ibice bya sandwich, n'ibikoresho byihariye, bityo byongera imikorere myiza y'ingufu z'uturemangingo no kugabanya imiterere y'imikorere, bigatuma byoroha kongera imbaraga. Iyi miterere itangwa itanga urubuga rwo guteza imbere inganda zihindura CO2 mu buryo bw'ikoranabuhanga no mu bukungu.
Keretse byavuzwe ukundi, ibikoresho byose bya shimi n'imiti byakoreshejwe uko byakiriwe. Bismuth oxide catalyst (Bi2O3, 80 nm) yaguzwe muri US Research Nanomaterials, Inc. Ifu ya polymer (AP1-CNN8-00-X) yatanzwe na IONOMR. Omnisolv® brand N-propanol (nPA) n'amazi meza cyane (18.2 Ω, Milli–Q® Advantage A10 water cleansing system) byaguzwe muri Millipore Sigma. Methanol na acetone byemejwe na ACS bigurwa muri VWR Chemicals BDH® na Fisher Chemical, uko bikurikirana. Ifu ya polymer yavanzwe n'uruvange rwa acetone na methanol ku gipimo cya 1:1 ukurikije uburemere kugira ngo haboneke polymer dispersion ifite ingano ya 6.5 wt.%. Tegura wino ya catalytic uvanze 20g Bi2O3, amazi meza cyane, nPA na ionomer dispersion mu kibindi cya 30ml. Ibigize byari birimo catalyst ya 30 wt.%, igipimo cy'uburemere bwa ionomer kuri catalyst cya 0.02 n'igipimo cy'uburemere bwa alcool ku mazi cya 2:3 (40 wt.% nPA). Mbere yo kuvanga, hongewemo garama 70 z'ibikoresho byo gusya bya Glen Mills 5mm zirconia. Ingero zashyizwe ku icupa rya Fisherbrand™ digital bottle roller ku muvuduko wa 80 rpm mu gihe cy'amasaha 26. Reka wino ihagarare iminota 20 mbere yo kuyishyiramo. Wino ya Bi2O3 yashyizwe kuri Qualtech automatic applicator (QPI-AFA6800) hakoreshejwe icyuma cya laboratwari cya 1/2″ x 16″ (RD Specialties - 60 mil diameter) kuri 22°C. 5 mL y'inyino ya catalytic yashyizwe kuri Sigraacet 39 BB carrier gaze diffusion carrier ya santimetero 7.5 x 8 (ububiko bw'uturemangingo twa lisansi) hakoreshejwe inkoni yo gushyiramo ku muvuduko uhoraho wa mm 55/segonda. Shyira izi electrode zipfundikiye mu itanura hanyuma wumishe kuri 80 °C. Uburyo bwo gupfundikira inkoni n'amashusho y'igipfundikizo cya GDE bigaragara ku mashusho ya S4a na b. Igikoresho cya X-ray fluorescence (XRF) (Fischerscope® XDV-SDD, Fischer-Technolgy Inc. USA) cyemeje ko umutwaro wa GDE wari 3.0 mg Bi2O3/cm2.
Ku bijyanye n'imiterere y'urukiramende rurimo urukiramende rw'ihindagurika ry'aminoni (AEM) na CEM ifite imyenge. Nafion NC700 (Chemours, USA) ifite ubugari bwa 15 µm yakoreshejwe nk'urwego rwa CEM. Kataloge ya anodi yasutswe kuri FEM hakoreshejwe ionome kuri karubone ya 0.83 n'ubuso bwo gutwikira bwa cm2 25. Platine ifite ubuso bunini (50 wt.% Pt / C, TEC 10E50E, TANAKA y'agaciro) ifite umutwaro wa 0.25 mg Pt / cm2 yakoreshejwe nk'ikataloge ya anode. Nafion D2020 (Ion Power, USA) yakoreshejwe nk'ikataloge ku rwego rwa anode rw'ikataloge. Kataloge ya CEM ikorwa hakoreshejwe gukata imirongo iteganye kuri firime ya CEM ku ntera ya mm 3. Ibisobanuro birambuye ku buryo bwo gutobora bigaragara ku mashusho S12b na c. Hakoreshejwe X-ray computed tomography, byemejwe ko icyuho cyo gutobora cyari 32.6 μm, nk'uko bigaragara ku Ishusho S12d na e. Mu gihe cyo guteranya uturemangingo, hashyizweho membrane ya CEM ifite imbobo ipfundikiye ku rupapuro rwa Toray rwa 25 cm2 (5 wt% PTFE yavuwe, Fuel Cell Store, USA). membrane ya AEM (PiperION, Versogen, USA) ifite ubugari bwa 25, 40 cyangwa 80 μm yashyizwe hejuru ya CEM hanyuma ishyirwa kuri cathode ya GDE. membrane ya AEM yaciwemo ibice bya 7.5 × 7.5 cm kugira ngo ipfuke umurima wose w'amazi maze iraswa ijoro ryose mu gikoresho cya potassium hydroxide ya 1 M mbere yo guteranya. Anode na cathode byombi bikoresha spacers za PTFE zifite ubugari buhagije kugira ngo bigere ku gukanda neza kwa GDE kwa 18%. Ibisobanuro birambuye ku buryo bateri iteranya bigaragara ku Ishusho S12a.
Mu gihe cyo gupima, akazu kari gateranijwe kagumanye ubushyuhe kuri 60 °C (30, 60, na 80 °C kugira ngo hakorwe inyigo ku bushyuhe) hamwe na 0.8 L/min ya gaze ya hydrogen yatanzwe kuri anode na 2 L/min ya gaze ya karuboni yatanzwe kuri cathode. Imyuka ya anodic na gaze ya kathodike byombi byashyizwemo ubushuhe ku bushyuhe bwa 100% na 259 kPa umuvuduko wa kathodike wuzuye. Mu gihe cyo gukora, umugezi wa gaze ya kathodike wavanzwe n'umuti wa 1 M KOH ku kigero cya 2 mL/min kugira ngo hakorwe neza ikoreshwa rya cathode catalyst bed na ionic conduction. Vanga umugezi wa gaze ya anode n'amazi ya deionized ku kigero cya 10 ml/min kugira ngo ukureho aside formic kuri anode. Ibisobanuro birambuye ku byinjira n'ibisohoka by'igikoresho bigaragara ku Ishusho ya S5. Gaze ya cathode isohoka irimo CO2 kandi ikora CO2 na H2. Umwotsi w'amazi ukurwamo unyuze muri condenser (ubushyuhe buri hasi kuri 2 °C). Gaze isigaye izakusanywa kugira ngo ikorerwe isesengura ry'igihe cya gaze. Urujya n'uruza rw'amazi (anode) ruzanyura mu cyuma gipima amazi (condenser) kugira ngo gitandukanye amazi na gaze. Amazi yanduye azakusanywa mu ducupa dusukuye hanyuma asesengurwe hakoreshejwe uburyo bwa "liquid chronometry" kugira ngo hamenyekane aside formic ikorwa. Ibizamini bya elegitoroniki byakozwe hakoreshejwe Garmy potentiostat (nimero 30K, Gamry, USA). Mbere yo gupima imiterere ya polarization, aside yashyizwe mu buryo inshuro 4 hagati ya 0 na 250 mA/cm2 hakoreshejwe linear voltammetry ifite igipimo cya scan cya 2.5 mA/cm2. Imiterere ya polarization yabonetse mu buryo bwa galvanostatic, aside iguma ku muvuduko runaka w'amashanyarazi mu gihe cy'iminota 4 mbere yo gupima gaze ya cathode na anolyte liquid.
Dukoresha electrode y’ifatizo rya hydrogen muri MEA kugira ngo dutandukanye cathode na anodic potentials. Imiterere ya electrode y’ifatizo igaragara ku Ishusho ya S6a. Urukiramende rwa Nafion (Nafion 211, IonPower, USA) rwakoreshejwe nk'ikiraro cya ionic kugira ngo ruhuze urukiramende rwa MEA na electrode y’ifatizo. Impera imwe y’urukiramende rwa Nafion yahujwe na electrode y’ikwirakwizwa rya gaz diffusion ya 1 cm2 (GDE) yuzuyemo 0.25 mg Pt/cm2 (50 wt% Pt/C, TEC10E50E, TANAKA Precious Metals) yashyizwe ku mpapuro za karuboni za 29BC (Fuel Cell Store, USA). ). Ibikoresho byihariye bya polyetherketone (PEEK) bikoreshwa mu gufunga gaze no kwemeza ko GDE na Nafion strips bikora neza, no guhuza electrode y’ifatizo n’ibikoresho bya lisansi. Impera yindi y’urukiramende rwa Nafion ihujwe n’inkombe igaragara ya bateri ya CEM. Ishusho ya S6b yerekana igice cy’urukiramende rw’ifatizo rwahujwe na MEA.
Nyuma y’uko umwuka usohoka unyuze mu cyuma gipima umwuka n’amazi, ingero za gazi zifatwa muri cathode. Imyuka yakusanyijwe yasesenguwe nibura inshuro eshatu hakoreshejwe icyuma cya 4900 Micro GC (10 μm molecular sieve, Agilent). Ingero zakusanyijwe mu dukapu tw’ingero za gazi za aluminiyumu twinshi tudafite ireme Supel™ (Sigma-Aldrich) mu gihe runaka (amasegonda 30) hanyuma zishyirwa mu imashini ya chromatograph ya microgas mu masaha abiri nyuma yo gukusanya. Ubushyuhe bwo guterwa bwashyizwe kuri 110°C. Monoxide ya karuboni (CO) na hydrogen (H2) byatandukanyijwe ku gipimo cya MS5A gishyushye (105°C) gifite umuvuduko (28 psi) wa metero 10 hakoreshejwe argon (Matheson Gas-Matheson Purity) nk’umwuka utwara. Izi mpande ziboneka hakoreshejwe icyuma cyabugenewe cyo gupima ubushyuhe (TCD). Ingero za GC chromatogram na CO na H2 calibration curves bigaragazwa ku Ishusho ya S7. Ingero za aside formike y'amazi zakusanyijwe muri anode mu gihe runaka (amasegonda 120) hanyuma ziyungururwa hakoreshejwe akayunguruzo ka PTFE ka 0.22 μm mu ducupa twa mL 2. Ibicuruzwa by'amazi mu ducupa byasesenguwe hakoreshejwe sisitemu ya Agilent 1260 Infinity II bioinert high-performance liquid chromatography (HPLC), aho 20 μl by'icyitegererezo byashyizwemo binyuze muri autosampler (G5668A) hamwe na aside sulfurike ya 4 mM (H2SO4). ) ku muvuduko wa 0.6 ml/min (quaternary pump G5654A). Ibicuruzwa byatandukanyijwe ku gikoresho gishyushye (35°C, column oven G7116A) Aminex HPX-87H 300 × 7.8 mm (Bio-Rad) cyabanje gutegurwa na Micro-Guard Cation H guard column. Aside formike yabonetse hakoreshejwe diode array detector (DAD). ku bunini bwa 210 nm na bandwidth ya 4 nm. Kromatogaramu ya HPL n'umurongo ngenderwaho wa aside formike bigaragazwa ku Ishusho S7.
Ibikomoka kuri gaze (CO na H2) FE bibarwa hakoreshejwe ikigereranyo gikurikira, naho ibipimo byose bya gaze bibarwa hakoreshejwe ikigereranyo cya gaze gikwiye:
Muri byo: \({n}_{i}\): umubare wa electrons muri reaction ya electrochemical. \(F\): Igipimo cya Faraday. \({C}_{i}\): Igipimo cy'ibicuruzwa by'amazi bya HPLC. \(V\): ingano y'icyitegererezo cy'amazi cyakusanyijwe mu gihe runaka t. \(j\): ubucucike bw'umuyoboro w'amashanyarazi. \(A\): Agace ka geometrike ka electrode (25 cm2). \(t\): igihe cyo gufata ingero. \(P\): igitutu cyuzuye. \({x}_{i}\): Ijanisha rya molekile ya gazi rigenwa na GC. \(R\): igipimo cya gazi. \(T\): ubushyuhe.
Igipimo cya anodic cations cyapimwe hakoreshejwe uburyo bwa inductively combined plasma atomic emission spectroscopy (ICP-OES). Cations zishobora kwinjira cyangwa gukwirakwira muri anode zirimo Ti, Pt, Bi na K. Uretse K, izindi cations zose zari munsi y'umupaka wo kuzimenya. Bikora iyoni mu gisubizo bigatuma anode ihuzwa na proton cyangwa izindi cations. Kubwibyo, ubuziranenge bwa aside formike bushobora kubarwa nka
Umusaruro wa Formate/FA ugaragaza ingano ya FA ikorwa kuri kWh y'amashanyarazi akoreshwa hakoreshejwe imiterere ya MEA runaka, muri mol/kWh. Ubarwa hashingiwe ku bucucike bw'amashanyarazi, voltage y'uturemangingo n'ubushobozi bwa Faraday mu bihe runaka by'imikorere.
Kubara ingano ya aside formike yakuwe kuri anode hashingiwe ku buringanire rusange bw'uburemere. Inzira eshatu zihanganye zibaho kuri cathode: ihindagurika rya hydrogen, kugabanuka kwa CO2 kuri CO, no kugabanuka kwa CO2 kuri aside formike. Kubera ko dufite inzira yo kugabanya aside formike muri Anton, aside formike FE ishobora kugabanywamo ibice bibiri: gukusanya aside formike na oxidation ya aside formike. Uburemere rusange bw'uburemere bushobora kwandikwa butya:
Twakoresheje GC kugira ngo tubare ingano ya aside formike, hydrogen, na CO byakusanyijwe na HPLC. Byagombye kumenyekana ko aside formike nyinshi zakusanyijwe muri anode dukoresheje uburyo bugaragara ku Ishusho y'inyongera S5. Ingano ya formatike yakusanyijwe mu cyumba cya cathode ni nto, ni nkeya cyane, kandi ni munsi ya 0.5% by'ingano yose ya SC.
Uburyo bwo gutwara abantu bukomeza gukoreshwa hano bushingiye ku mirimo yakozwe mbere kuri sisitemu zisa34. Sisitemu ihujwe ya Poisson-Nerst-Planck (PNP) equations ikoreshwa mu kumenya ingano y'amazi n'ubushobozi bwa electrostatic mu byiciro by'ikoranabuhanga na ionically conducting. Incamake irambuye y'ibigereranyo by'ibanze n'imiterere y'icyitegererezo iratangwa muri SI.
Ubu buryo bugena ingano y'ibintu umunani by'amazi (\({{{{{\rm{C}}}}}}}{{{{{\rm{O}}}}}}}}_{2 \left ({{{{{\rm{aq}}}}}}}\right)}\), \({{{{{{\rm{H}}}}}}}}}^{+ }\ ), \ ({{{{\rm{O}}}}}}{{{{{\rm{H}}}}}}^{-}\), \({{{ {{ \rm{HCO}}}}}}_{3}^{-}\), \({{{{{\rm{CO}}}}}}_{3}^{ 2-} \ ),\ ({{{{\rm{HCOOH}}}}}}\), \({{{{{\rm{HCOO}}}}}}}}}^{- }\) na \({{{ {{\rm{K}}}}}}}^{+}\)), ubushobozi bwa electrostatic mu cyiciro cya ionic conducting (\({\phi }_{I}\ )) na anodic na cathodic electron conductivity. Electrostatic potentials mu byiciro (\({\phi }_{A}\) na \({\phi }_{C}\) uko bikurikirana). Ahubwo, nta mikorere ya local electrical neutral cyangwa charge distribution igerwaho, space charge region ikemurwa mu buryo butaziguye hakoreshejwe ikigereranyo cya Poisson; Ubu buryo budufasha kwigana neza ingaruka za Donnan repulsion kuri CEM|AEM, CEM|Pore, na AEM|Pore interfaces. Byongeye kandi, porous electrode theory (PET) ikoreshwa mu gusobanura charge transport mu byiciro bya anodic na cathodic bya catalyst. Mu bumenyi bw'abanditsi, iki gikorwa kigaragaza ikoreshwa rya mbere rya PET muri sisitemu zifite uturere twinshi two gushyushya umwanya.
Ingero za GDE BOT na EOT cathode zapimwe hakoreshejwe Zeiss Xradia 800 Ultra ifite aho ituruka X-ray ya 8.0 keV, uburyo bwo kwinjiza no gukoresha ikoranabuhanga ryagutse, hamwe n'uburyo bwo guhuza amashusho1. Amashusho 901 yakusanyijwe kuva kuri -90° kugeza kuri 90° mu gihe cyo kwerekana amasegonda 50. Ivugurura ryakozwe hakoreshejwe akayunguruzo kerekana inyuma gafite ingano ya voxel ya 64 nm. Isesengura ry'uburyo ibice bitandukaniye n'ingano y'uduce byakozwe hakoreshejwe kode yihariye yanditse.
Gupima mikorosikopi ya elegitoroni bikubiyemo gushyira MEAs zo mu igerageza muri epoxy resin mu rwego rwo kwitegura gukatamo ibice bito cyane hakoreshejwe icyuma cya diyama. Igice cya buri MEA cyaciwe ku bunini bwa nanometero 50 kugeza kuri 75. Mikorosikopi ya Talos F200X transmission electron (Thermo Fisher Scientific) yakoreshejwe mu gupima mikorosikopi ya elegitoroni (STEM) no gupima X-ray spectroscopy (EDS). Mikorosikopi ifite sisitemu ya EDS Super-X ifite ibikoresho bine bipima SDD bidafite amadirishya kandi ikora kuri kV 200.
Imiterere ya X-ray diffraction y'ifu (PXRD) yabonetse kuri Bruker Advance D8 powder X-ray diffractometer ifite imirasire ya Cu Kα yayunguruwe na Ni ikora kuri 40 kV na 40 mA. Intera yo gushakisha ni kuva kuri 10° kugeza kuri 60°, ingano y'intambwe ni 0.005°, kandi umuvuduko wo kubona amakuru ni isegonda 1 kuri buri ntambwe.
Ishusho ya RAS iri ku nkengero za katalyst ya Bi2O3 Bi L3 yapimwe nk'uko ubushobozi buhagaze hakoreshejwe akaremangingo kakozwe mu rugo. Wino ya ionomer ya Bi2O3 yakozwe hakoreshejwe 26.1 mg ya Bi2O3 ivanze n'umuti wa ionomer wa 156.3 μL (6.68%) kandi yahinduwe hakoreshejwe 1 M KOH, amazi (157 μL) na alcohol ya isopropyl (104 μL) kugira ngo haboneke winomer. Igipimo cya katalyst ni 0.4. Wino yashyizwe ku mpapuro za graphene mu duce twa mpandeshatu (10 × 4 mm) kugeza igihe umutwaro wa katalyst ya Bi2O3 ugeze kuri 0.5 mg / cm2. Igice gisigaye cy'urupapuro rwa graphene gisizwe na Kapton kugira ngo hatandukane utwo duce n'amashanyarazi. Urupapuro rwa graphene rwashyizwe hagati ya PTFE ebyiri kandi ruhambirwa ku mubiri w'akaremangingo (PEEK) hakoreshejwe vis, Ishusho S8. Hg / HgO (1 M NaOH) rwakoreshejwe nk'amashanyarazi, naho impapuro za karuboni zikoreshwa nk'amashanyarazi. Electrode y’icyerekezo cya Hg/HgO yagenzuwe hakoreshejwe insinga ya platine yinjijwe muri 0.1 M KOH ya hydrogen-saturated kugira ngo ihindure potentials zose zapimwe zibe electrode ya hydrogen isubira inyuma (RHE). XRD spectra yabonetse hagenzurwa potential ya electrode ikora ya Bi2O3/graphene sheet working electrode yinjijwe muri 0.1 M KOH, ishyushye kugeza kuri 30 °C. Electrolyte izenguruka muri bateri, aho electrolyte yinjira hasi mu karemangingo n'aho isohoka hejuru kugira ngo electrolyte ihure n'urwego rwa catalyst iyo uduheri twikoze. CH Instruments 760e potentiostat yakoreshejwe mu kugenzura potential ya electrode ikora. Itsinda ry’potential ryari potential ya open circuit: -100, -200, -300, -400, -500, -800, -850, -900, -1000, -1100, -1500 na +700 mV bitewe na RHE. potentials zose za iR zarahinduwe.
Isuzuma rya Bi L3 edge (~13424 eV kuri Bi metal) rya X-ray absorption fine structure (XAFS) ryakozwe kuri channel 10-ID, Advanced Photon Source (APS), Argonne National Fluorescence Laboratory. Laboratwari y'Igihugu yo gupima modele. Hakoreshejwe monochromator ya Si (111) ikonjeshejwe na azote y'amazi kugira ngo ihindure ingufu za X-ray, kandi hakoreshejwe indorerwamo ifite rhodium-coated kugira ngo igabanye ingano ya harmonic. Ingufu za scan zaratandukanye kuva kuri 13200 kugeza kuri 14400 eV, kandi fluorescence yapimwe hakoreshejwe silicon PIN diode ya 5 × 5 nta filters cyangwa Soller slits. Ingufu za zero crossing za derivative ya kabiri zipimwa kuri 13271.90 eV binyuze ku nkengero za L2 za foil ya Pt. Kubera ubunini bw'akaremangingo ka electrochemical, ntibyashobokaga gupima icyarimwe spectrum y'ikigereranyo cy'icyitegererezo. Bityo, impinduka zakozwe mu gupima no gupima mu ngufu za X-ray zibaye ni ±0.015 eV hashingiwe ku bipimo bisubiwemo mu igerageza ryose. Ubunini bw'urwego rwa Bi2O3 butuma urumuri rwinjira mu buryo runaka; electrodes zigumana icyerekezo gihamye ugereranyije n'umuraba w'ibintu n'icyuma gipima, bigatuma scan zose zisa. Near-field XAFS spectrum yakoreshejwe mu kumenya imiterere ya oxidation n'imiterere ya shimi ya bismuth ugereranije n'akarere ka XANES k'ibipimo bya Bi na Bi2O3 hakoreshejwe algorithme ya linear combination fitting ya software ya Athena (version 0.9.26). hakoreshejwe code IFEFFIT 44.
Amakuru ashyigikira imibare iri muri iyi nkuru hamwe n'indi myanzuro y'ubu bushakashatsi araboneka ku mwanditsi ubisabye mu buryo bwumvikana.
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