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Mbelata carbon dioxide na formic acid site na electrochemical bụ ụzọ dị mma isi melite ojiji carbon dioxide ma nwee ike itinye ya n'ọrụ dị ka ihe nchekwa hydrogen. N'ọrụ a, a na-emepụta usoro nhazi electrode membrane nke na-enweghị oghere maka njikọ electrochemical kpọmkwem nke formic acid site na carbon dioxide. Isi ihe dị mkpa na teknụzụ bụ membrane mgbanwe cation nke nwere oghere, nke, mgbe ejiri ya na nhazi membrane bipolar nke na-adịghị mma n'ihu, na-ekwe ka formic acid nke e mepụtara na njikọ membrane ahụ gbanwee site na ubi mmiri anodic na mkpokọta dị ala dị ka 0.25 M. Na-enweghị ihe ndị ọzọ dị n'etiti anode na cathode, echiche ahụ na-achọ iji ihe batrị dị ugbu a na atụmatụ ndị a na-ahụkarị na mkpụrụ ndụ mmanụ na hydrogen electrolysis, na-enye ohere maka mgbanwe ngwa ngwa na mmụba na azụmaahịa. Na sel 25 cm2, nhazi membrane mgbanwe cation nke nwere oghere na-enye arụmọrụ Faraday >75% maka formic acid na <2 V na 300 mA/cm2. Ihe kacha mkpa bụ na nnwale nkwụsi ike awa 55 na 200 mA/cm2 gosipụtara arụmọrụ Faraday kwụsiri ike na voltaji sel. A na-eji nyocha teknụzụ na akụ na ụba iji gosi ụzọ isi nweta nha nha ọnụ ahịa site na iji usoro mmepụta formic acid dị ugbu a.
A gosila na mbelata elektrọnik nke carbon dioxide gaa na formic acid site na iji ọkụ eletrik emeghari ebelatala ọnụ ahịa mmepụta ruo 75%1 ma e jiri ya tụnyere ụzọ ndị e si eji mmanụ ọkụ eme ihe n'oge ochie. Dịka egosiri na akwụkwọ2,3, formic acid nwere ọtụtụ ojiji, site na ụzọ dị irè na nke bara uru nke ịchekwa na ibuga hydrogen na ebe a na-azụ ihe maka ụlọ ọrụ kemịkalụ4,5 ma ọ bụ ụlọ ọrụ biomass6. Achọpụtala ọbụna formic acid dị ka ebe a na-azụ ihe maka mgbanwe ọzọ ka ọ bụrụ ebe a na-etinye mmanụ ọkụ jet na-adịgide adịgide site na iji injinia metabolic7,8. Site na mmepe nke akụnụba formic acid1,9, ọtụtụ ọrụ nyocha elekwasị anya na imeziwanye nhọrọ catalyst10,11,12,13,14,15,16. Agbanyeghị, ọtụtụ mgbalị na-aga n'ihu na-elekwasị anya na obere mkpụrụ ndụ H ma ọ bụ mkpụrụ ndụ mmiri mmiri na-arụ ọrụ na obere njupụta ugbu a (<50 mA/cm2). Iji belata ọnụ ahịa, nweta azụmaahịa ma mee ka ahịa dịkwuo mma, a ga-eme mbelata carbon dioxide (CO2R) na njupụta dị elu (≥200 mA/cm2) na arụmọrụ Faraday (FE)17 ebe a na-eme ka ojiji ihe onwunwe dịkwuo elu ma jiri ihe ndị mejupụtara batrị sitere na Teknụzụ na sel mmanụ na electrolysis mmiri na-enye ngwaọrụ CO2R ohere iji uru nke scale18. Na mgbakwunye, iji mee ka uru mmepụta dịkwuo elu ma zere nhazi ọzọ dị n'okpuru ala, a ga-eji formic acid dị ka ngwaahịa ikpeazụ kama ịmepụta nnu19.
N'ụzọ a, emeela mgbalị ndị na-adịbeghị anya iji mepụta ngwaọrụ CO2R formate/formic acid based gas diffusion electrode (GDE) nke metụtara ụlọ ọrụ mmepụta ihe. Nyocha zuru oke nke Fernandez-Caso et al.20 chịkọtara nhazi sel electrochemical niile maka mbelata CO2 na-aga n'ihu na formic acid/formate. N'ozuzu, enwere ike kewaa nhazi niile dị ugbu a n'ime ụdị atọ dị mkpa: 1. Katolita-na-agafe 19,21,22,23,24,25,26,27, 2. Otu akpụkpọ ahụ (akpụkpọ mgbanwe cation (CEM)28 ma ọ bụ akpụkpọ ahụ mgbanwe anion (AEM)29 na 3. Nhazi Sanwichi15,30,31,32. E gosiri akụkụ ndị a dị mfe na eserese 1a. Maka nhazi usoro nke catolita, a na-emepụta ụlọ elektrọl n'etiti akpụkpọ ahụ na katolita nke GDE. A na-eji katolita-na-agafe agagharị emepụta ọwa ion na oyi akwa katolita33, ọ bụ ezie na a na-arụrịta ụka mkpa ọ dị ijikwa nhọrọ formate34. Agbanyeghị, Chen et al jiri nhazi a. Site na iji katodi SnO2 na ihe mkpuchi carbon nwere oyi akwa katolita 1.27 mm dị arọ, ruo 90% FE 35 na 500 mA/cm2 ka e nwetara. E nwetara njikọta nke katolita dị arọ oyi akwa na akpụkpọ ahụ bipolar nke na-agbanwe agbanwe (BPM) nke na-egbochi mbufe ion na-enye voltaji ọrụ nke 6 V na arụmọrụ ike nke 15%. Iji melite arụmọrụ ike, Li et al., site na iji otu nhazi CEM, nwetara FE 29 nke 93.3% na njupụta ugbu a nke 51.7 mA/cm2. Diaz-Sainz et al.28 jiri igwe nzacha nwere otu akpụkpọ ahụ CEM na njupụta ugbu a nke 45 mA/cm2. Agbanyeghị, ụzọ niile mepụtara ụdị kama ngwaahịa a họọrọ, formic acid. Na mgbakwunye na ihe ndị ọzọ achọrọ maka nhazi, na nhazi CEM, ụdị dịka KCOOH nwere ike ịgbakọ ngwa ngwa na GDE na ubi mmiri, na-akpata mmachi njem na ọdịda mkpụrụ ndụ n'ikpeazụ.
Ntụnyere nke CO2R atọ kachasị pụta ìhè na nhazi ngwaọrụ mgbanwe formate/formic acid na usoro a tụrụ aro na ọmụmụ ihe a. b Ntụnyere nke mkpokọta mmepụta ugbu a na formate/formic acid maka nhazi catholyte, nhazi sanwichi, nhazi otu CEM na akwụkwọ (egosiri na Tebụl Mgbakwunye S1) na ọrụ anyị. Akara mepere emepe na-egosi mmepụta nke ngwọta formate, akara siri ike na-egosi mmepụta nke formic acid. * Nhazi egosiri site na iji hydrogen na anode. c Nhazi MEA efu-oghere site na iji akpụkpọ ahụ bipolar nwere oyi akwa mgbanwe cation nke nwere oghere na-arụ ọrụ na ọnọdụ ihu.
Iji gbochie nhazi usoro, Proietto na ndị otu ya jiri nhazi igwe nzacha na-enweghị nkewa nke mmiri deionized na-agafe na interlayer ahụ. Sistemụ ahụ nwere ike iru ihe karịrị 70% CE na oke njupụta dị ugbu a nke 50–80 mA/cm2. N'otu aka ahụ, Yang na ndị otu ya 14 tụrụ aro ka e jiri akwa siri ike nke electrolyte dị n'etiti CEM na AEM iji kwalite mmepụta nke formic acid. Yang na ndị otu ya 31,36 nwetara 91.3% FE na sel 5 cm2 na 200 mA/cm2, na-emepụta ngwọta formic acid 6.35 wt%. Xia na ndị otu ya site na iji nhazi yiri nke ahụ, e nwetara 83% mgbanwe nke carbon dioxide (CO2) gaa na formic acid FE na 200 mA/cm2, a nwalekwara ike sistemụ ahụ ruo awa 100 na nkeji iri atọ. Ọ bụ ezie na nsonaazụ obere nha na-ekwe nkwa, mmụba ọnụ ahịa na mgbagwoju anya nke resin mgbanwe ion porous na-eme ka o sie ike ịhazi nhazi dị n'etiti oyi akwa na sistemụ ndị buru ibu (dịka ọmụmaatụ, 1000 cm2).
Iji hụ mmetụta dị n'etiti ihe dị iche iche, anyị depụtara mmepụta formate/formic acid kwa kWh maka sistemụ niile a kpọtụrụ aha na mbụ ma see ha na Foto 1b. O doro anya ebe a na sistemụ ọ bụla nwere catholyte ma ọ bụ interlayer ga-arụ ọrụ ya nke ọma na obere njupụta ugbu a ma mebie na njupụta ugbu a dị elu, ebe oke ohmic nwere ike ikpebi voltaji sel. Ọzọkwa, ọ bụ ezie na nhazi CEM nke na-arụ ọrụ ike na-enye mmepụta molar formic acid kachasị elu kwa kWh, mmụba nnu nwere ike ibute mmebi arụmọrụ ngwa ngwa na njupụta ugbu a dị elu.
Iji belata ụdị ọdịda a tụlere na mbụ, anyị mepụtara mgbakọ elektrọd membrane (MEA) nke nwere BPM nwere njikọ ihu na-enweghị isi yana akpụkpọ mgbanwe cation (PCEM). E gosiri usoro ihe owuwu ahụ na Foto 1c. A na-ewebata hydrogen (H2) n'ime anode iji mepụta protons site na mmeghachi omume oxidation hydrogen (HOR). A na-ewebata oyi akwa PCEM n'ime sistemụ BPM iji kwe ka ion formatic emepụtara na cathode gafere AEM, jikọta ya na protons iji mepụta formic acid na njikọ BPM na pores interstitial nke CEM, wee pụọ site na GDE anode na flow field. . Site na nhazi a, anyị nwetara >75% FE nke formic acid na <2 V na 300 mA/cm2 maka mpaghara sel 25 cm2. Ihe kachasị mkpa bụ na imewe ahụ na-eji ihe ndị dị na azụmaahịa na usoro ngwaike maka osisi mmanụ ọkụ na electrolysis mmiri, na-enye ohere maka oge ngwa ngwa iji tụọ. Nhazi Catholyte nwere ụlọ mmiri catholyte nke nwere ike ibute enweghị nguzozi nrụgide n'etiti usoro gas na mmiri mmiri, ọkachasị na nhazi sel buru ibu. Maka nhazi sanwichi nwere oghere mmiri mmiri, a chọrọ mgbalị dị ukwuu iji melite oghere dị n'etiti oghere iji belata mbelata nrụgide na mkpokọta carbon dioxide n'ime akwa dị n'etiti. Ihe abụọ a nwere ike ibute nsogbu nke nkwukọrịta sel. Ọ na-esikwa ike imepụta akwa dị gịrịgịrị nke na-eguzo n'otu ebe n'ọtụtụ buru ibu. N'ụzọ dị iche, nhazi ọhụrụ a tụrụ aro bụ nhazi MEA efu nke na-enweghị oghere mmiri ma ọ bụ akwa dị n'etiti. Ma e jiri ya tụnyere sel electrochemical ndị ọzọ dị adị, nhazi a tụrụ aro pụrụ iche n'ihi na ọ na-enye ohere maka njikọ kpọmkwem nke formic acid na nhazi dị mfe, nke na-arụ ọrụ nke ọma, nke na-enweghị oghere efu.
Iji gbochie evolushọn hydrogen, nnukwu mgbalị mbelata CO2 ejirila nhazi akpụkpọ ahụ MEA na AEM yana electrolytes dị elu (dịka egosiri na Foto 2a). Na nhazi ndị a, ion formula nke e guzobere na cathode na-agafe na akpụkpọ ahụ dị ka ụdị chajị na-adịghị mma, mgbe ahụ a na-emepụta KCOOH ma na-apụ na sistemụ ahụ site na iyi anodic KOH. Ọ bụ ezie na voltaji FE na sel dị mma na mbụ dịka egosiri na Foto 2b, nnwale nkwụsi ike butere mbelata na FE nke ihe dị ka 30% naanị awa 10 (Foto S1a–c). E kwesịrị ịmara na iji 1 M KOH anolyte dị oke mkpa iji belata oke voltaji anodic na sistemụ alkaline oxygen evolushọn reaction (OER)37 ma nweta ohere ion n'ime cathode catalyst bed33. Mgbe e belatara njupụta anolyte ruo 0.1 M KOH, ma voltaji sel na oxidation formic acid (ọnwụ nke formic acid) na-abawanye (Foto S1d), na-egosi mgbanwe efu. E jiri nhazi oke zuru oke nyochaa ogo oxidation formate; maka nkọwa ndị ọzọ, lee ngalaba "Ụzọ". A mụkwara arụmọrụ site na iji nhazi MEA na otu CEM membrane, a na-egosikwa nsonaazụ ya na Foto S1f,g. Ụdị FE anakọtara na cathode ahụ dị >60% na 200 mA/cm2 na mmalite nke ule ahụ, mana ọ gbawara ngwa ngwa n'ime awa abụọ n'ihi nchịkọta nnu cathode a tụlere na mbụ (Foto S11).
Usoro nke oghere efu nke MEA nwere CO2R na kathode, mmeghachi omume oxidation hydrogen (HOR) ma ọ bụ OER na anode, na otu akpụkpọ ahụ AEM n'etiti. b FE na voltaji sel maka nhazi a na 1 M KOH na OER na-asọ na anode. Ogwe njehie na-anọchite anya ọdịiche ọkọlọtọ nke nha atọ dị iche iche. na FE na voltaji sel sistemụ yana H2 na HOR na anode. A na-eji agba dị iche iche amata mmepụta formate na formic acid. d Usoro eserese nke MEA na BPM gbanwere n'ihu n'etiti. FE na voltaji batrị megide oge na 200 mA/cm2 site na iji nhazi a. f Foto obe nke BPM MEA nke nwere echiche ihu mgbe obere ule gasịrị.
Iji mepụta formic acid, a na-enye hydrogen na ihe na-akpali Pt-on-carbon (Pt/C) na anode. Dịka egosiri na Foto 2d, a nyochaburu na mbụ na protons BPM na-emepụta n'ihu na anode iji nweta mmepụta formic acid. Ngalaba nhazi BPM dara ada mgbe nkeji iri anọ nke ọrụ na ugbu a nke 200 mA/cm2, ya na mmụba voltaji nke karịrị 5 V (Fig. 2e). Mgbe anwalechara ya, a hụrụ delamination doro anya na interface CEM/AEM. E wezụga formate, anions dị ka carbonate, bicarbonate na hydroxide nwekwara ike ịgafe akpụkpọ ahụ AEM ma meghachi omume na protons na interface CEM/AEM iji mepụta gas CO2 na mmiri mmiri, na-eduga na delamination BPM (Fig. 2f) na , n'ikpeazụ na-eduga na ọdịda sel.
Dabere na usoro arụmọrụ na ọdịda nke nhazi dị n'elu, a na-atụ aro usoro MEA ọhụrụ dịka egosiri na Foto 1c ma kọwaa ya na Foto 3a38. N'ebe a, oyi akwa PCEM na-enye ụzọ maka mbugharị nke formic acid na anions site na njikọ CEM/AEM, si otú a na-ebelata mkpokọta nke ihe ahụ. N'otu oge ahụ, ụzọ PCEM interstitial na-eduga formic acid n'ime usoro mgbasa na ubi mmiri, na-ebelata ohere nke oxidation formic acid. Nsonaazụ polarization site na iji AEMs nwere ọkpụrụkpụ nke 80, 40 na 25 mm ka egosiri na Foto 3b. Dịka a tụrụ anya ya, ọ bụ ezie na voltaji sel zuru oke na-abawanye ka ọkpụrụkpụ AEM na-abawanye, iji AEM dị arọ na-egbochi mgbasa azụ nke formic acid, si otú a na-amụba pH cathode ma na-ebelata mmepụta H2 (Fig. 3c–e).
Ihe osise nke usoro MEA nwere AEM na CEM nwere oghere na ụzọ njem formic acid dị iche iche. b Voltaji sel na njupụta ugbu a dị iche iche na ọkpụrụkpụ AEM dị iche iche. na EE na njupụta ugbu a dị iche iche nwere ọkpụrụkpụ AEM nke 80 μm (d) 40 μm, e) 25 μm. Ogwe njehie na-anọchite anya ọdịiche ọkọlọtọ nke a tụrụ site na ihe atụ atọ dị iche iche. f Nsonaazụ nṅomi nke mkpokọta formic acid na uru pH na njikọ CEM/AEM dị iche iche na ọkpụrụkpụ AEM dị iche iche. f PC na pH na oyi akwa cathode nke ihe na-akpali akpali nwere ọkpụrụkpụ ihe nkiri AEM dị iche iche. g Nkesa akụkụ abụọ nke mkpokọta formic acid na njikọ CEM/AEM na oghere.
Foto S2 na-egosi nkesa nke mkpokọta formic acid na pH n'ofe ọkpụrụkpụ MEA site na iji ihe nlereanya Poisson-Nernst-Planck finite element. Ọ bụghị ihe ijuanya na a na-ahụ mkpokọta kachasị elu nke formic acid, 0.23 mol/L, na njikọ CEM/AEM, ebe ọ bụ na a na-emepụta formic acid na interface a. Mkpokọta nke formic acid site na AEM na-ebelata ngwa ngwa ka ọkpụrụkpụ nke AEM na-abawanye, na-egosi iguzogide ibufe oke na obere mmiri formic acid n'ihi mgbasa azụ. Foto 3 f na g na-egosi ụkpụrụ pH na formic acid n'ime akwa cathode catalyst nke mgbasa azụ na nkesa akụkụ abụọ nke mkpokọta formic acid kpatara, n'otu n'otu. Ka akpụkpọ ahụ AEM dị gịrịgịrị, ka mkpokọta formic acid dị elu dị nso na cathode, na pH nke cathode na-aghọ acidic. Ya mere, ọ bụ ezie na akpụkpọ ahụ AEM dị arọ na-ebute mfu ohmic dị elu, ha dị oke mkpa iji gbochie mgbasa azụ nke formic acid na kathode ma mee ka ịdị ọcha dị elu nke sistemụ FE formic acid dịkwuo elu. N'ikpeazụ, ịbawanye ọkpụrụkpụ AEM ruo 80 μm mere ka FE >75% maka formic acid na <2 V na 300 mA/cm2 maka mpaghara sel 25 cm2.
Iji nwalee nkwụsi ike nke usoro PECM a, a na-ejigide ọkụ eletrik batrị na 200 mA/cm2 ruo awa 55. E gosipụtara nsonaazụ niile na Foto 4, yana nsonaazụ sitere na awa 3 mbụ na Foto S3. Mgbe ejiri Pt/C anodic catalyst, voltaji sel mụbara nke ukwuu n'ime nkeji 30 mbụ (Foto S3a). N'ime oge dị ogologo, voltaji sel ahụ nọgidere na-agbanwe agbanwe, na-enye ọnụego mmebi nke 0.6 mV/h (Foto 4a). Na mbido ule ahụ, PV nke formic acid a chịkọtara na anode bụ 76.5% na PV nke hydrogen a chịkọtara na katode bụ 19.2%. Mgbe awa mbụ nke nnwale gasịrị, hydrogen FE dara ruo 13.8%, na-egosi mma nhọrọ formate. Agbanyeghị, ọnụego oxidation nke formic acid dị na sistemụ ahụ dara ruo 62.7% n'ime otu awa, ọnụego oxidation nke anodic formic acid mụbara site na ihe fọrọ nke nta ka ọ bụrụ efu na mmalite ule ahụ ruo 17.0%. Mgbe nke ahụ gasịrị, FE nke H2, CO, formic acid na ọnụego oxidation anodic nke formic acid nọgidere na-akwụsi ike n'oge nnwale ahụ. Mmụba nke oxidation formic acid n'ime awa mbụ nwere ike ịbụ n'ihi mkpokọta formic acid na njikọ PCEM/AEM. Ka njupụta nke formic acid na-abawanye, ọ bụghị naanị na ọ na-apụ site na oghere nke membrane ahụ, kamakwa ọ na-agbasa site na FEM n'onwe ya ma banye na oyi akwa anode Pt/C. Ebe ọ bụ na formic acid bụ mmiri mmiri na 60°C, nchịkọta ya nwere ike ibute nsogbu mbufe oke ma bute oxidation kacha mma karịa hydrogen.
voltaji sel megide oge (200 mA/cm2, 60 °C). Ihe dị n'ime ya na-egosi onyonyo mikroskopu anya nke akụkụ obe nke MEA nwere EM nwere oghere. Ogwe nha: 300 µm. b Ịdị ọcha nke PE na formic acid dịka ọrụ oge na 200 mA/cm2 site na iji Pt/C anode.
E ji usoro ihe nlele ndị a na mmalite nnwale (BOT) n'oge nkwadebe na na njedebe nke nnwale (EOT) mara ihe atụ nke ule nkwụsi ike site na iji nano-X-ray computed tomography (nano-CT), dịka egosiri na Foto 5 a. Ihe nlele EOT nwere nnukwu nha ihe mkpali nwere dayameta nke 1207 nm ma e jiri ya tụnyere 930 nm maka BOT. E gosiri onyonyo igwe nyocha elektrọn gbara ọchịchịrị nke nwere ike ịgbasa (HAADF-STEM) na nsonaazụ X-ray spectroscopy (EDS) na Foto 5b. Ọ bụ ezie na oyi akwa ihe mkpali BOT nwere ọtụtụ obere ihe mkpali yana ụfọdụ agglomerates buru ibu, na ọkwa EOT, enwere ike kewaa oyi akwa ihe mkpali ahụ n'ime mpaghara abụọ dị iche iche: otu nwere obere ihe siri ike buru ibu na nke ọzọ nwere mpaghara oghere. Ọnụọgụ obere ihe. Foto EDS na-egosi na nnukwu ihe siri ike bara ụba na Bi, ikekwe Bi metal, na mpaghara oghere bara ụba na oxygen. Mgbe a na-arụ ọrụ na sel ahụ na 200 mA/cm2, ikike adịghị mma nke cathode ahụ ga-eme ka Bi2O3 belata, dịka nsonaazụ X-ray absorption spectroscopy nke a tụlere n'okpuru gosiri. Nsonaazụ maapụ HAADF-STEM na EDS na-egosi na Bi2O3 na-agafe usoro mbelata, na-eme ka ha ghara inwe oxygen ma jikọta ha ka ha bụrụ obere ihe ígwè. Ụdị mgbasa ozi X-ray nke cathodes BOT na EOT na-akwado nkọwa nke data EDS (Foto 5c): naanị Bi2O3 kristal ka achọpụtara na cathode BOT, a hụkwara bimetal kristal na cathode EOT. Iji ghọta mmetụta nke cathode potential na ọnọdụ oxidation nke cathode Bi2O3, a gbanwere okpomọkụ site na ike sekit mepere emepe (+0.3 V vs RHE) ruo -1.5 V (vs RHE). A hụrụ na usoro Bi2O3 na-amalite ibelata na -0.85 V ma e jiri ya tụnyere RHE, mbelata na ike nke ahịrị ọcha na mpaghara nsọtụ nke spectrum na-egosi na a na-ebelata Metal Bi ruo 90% nke RHE na -1.1. V megide RHE (Foto 5d). N'agbanyeghị usoro ahụ, nhọrọ zuru oke nke format na katod agbanweghị, dịka esi chọpụta site na H2 na CO FE na nhazi formic acid, n'agbanyeghị mgbanwe dị ukwuu na ọdịdị katod, ọnọdụ oxidation catalyst, na nhazi microcrystalline.
Nhazi akụkụ atọ nke oyi akwa catalyst na nkesa nke ihe ndị na-akpali akpali nke e nwetara site na iji nano-X-ray CT. Ogwe nha: 10 µm. b Top 2: Foto HAADF-STEM nke oyi akwa cathode nke BOT na EOT catalyst. Ogwe nha: 1 µm. Ala 2: Foto HADF-STEM na EDX buru ibu nke oyi akwa cathode nke ihe na-akpali akpali EOT. Ogwe nha: 100 nm. c Ụdị mgbasa ozi X-ray nke ihe nlele BOT na EOT cathode. d In situ X-ray absorption spectra nke electrode Bi2O3 na 0.1 M KOH dị ka ọrụ nke ike (0.8 V ruo -1.5 V vs. RHE).
Iji chọpụta kpọmkwem ohere dị maka imeziwanye arụmọrụ ike site na igbochi oxidation formic acid, ejiri electrode ntụaka H2 chọpụta onyinye nke mfu voltaji39. Na njupụta ugbu a na-erughị 500 mA/cm2, ikike cathode ka dị n'okpuru -1.25 V. A na-ekewa ikike anodic n'ime akụkụ abụọ bụ isi: njupụta ugbu a mgbanwe HOR na oke voltaji HOR 40 nke e buru amụma ya site na nha anya Bulter-Volmer a tụrụ na mbụ, akụkụ fọdụrụ bụ n'ihi oxidation formic acid. N'ihi kinetics mmeghachi omume dị nwayọ ma e jiri ya tụnyere HOR41, obere ọnụego nke mmeghachi omume oxidation formic acid na anode nwere ike ibute mmụba dị ukwuu na ikike anodic. Nsonaazụ ya na-egosi na mgbochi zuru oke nke oxidation anodic formic acid nwere ike iwepụ ihe fọrọ nke nta ka ọ bụrụ 500 mV overvoltage.
Iji nwalee atụmatụ a, a gbanwere ọsọ mmiri deionized (DI) na ntinye anode iji belata mkpokọta formic acid na-esi n'ime mmiri pụta. Foto 6b na c na-egosi FE, mkpokọta formic acid, na voltaji sel dịka ọrụ nke flux DI na anode na 200 mA/cm2. Ka ọnụego mmiri deionized mụbara site na 3.3 mL/min ruo 25 mL/min, mkpokọta formic acid na anode belatara site na 0.27 mol/L ruo 0.08 mol/L. Ma e jiri ya tụnyere, site na iji usoro sandwich nke Xia et al. 30 tụrụ aro, enwetara formic acid nke 1.8 mol/L na 200 mA/cm2. Ibelata mkpokọta ahụ na-eme ka FE zuru oke nke formic acid dịkwuo mma ma na-ebelata FE nke H2 ka kathode pH na-aghọ alkaline karịa n'ihi mbelata mgbasa azụ nke formic acid. Mbelata nke mkpokọta formic acid na oke mmiri DI na-ewepụkwara oxidation formic acid n'ihe fọrọ nke nta ka ọ bụrụ, na-ebute voltaji sel niile nke dị ihe na-erughị 1.7 V na 200 mA/cm2. Okpomọkụ batrị na-emetụtakwa arụmọrụ zuru oke, a na-egosikwa nsonaazụ ya na Foto S10. Agbanyeghị, usoro nhazi PCEM nwere ike imeziwanye arụmọrụ ike nke ukwuu n'igbochi oxidation formic acid, ma ọ bụ site na iji ihe ndị na-eme ka anodic catalysts nwere nhọrọ hydrogen ka mma na formic acid ma ọ bụ site na ọrụ ngwaọrụ.
a Ndahie voltaji sel site na iji elektrọd H2 ntụaka sel na-arụ ọrụ na 60 °C, Pt/C anode na 80 µm AEM. b FE na mkpokọta acid formic anakọtara na 200 mA/cm2 site na iji ọnụego mmiri anodic deionized dị iche iche. c Mgbe anode na-anakọta formic acid na mkpokọta dị iche iche, voltaji sel bụ 200 mA/cm2. Ogwe njehie na-anọchite anya mgbanwe ọkọlọtọ nke nha atọ dị iche iche. d Ọnụ ahịa ire ere kacha nta nke a na-ekewa site na arụmọrụ na ọnụego mmiri deionized dị iche iche site na iji ọnụ ahịa ọkụ eletrik mba nke US $0.068/kWh na US $4.5/kg hydrogen. (*: A na-eche na oxidation kacha nta nke formic acid na anode bụ 10 M FA, nkezi ọnụahịa ọkụ eletrik ụlọ ọrụ mba bụ $0.068/kWh, na hydrogen bụ $4.5/kg. **: A na-eche na oxidation kacha nta bụ formic acid. Ọnụọgụ nke FA na anode bụ 1.3 M anode, a na-atụ anya na ọnụahịa ọkụ eletrik n'ọdịnihu bụ $0.03/kWh, akara ntụpọ na-anọchite anya ọnụahịa ahịa nke 85 wt% FA.
E mere nyocha teknụzụ-akụnụba (TEA) iji nweta ọnụahịa kacha nta nke njikọta mmanụ ọkụ n'okpuru ọtụtụ ọnọdụ ọrụ, dịka egosiri na Foto 5d. Enwere ike ịchọta ụzọ na data ndabere maka TEA na SI. Mgbe ntinye LC dị na ikuku anode dị elu, n'agbanyeghị voltaji sel dị elu, ọnụ ahịa mkpokọta nke njikọta mmanụ ọkụ na-ebelata n'ihi mbelata na ọnụ ahịa nkewa. Ọ bụrụ na enwere ike ibelata oxidation anodic nke formic acid site na mmepe catalyst ma ọ bụ teknụzụ electrode, njikọta nke voltaji sel dị ala (1.66 V) na ntinye FA dị elu na mmiri ọkụ (10 M) ga-ebelata ọnụ ahịa mmepụta electrochemical FA na 0.74 US dollar/kg (dabere na ọnụahịa ọkụ eletrik). $0.068/kWh na $4.5/kg hydrogen42. Ọzọkwa, mgbe ejikọtara ya na atụmatụ ọdịnihu nke ọkụ eletrik a na-emegharị emegharị nke $0.03/kWh na hydrogen nke $2.3/kg, ebumnuche mmiri mkpofu FA ga-ebelata ruo nde 1.3, nke na-eme ka atụmatụ ikpeazụ nke mmepụta bụrụ US$0.66/kg43. Nke a yiri ọnụahịa ahịa dị ugbu a. Ya mere, mgbalị ndị a na-eme n'ọdịnihu lekwasịrị anya na ihe na nhazi elektrọd nwere ike ibelata anodization ma na-ekwe ka ọrụ na obere voltaji sel mepụta mkpokọta LC dị elu.
Na nchịkọta, anyị amụọla ọtụtụ nhazi MEA efu maka mbelata CO2 gaa na formic acid ma tụọ aro nhazi nwere akpụkpọ ahụ bipolar nke nwere ihu-obi abụọ gụnyere akpụkpọ ahụ mgbanwe cation (PECM) nke nwere oghere iji mee ka njikọ mbufe membrane dị mfe maka formic acid sikwuo ike. Nhazi a na-emepụta >96% formic acid na mkpokọta ruo 0.25 M (na ọnụego mmiri anode DI nke 3.3 mL/min). Na ọnụego mmiri DI dị elu (25 mL/min), nhazi a nyere njupụta ugbu a nke >80% FE nke 200 mA/cm2 na 1.7 V site na iji mpaghara sel 25 cm2. Na ọnụego mmiri anodic DI dị ala (10 mL/min), nhazi PECM nọgidere na-enwe voltaji kwụsiri ike na ọkwa FE dị elu maka awa 55 nke nnwale na 200 mA/cm2. Enwere ike ime ka nkwụsi ike na nhọrọ dị elu nke ndị na-akpali akpali na ihe polymeric membrane nwetara site na ijikọta ha na electrocatalysts kachasị mma. Ọrụ ndị ọzọ ga-elekwasị anya n'ịgbanwe ọnọdụ ọrụ, nhọrọ nke ihe na-akpali akpali nke anode, na nhazi MEA iji belata oxidation nke formic acid, na-ebute mmụba nke ihe na-esi na ya pụta na obere voltaji sel. Ụzọ dị mfe iji carbon dioxide maka formic acid dị ebe a na-ewepụ mkpa maka ụlọ anolyte na catholyte, ihe ndị dị na sandwich, na ihe pụrụ iche, si otú a na-eme ka arụmọrụ ike cell dịkwuo elu ma na-ebelata mgbagwoju anya sistemụ, na-eme ka ọ dịkwuo mfe ịbawanye. Nhazi a tụrụ aro na-enye ikpo okwu maka mmepe n'ọdịnihu nke osisi ntụgharị CO2 dị irè na nke akụ na ụba.
Ọ gwụla ma e kwuru ihe ọzọ, e jiri ihe niile dị na kemịkal na ihe mgbaze mee ihe dịka e si nabata ya. E zụtara Bismuth oxide catalyst (Bi2O3, 80 nm) site na US Research Nanomaterials, Inc. IONOMR nyere ntụ ntụ Polymer (AP1-CNN8-00-X). E zụtara Omnisolv® nke aha ya bụ N-propanol (nPA) na mmiri ultrapure (18.2 Ω, Milli–Q® Advantage A10 water purification system) site na Millipore Sigma. A zụtara methanol na acetone nke ACS kwadoro site na VWR Chemicals BDH® na Fisher Chemical, n'otu n'otu. E gwakọtara ntụ ntụ polymer ahụ na ngwakọta nke acetone na methanol n'ogo nke 1:1 site na ibu iji nweta mgbasa polymer nwere mkpokọta nke 6.5 wt.%. Kwadebe ink catalytic site na ịgwakọta 20g Bi2O3, mmiri ultrapure, nPA na mgbasa ionomer n'ime ite 30ml. Ihe mejupụtara ya nwere ihe na-akpali akpali nke 30 wt.%, oke oke nke ionomer na ihe na-akpali akpali nke 0.02 na oke oke mmanya na mmiri nke 2:3 (40 wt.% nPA). Tupu agwakọta ya, etinyere 70g nke ihe e ji egweri Glen Mills 5mm zirconia na ngwakọta ahụ. E tinyere ihe nlele na ihe eji atụgharị karama dijitalụ Fisherbrand™ na 80 rpm maka awa 26. Hapụ ink ahụ ka ọ nọdụ ala ruo nkeji 20 tupu etinye ya. E tinyere ink Bi2O3 na ihe na-etinye Qualtech akpaka (QPI-AFA6800) site na iji ihe na-eme ka waya ụlọ nyocha dị 1/2″ x 16″ (RD Specialties - dayameta mil 60) na 22°C. E tinyere ink catalytic 5 mL na ihe na-ebufe gas carbon Sigraacet 39 BB 7.5 x 8 inch (nchekwa sel mmanụ) site na itinye mkpanaka na ọsọ a kapịrị ọnụ nke 55 mm/sekọnd. Bufee elektrọd ndị a e ji ekpuchi ihe n'ime oven wee kpọọ nkụ na 80 °C. Usoro mkpuchi mkpanaka na onyonyo nke mkpuchi GDE ka egosiri na Foto S4a na b. Ngwa X-ray fluorescence (XRF) (Fischerscope® XDV-SDD, Fischer-Technolgy Inc. USA) kwadoro na ibu GDE a kpuchiri bụ 3.0 mg Bi2O3/cm2.
Maka nhazi akpụkpọ ahụ mejupụtara nke nwere akpụkpọ mgbanwe anion (AEM) na CEM nwere oghere, ejiri Nafion NC700 (Chemours, USA) nke nwere ọkpụrụkpụ aha nke 15 µm dị ka oyi akwa CEM. A fesa ihe na-akpali anodic ahụ ozugbo na FEM site na oke ionomer na carbon nke 0.83 na mpaghara mkpuchi nke 25 cm2. Ejiri platinum akwadoro nke nwere nnukwu mpaghara elu (50 wt.% Pt/C, TEC 10E50E, TANAKA ọla dị oké ọnụ ahịa) nke nwere ibu nke 0.25 mg Pt/cm2 dị ka ihe na-akpali anode. Ejiri Nafion D2020 (Ion Power, USA) dị ka ionomer maka oyi akwa anode nke ihe na-akpali akpali. A na-eme oghere CEM site na ịbe ahịrị ndị yiri ya na ihe nkiri CEM na oge 3mm. E gosiri nkọwa nke usoro oghere na Foto S12b na c. Site na iji X-ray computed tomography, e gosiri na oghere oghere ahụ bụ 32.6 μm, dịka egosiri na Foto S12d na e. N'oge njikọta sel, e tinyere akpụkpọ ahụ CEM nke nwere oghere a kpuchiri catalyst na akwụkwọ Toray 25 cm2 (5 wt% PTFE treated, Fuel Cell Store, USA). E tinyere akpụkpọ ahụ AEM (PiperION, Versogen, USA) nke nwere ọkpụrụkpụ nke 25, 40 ma ọ bụ 80 μm n'elu CEM wee tinye ya na cathode GDE. E bepụrụ akpụkpọ ahụ AEM n'ime iberibe 7.5 × 7.5 cm iji kpuchie ubi mmiri niile ma mikpuo ya n'ime mmiri potassium hydroxide 1 M n'abalị tupu e jikọta ya. Ma anode na cathode na-eji oghere PTFE nke buru ibu iji nweta mkpakọ GDE kacha mma nke 18%. Nkọwa nke usoro njikọta batrị egosiri na Foto S12a.
N'oge nnwale ahụ, a na-edobe sel ahụ a chịkọtara na 60 °C (30, 60, na 80 °C maka ọmụmụ ihe gbasara okpomọkụ) yana 0.8 L/min nke hydrogen gas enyere na anode na 2 L/min nke carbon dioxide enyere na cathode. E tinyere mmiri mmiri ma mmiri anodic na cathodic na 100% iru mmiri na 259 kPa oke nrụgide cathodic. N'oge ọrụ ahụ, a gwakọtara mmiri gas cathode na 1 M KOH na ọnụego 2 mL/min iji kwalite ojiji nke cathode catalyst bed na ionic conduction. Gwakọta mmiri anode na mmiri deionized na ọnụego 10 ml/min iji wepụ formic acid na anode. E gosiri nkọwa nke ntinye na mmepụta ngwaọrụ na Foto S5. Gas ikuku cathode nwere CO2 ma na-emepụta CO na H2. A na-ewepụ uzuoku mmiri site na condenser (okpomọkụ dị ala na 2°C). A ga-anakọta gas fọdụrụnụ maka nyocha oge gas. Mmiri anode ahụ ga-agafekwa na condenser iji kewaa mmiri mmiri ahụ na gas ahụ. A ga-anakọta mmiri mkpofu ahụ na vials dị ọcha ma nyochaa ya site na iji chronometry mmiri mmiri iji chọpụta acid formic e mepụtara. E mere ule electrochemical site na iji Garmy potentiostat (nọmba ntụaka 30K, Gamry, USA). Tupu a tụọ usoro polarization, e tinyere mkpụrụ ndụ ahụ n'ọnọdụ ugboro anọ site na 0 ruo 250 mA/cm2 site na iji voltammetry linear na ọnụego nyocha nke 2.5 mA/cm2. E nwetara usoro polarization na ọnọdụ galvanostatic na sel ahụ ejirigide na njupụta ugbu a maka nkeji anọ tupu a nwalee gas cathode na mmiri anolyte.
Anyị na-eji elektrọd ntụaka hydrogen na MEA kewaa kathode na ike anodic. E gosiri nhazi nke elektrọd ntụaka na Foto S6a. E jiri akpụkpọ ahụ Nafion (Nafion 211, IonPower, USA) dị ka àkwà mmiri ionic iji jikọọ akpụkpọ ahụ MEA na elektrọd ntụaka. E jikọtara otu nsọtụ nke eriri Nafion na elektrọd mgbasa gas 1 cm2 (GDE) nke ejiri 0.25 mg Pt/cm2 (50 wt% Pt/C, TEC10E50E, TANAKA Precious Metals) gbasaa na akwụkwọ carbon 29BC (Fuel Cell Store, USA). ). A na-eji ngwaike polyetheretherketone (PEEK) pụrụ iche iji mechie gas ma hụ na enwere ezigbo njikọ n'etiti eriri GDE na Nafion, yana iji jikọọ elektrọd ntụaka na ngwaike sel mmanụ. A na-ejikọ nsọtụ nke ọzọ nke eriri Nafion na nsọtụ pụtara ìhè nke batrị CEM. Foto S6b na-egosi akụkụ obe nke elektrọd ntụaka ejikọtara na MEA.
Mgbe gas ikuku na-apụ apụ gafere na condenser na gas-liquid separator, a na-ewere ihe nlele gas site na kathode. A nyochachara gas ahụ ma ọ dịkarịa ala ugboro atọ site na iji 4900 Micro GC (10 μm molecular sieve, Agilent). A chịkọtara ihe nlele na akpa ihe nlele gas aluminom foil multi-layer Supel™ (Sigma-Aldrich) nke na-adịghị arụ ọrụ ruo oge akọwapụtara (sekọnd 30) ma tinye aka na microgas chromatograph n'ime awa abụọ nke nchịkọta. E debere okpomọkụ ọgwụ ahụ na 110°C. E kewara carbon monoxide (CO) na hydrogen (H2) na kọlụm MS5A nke a kpụ ọkụ n'ọnụ (105 °C) nke nwere nrụgide (28 psi) 10 m site na iji argon (Matheson Gas-Matheson Purity) dị ka gas na-ebu. A na-achọpụta njikọ ndị a site na iji ihe nchọpụta Thermal Conductivity Detector (TCD) arụnyere n'ime ya. E gosiri chromatograms GC na usoro nhazi CO na H2 na Foto S7. E si na anode chịkọta ihe nlele formic acid mmiri mmiri ruo oge a kapịrị ọnụ (sekọnd 120) wee jiri nzacha sirinji PTFE 0.22 μm sachaa ya n'ime karama 2 mL. E jiri sistemụ Agilent 1260 Infinity II bioinert high-performance liquid chromatography (HPLC) nyochaa ngwaahịa mmiri mmiri dị na karama ndị ahụ, nke a gbara 20 μl nke ihe nlele site na autosampler (G5668A) na usoro mkpanaka nke 4 mM sulfuric acid (H2SO4). na ọnụego mmiri nke 0.6 ml/min (quaternary pump G5654A). E kewara ngwaahịa ndị ahụ na ọkụ (35°C, oven kọlụm G7116A) Aminex HPX-87H 300 × 7.8 mm (Bio-Rad) nke kọlụm nche Micro-Guard Cation H tupu ya. E ji ihe nchọpụta diode array (DAD) chọpụta Formic acid. Na ogologo ebili mmiri nke 210 nm na bandwit nke 4 nm. E gosiri usoro nhazi HPL chromatogram na formic acid ọkọlọtọ na eserese S7.
A na-eji usoro a gbakọọ ngwaahịa gas (CO na H2) FE, a na-agbakọkwa mkpokọta moles nke gas site na iji usoro gas kacha mma:
N'ime ha: \({n}_{i}\): ọnụọgụ elektrọn dị na mmeghachi omume electrochemical. \(F\): Ihe na-agbanweghi agbanwe nke Faraday. \({C}_{i}\): Njupụta ngwaahịa mmiri HPLC. \(V\): olu nke ihe nlele mmiri anakọtara n'oge a kapịrị ọnụ t. \(j\): njupụta ugbu a. \(A\): Mpaghara geometric nke elektrọd (25 cm2). \(t\): oge ​​nlele. \(P\): nrụgide zuru oke. \({x}_{i}\): Pasentị Mole nke gas nke GC kpebiri. \(R\): ihe na-agbanweghi agbanwe nke gas. \(T\): okpomọkụ.
E jiri inductively coupled plasma atomic emission spectroscopy (ICP-OES) chọpụta ọnụọgụ nke anodic cations. Cations ndị nwere ike ịbanye ma ọ bụ gbasaa n'ime anode gụnyere Ti, Pt, Bi na K. Ewezuga K, cations ndị ọzọ niile dị n'okpuru oke nchọpụta. Ọdịdị ion dị na ngwọta ahụ na-ahapụ anode ka ọ jikọọ na protons ma ọ bụ cations ndị ọzọ. Ya mere, enwere ike ịgbakọ ịdị ọcha nke formic acid dị ka
Mmepụta Formate/FA na-anọchite anya ọnụọgụ FA e mepụtara kwa kWh nke ọkụ eletrik e ji otu nhazi MEA mee, na mol/kWh. A na-agbakọ ya dabere na njupụta ugbu a, voltaji sel na arụmọrụ Faraday n'okpuru ọnọdụ ọrụ akọwapụtara.
Gbakọọ ọnụọgụgụ formic acid e tinyere na anode dabere na nguzozi oke ahụ dum. Mmeghachi omume atọ na-asọmpi na-eme na kathode: evolushọn hydrogen, mbelata nke CO2 na CO, na mbelata nke CO2 na formic acid. N'ihi na anyị nwere usoro oxidation formic acid na Anton, enwere ike kewaa formic acid FE n'ime akụkụ abụọ: nchịkọta formic acid na oxidation formic acid. Enwere ike ide nhazi oke ahụ dum dị ka:
Anyị jiri GC tụọ ọnụọgụ formic acid, hydrogen, na CO nke HPLC chịkọtara. Ọ dị mkpa ịmara na e si na anode chịkọta ọtụtụ formic acid site na iji ntọala egosiri na Mgbakwunye Foto S5. Ọnụọgụ formate anakọtara na katod chamber adịghị obere, ihe dị ka nha abụọ pere mpe, ma ọ bụ ihe na-erughị 0.5% nke mkpokọta SC.
Ụdị njem na-aga n'ihu ejiri mee ihe ebe a dabere na ọrụ gara aga na sistemụ ndị yiri ya34. A na-eji usoro njikọ nke nha nha Poisson-Nerst-Planck (PNP) iji chọpụta mkpokọta mmiri na ikike electrostatic na usoro ndị na-eduzi eletrọnịkị na ionic. E nyere nkọwa zuru ezu nke nha nha na geometry nlereanya na SI.
Sistemụ a na-ekpebi mkpokọta ihe asatọ dị n'ime mmiri (\({{{{{\rm{C}}}}}}}}{{{{{\rm{O}}}}}}}_{2 \left ({{{{{\rm{aq}}}}}}\right)}\), \({{{{{{\rm{H}}}}}}}}^{+ }\ ), \ ({{{{{\rm{O}}}}}}}}{{{{\rm{H}}}}}}}^{-}\), \({{{ {{ \rm{ HCO}}}}}}}_{3}^{-}\), \({{{{{\rm{CO}}}}}}_{3}^{ 2-} \ ),\ ({{{{\rm{HCOOH}}}}}}}\), \({{{{{{\rm{HCOO}}}}}}}}^{- }\) na \({{{ {{\rm{K}}}}}}^{+}\)), ikike electrostatic na usoro ionic conduction (\({\phi }_{I}\ )) na conductivity electron anodic na cathodic. Ike electrostatic na usoro (\({\phi }_{A}\) na \({\phi }_{C}\) n'otu n'otu). Kama nke ahụ, a naghị emezu ọrụ nnọpụiche eletriki mpaghara ma ọ bụ nkesa chajị, a na-edozi mpaghara chajị oghere ozugbo site na iji nha nha Poisson; Ụzọ a na-enye anyị ohere ịmepụta mmetụta repulsion Donnan ozugbo na njikọ CEM|AEM, CEM|Pore, na AEM|Pore. Na mgbakwunye, a na-eji ozizi electrode porous (PET) akọwa njem chajị na oyi akwa anodic na cathodic nke ihe mkpali ahụ. Dịka ndị edemede si mara, ọrụ a na-anọchite anya ngwa mbụ nke PET na sistemụ nwere ọtụtụ mpaghara chajị oghere.
E jiri Zeiss Xradia 800 Ultra nwalee ihe nlele GDE BOT na EOT kathode yana isi iyi X-ray 8.0 keV, ụdị nnabata na ụdị ubi sara mbara, na njikọ onyonyo1. E chịkọtara onyonyo 901 site na -90° ruo 90° na oge mkpughe nke sekọnd 50. E mere nhazigharị site na iji nzacha projection azụ nwere nha voxel nke 64 nm. E mere nyocha nke nkewa na nkesa nha ihe site na iji koodu edere kpọmkwem.
Nkọwapụta microscope nke elektrọn gụnyere itinye MEA ule na epoxy resin iji kwadebe maka nhazi ultrathin na mma diamond. E bepụrụ akụkụ obe nke MEA ọ bụla ruo ọkpụrụkpụ nke 50 ruo 75 nm. Ejiri igwe microscope transmission Talos F200X transmission (Thermo Fisher Scientific) mee ihe maka inyocha igwe microscopy transmission transmission (STEM) na nha strength-dispersive X-ray spectroscopy (EDS). Igwe microscope ahụ nwere sistemụ EDS Super-X nwere ihe nchọpụta SDD anọ na-enweghị windo ma na-arụ ọrụ na 200 kV.
E nwetara usoro ntụgharị X-ray ntụ ntụ (PXRD) na ntụ Bruker Advance D8 X-ray diffractometer ya na radieshon Cu Kα Ni-filtered na-arụ ọrụ na 40 kV na 40 mA. Oke nyocha ahụ dị site na 10° ruo 60°, nha nzọụkwụ ahụ bụ 0.005°, ọsọ inweta data bụkwa 1 sekọnd kwa nzọụkwụ.
A tụrụ spectrum RAS dị n'ọnụ ọnụ Bi2O3 Bi L3 catalyst dịka ọrụ nke ike site na iji sel e ji aka rụọ. E ji 26.1 mg Bi2O3 gwakọtara ya na 156.3 μL ionomer solution (6.68%) kwadebe ink ionomer catalytic Bi2O3 ma jiri 1 M KOH, mmiri (157 μL) na isopropyl alcohol (104 μL) mee ka ọ dị n'otu iji nweta ink ionomer. Ọnụọgụ catalyst bụ 0.4. E tinyere ink ahụ na mpempe akwụkwọ graphene n'ebe akụkụ anọ (10 × 4 mm) ruo mgbe ibu catalyst Bi2O3 ruru 0.5 mg/cm2. E ji Kapton kpuchie mpempe akwụkwọ graphene ndị ọzọ iji kewapụ ebe ndị a site na electrolyte. E tinyere mpempe akwụkwọ graphene a kpuchiri catalyst n'etiti PTFE abụọ ma jiri skru kpuchie ya na ahụ sel (PEEK), Foto S8. Hg/HgO (1 M NaOH) jere ozi dị ka elektrọd ntụaka, a na-ejikwa akwụkwọ carbon arụ ọrụ dị ka elektrọd counter. E jiri waya platinum nke e tinyere na hydrogen nke jupụtara na 0.1 M KOH mee ka elektrọd ntụaka Hg/HgO gbanwee ikike niile a tụrụ ka ọ bụrụ nha hydrogen electrode (RHE) a na-agbanwe agbanwe. E nwetara spectra XRD site na ileba anya na ike nke elektrọd na-arụ ọrụ mpempe akwụkwọ Bi2O3/graphene nke e tinyere na 0.1 M KOH, nke a na-ekpo ọkụ ruo 30 °C. Elektrọd ahụ na-agagharị na batrị ahụ, ya na ntinye elektrọd dị n'ala sel ahụ na ebe a na-esi na ya pụta iji hụ na elektrọd ahụ na-akpakọrịta na oyi akwa catalyst mgbe afụfụ na-etolite. E jiri CH Instruments 760e potentiostat chịkwaa ike elektrọd na-arụ ọrụ. Usoro ike bụ ike sekit mepere emepe: -100, -200, -300, -400, -500, -800, -850, -900, -1000, -1100, -1500 na +700 mV dabere na RHE. A gbanweela ikike iR niile.
E mere X-ray absorption fine structure (XAFS) spectroscopy na channel 10-ID, Advanced Photon Source (APS), Argonne National Fluorescence Laboratory. National Model Measurement Laboratory. E jiri monochromator Si(111) abụọ nke ejiri nitrogen mmiri mee ka ike X-ray dị jụụ, e jikwa enyo rhodium kpuchie mee ka ọdịnaya harmonic dị ntakịrị. E nwere ike ịgbanwe ike nyocha site na 13200 ruo 14400 eV, a tụrụkwa fluorescence site na iji usoro diode silicon PIN 5 × 5 na-enweghị nzacha ma ọ bụ obere Soller. A na-ahazi ike ngafe efu nke ihe nke abụọ na 13271.90 eV site na nsọtụ L2 nke Pt foil. N'ihi ọkpụrụkpụ nke sel electrochemical, ọ gaghị ekwe omume ịtụ spectrum nke ọkọlọtọ ntụaka n'otu oge. Ya mere, mgbanwe nyocha-na-scan nke agbakọrọ na ike X-ray nke ihe merenụ bụ ±0.015 eV dabere na nha ugboro ugboro n'oge nnwale ahụ. Ọkpụrụkpụ nke oyi akwa Bi2O3 na-eduga na ụfọdụ oke nke ịmịkọrọ onwe ya nke fluorescence; elektrọd ndị ahụ na-enwe nhazi kwụ ọtọ ma e jiri ya tụnyere ihe merenụ na ihe nchọpụta, na-eme ka nyocha niile yie otu. Ejiri ụdị XAFS dị nso chọpụta ọnọdụ oxidation na ụdị kemịkalụ nke bismuth site na iji ya tụnyere mpaghara XANES nke ọkọlọtọ Bi na Bi2O3 site na iji algọridim njikọ linear nke ngwanrọ Athena (ụdị 0.9.26). site na koodu IFEFFIT 44.
A na-enweta data ndị na-akwado ọnụọgụgụ dị n'isiokwu a na mmechi ndị ọzọ nke ọmụmụ a site n'aka onye dere ya ma ọ bụrụ na ọ rịọ ya nke ọma.
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