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Elektrokemikal ni akɛjieɔ kɔɔyɔɔ ni ji carbon dioxide lɛ shi kɛyaa formic acid mli lɛ ji gbɛ ni hi jogbaŋŋ ni atsɔɔ nɔ ahaa kɔɔyɔɔ ni ji carbon dioxide lɛ tsuɔ nii jogbaŋŋ ni eyɛ nitsumɔi ni baanyɛ aba akɛ hydrogen ni akɛtoɔ. Yɛ nitsumɔ nɛɛ mli lɛ, afee tsɔne ko ni haa tsɔne ni haa hulu kpɛɔ lɛ feɔ tsɔne ni akɛfeɔ formic acid kɛjɛɔ carbon dioxide mli lɛ. Nɔ ni he hiaa waa yɛ ŋaalee mli hiɛyaa mli ji tsɔne ni akɛtsakeɔ tsɔne ni akɛwoɔ tsɔne mli lɛ mli, ni kɛ akɛtsu nii yɛ tsɔne ni akɛwoɔ tsɔne mli lɛ mli lɛ, ehaa formic acid ni afee yɛ tsɔne lɛ teŋ lɛ tsɔɔ anodic flow field lɛ mli yɛ 0.25 M mli. nibii kɛ gbɛjianɔtoi ni afɔɔ namɔ yɛ fuel cells kɛ hydrogen electrolysis mli, ni haa anyɛɔ atsakeɔ oya kɛyaa ŋwɛi ŋta kɛ jarayeli mli. Yɛ 25 cm2 mli lɛ, tsɔne ni akɛtsakeɔ nibii ni yɔɔ mli lɛ haa >75% Faraday nitsumɔ kɛha formic acid yɛ <2 V kɛ 300 mA/cm2. Nɔ ni he hiaa fe fɛɛ lɛ, ŋmɛlɛtswai 55 mli shidaamɔ he kaa ni afeɔ yɛ 200 mA/cm2 lɛ tsɔɔ Faraday nitsumɔ ni yɔɔ shiŋŋ kɛ tsɔne ni haa wala yibii lɛ mli la lɛ. Akɛ tɛkno-shika helɛtemɔ mlipɛimɔ tsuɔ nii kɛtsɔɔ gbɛi ni atsɔɔ nɔ anáa shika ni kɛ formic acid feemɔ gbɛi ni yɔɔ amrɔ nɛɛ yeɔ egbɔ.
Atsɔɔ akɛ, kɛ́ akɛ srawa hewalɛ ni anyɛɔ atsakeɔ lɛ tsuɔ nii kɛjieɔ kɔɔyɔɔ ni ji carbon dioxide lɛ shi kɛyaa formic acid nɔ lɛ, ebaa nibii ni afeɔ lɛ ahe nyɔmɔwoo shi kɛyashɛɔ 75%1 kɛ akɛto blema gbɛi ni akɛ sũ mli tsofa tsuɔ nii yɛ mli lɛ ahe. Taakɛ atsɔɔ yɛ woji amli2,3 lɛ, formic acid yɛ nitsumɔi srɔtoi babaoo, kɛjɛ gbɛ ni hi jogbaŋŋ ni shika helɛtemɔ he ehiaaa ni akɛtoɔ hydrogen kɛyaa niyenii ni akɛtsuɔ tsofafeemɔ nitsumɔhe4,5 loo biomass nitsumɔhe6 lɛ nɔ. Ayɔse Formic acid po akɛ niyenii ni akɛtsakeɔ kɛyaa jet fuel ni yaa nɔ daa kɛtsɔ metabolic engineering nɔ7,8. Kɛ formic acid shika helɛtemɔ he nilee 1,9 lɛ, niiamlitaomɔ nitsumɔi babaoo ekɛ amɛjwɛŋmɔ ema nɔ ni haa nɔ ko yaa hiɛ lɛ nɔ 10,11,12,13,14,15,16. Shi kɛlɛ, mɔdɛŋbɔɔ babaoo yaa nɔ ekɛ amɛjwɛŋmɔ maa H-cells bibii loo nu ni hoɔ ni tsuɔ nii yɛ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛlɛtswaa ni baa shi (<50 mA/cm2) lɛ nɔ. Kɛji akɛ abaashɛ shika nɔ, ni anyɛ atsu jarayeli he nii ni aha jarayeli mlibotemɔ ni nyiɛ sɛɛ lɛ aya hiɛ lɛ, esa akɛ afee electrochemical carbon dioxide shibaa (CO2R) yɛ ŋmɛnɛŋmɛnɛ beaŋ densities ni nɔ kwɔ (≥200 mA/cm2) kɛ Faraday cell efficiency (FE)17 yɛ be mli ni akɛ nibii ni akɛtsuɔ nii babaoo kɛ electrochecal wallow fuel nibii ni jɛ CO2 mli lɛ tsuɔ nii. nibii ni akɛbaatsu nii koni akɛná shika helɛtemɔ he sɛɛ18. Kɛfata he lɛ, koni nibii ni afeɔ lɛ aya hiɛ ni ajie nibii krokomɛi ni fata he lɛ, esa akɛ akɛ formic acid atsu nii akɛ naagbee nibii moŋ fe formate salts19.
Yɛ gbɛ nɛɛ nɔ lɛ, abɔ mɔdɛŋ nyɛsɛɛ nɛɛ koni afee CO2R formate/formic acid ni damɔ kɔɔyɔɔ ni gbɛɔ eshwaa (GDE) nibii ni he hiaa nitsumɔhei lɛ anɔ. Nibii amlipɛimɔ ni mli kwɔ ni Fernandez-Caso kɛ ekrokomɛi fee lɛ gbala tsɔne ni akɛtsuɔ nii yɛ tsɔne mli lɛ fɛɛ mli kuku kɛha CO2 ni baa shi kɛyaa formic acid/formate nɔ lɛ. Yɛ fɛɛ mli lɛ, abaanyɛ aja gbɛjianɔtoi fɛɛ ni yɔɔ lɛ amli awo kui titrii etɛ mli: 1. Katolits ni hoɔ kɛtsɔɔ mli lɛ19,21,22,23,24,25,26,27, 2. Mɔ kome (kation tsakemɔ mli (CEM.)28 loo anion tsakemɔ mli (AEM)29 kɛ 3. 1a lɛ mli lɛ, abɔ electrolyte tsu ko yɛ membrane lɛ kɛ GDE lɛ katod lɛ teŋ, ni akɛfee ion gbɛi yɛ katod layer ni ji catalyst lɛ nɔkwɛmɔ he lɛ mli, eyɛ mli akɛ i4 1.27 mm katolite ŋtayaa ni mli tse lɛ nɔ lɛ, aná 90% FE 35 yɛ 500 mA/cm2 nɔ. energy efficiency of 15%. To improve energy efficiency, Li et al., using a single CEM configuration, achieved an FE 29 of 93.3% at a fractional current density of 51.7 mA/cm2. Diaz-Sainz et al.28 used a filter press with a single CEM membrane at a current density of 45 mA/cm2. Shi kɛlɛ, gbɛi fɛɛ ni atsɔɔ nɔ afeɔ formate lɛ fe nɔ ni asumɔɔ lɛ, formic acid Kɛfata nitsumɔ he taomɔ nii krokomɛi ahe lɛ, yɛ CEM gbɛjianɔtoi amli lɛ, formats tamɔ KCOOH baanyɛ abua amɛhe naa oya yɛ GDE kɛ flow field lɛ mli, ni ekɛ gbɛfaa mli naatsii baa kɛ naagbee lɛ, cell lɛ fitemɔ.
CO2R kɛ formate/formic acid tsakemɔ tsɔnei etɛ ni he gbɛi fe fɛɛ lɛ atomɔ kɛ tsumaa he gbɛjianɔtoo ni atsɔɔ yɛ nikasemɔ nɛɛ mli lɛ. b Nɔ ni akɛtoɔ ŋmɛnɛŋmɛnɛ beaŋ fɛɛ kɛ formate/formic acid yibiiwoo he kɛha catholyte gbɛjianɔtoi, sandwich gbɛjianɔtoi, CEM gbɛjianɔtoo kome ni yɔɔ woji amli (ni atsɔɔ yɛ Supplementary Table S1) kɛ wɔ nitsumɔ lɛ. Okadii ni agbele naa lɛ tsɔɔ akɛ afee formate solution, ni okadii ni wa tsɔɔ akɛ afee formic acid. *Atsɔɔ gbɛjianɔtoo ni akɛ hydrogen tsuɔ nii yɛ anode lɛ nɔ. c Zero-gap MEA gbɛjianɔtoo ni akɛ bipolar membrane ni yɔɔ ŋwɛi ŋta ni tsuɔ nii yɛ hiɛyaa gbɛ nɔ lɛ tsuɔ nii.
Bɔni afee ni atsĩ formate feemɔ naa lɛ, Proietto kɛ ekrokomɛi. 32 kɛ filta press ni mli ejaaa ni nu ni mli ewo muji lɛ hoɔ kɛtsɔɔ ŋwɛi ŋta lɛ mli lɛ tsu nii. Gbɛjianɔtoo lɛ baanyɛ ashɛ >70% CE yɛ ŋmɛnɛŋmɛnɛ 50–80 mA/cm2 mli. Nakai nɔŋŋ hu, Yang kɛ ekrokomɛi. 14 Ewo ŋaa akɛ akɛ electrolyte ni mli wa ni yɔɔ CEM kɛ AEM teŋ lɛ atsu nii koni akɛwo formic acid lɛ feemɔ he hewalɛ. 31,36 91.3% FE yɛ 5 cm2 tsɛŋemɔ hela mli yɛ 200 mA/cm2, ni ekɛ 6.35 wt% fɔmik acid mli nu lɛ ba. Xia kɛ ekrokomɛi. Kɛtsɔ gbɛjianɔtoo ni tamɔ nakai nɔŋŋ nɔ lɛ, aná 83% tsakemɔ ni ji carbon dioxide (CO2) kɛtee formic acid FE mli yɛ 200 mA/cm2, ni aka gbɛjianɔtoo lɛ shihilɛ ni sɛɛ tsɛɔ lɛ akwɛ ŋmɛlɛtswai 100 kɛ minitii 30. Eyɛ mli akɛ nɔ ni jɛɔ mli baa lɛ ji shiwoo moŋ, shi shika ni yaa hiɛ kɛ bɔ ni porous ion exchange resins lɛ mli wa ha lɛ haa ewaa akɛ aaasusu interlayer gbɛjianɔtoi lɛ ahe kɛya gbɛjianɔtoi wuji amli (tamɔ, 1000 cm2).
Kɛha nɔ ni jɛɔ tsɔnei srɔtoi lɛ amli baa lɛ he mfonirifeemɔ lɛ, wɔkɛ formate/formic acid ni ajieɔ lɛ kpo yɛ kWh kome mli lɛ to gbɛjianɔtoi fɛɛ ni atsĩ tã kɛtsɔ hiɛ lɛ ahe gbɛjianɔ ni wɔkɛto mfoniri 1b lɛ he. Eyɛ faŋŋ yɛ biɛ akɛ gbɛjianɔtoo fɛɛ gbɛjianɔtoo ni catholyte loo interlayer yɔɔ mli lɛ baashɛ enitsumɔ he yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei ni baa shi lɛ amli ni ebaafite yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei ni fa babaoo lɛ amli, he ni ohmic husu lɛ baanyɛ atsɔɔ tsɔne lɛ mli tsɔne lɛ mli la lɛ. Kɛfata he lɛ, eyɛ mli akɛ CEM gbɛjianɔtoo ni tsuɔ nii jogbaŋŋ lɛ haa molar formic acid ni fa fe fɛɛ yɛ kWh mli moŋ, shi ŋmei ni abua naa lɛ baanyɛ aha nitsumɔ lɛ afite oya yɛ ŋmɛnɛŋmɛnɛ beaŋ densities ni fa babaoo mli.
Kɛha sɛɛnamɔi ni awie he tsutsu lɛ ahe nitsumɔ lɛ, wɔfee membrane electrode assembly (MEA) ni BPM ni yɔɔ hiɛ ni tsɔɔ hiɛ ni akɛ membrane ni akɛtsakeɔ tsɔne (PCEM) ni yɔɔ mli lɛ yɔɔ mli lɛ. Atsɔɔ tsu lɛ he gbɛjianɔtoo lɛ yɛ mfoniri 1c lɛ mli. Akɛ hydrogen (H2) woɔ anode lɛ mli koni ekɛ protons aba kɛtsɔ hydrogen oksideshin nifeemɔ (HOR) nɔ. Akɛ PCEM fã ko woɔ BPM gbɛjianɔtoo lɛ mli koni eha formate ions ni jɛɔ cathode lɛ mli lɛ atsɔ AEM lɛ mli, ni ekɛ protons lɛ afee ekome ni efee formic acid yɛ BPM lɛ teŋgbɛ kɛ CEM lɛ teŋgbɛ ŋmeii lɛ amli, ni no sɛɛ lɛ eje kpo kɛtsɔ GDE anode kɛ flow field lɛ nɔ. . Kɛtsɔ gbɛjianɔtoo nɛɛ nɔ lɛ, wɔnine shɛ >75% FE ni ji formic acid nɔ yɛ <2 V kɛ 300 mA/cm2 kɛha 25 cm2 tsɛŋemɔ hela ko. Nɔ ni he hiaa fe fɛɛ lɛ, gbɛjianɔtoo lɛ kɛ nibii ni yɔɔ jarayeli mli kɛ hardware tsumaa he ŋaa kɛha fuel cell kɛ nu mli electrolysis nitsumɔhei tsuɔ nii, ni ehaa be ni akɛtsuɔ nii oya lɛ yaa hiɛ. Catholyte gbɛjianɔtoi lɛ yɛ catholyte flow chambers ni baanyɛ aha nɔnyɛɛ ni kɛ gas kɛ nu mli nibii lɛ ateŋ lɛ akafee ekome, titri lɛ yɛ cell gbɛjianɔtoi wuji amli. Kɛha sandwich tsɔnei ni nu ni hoɔ yɛ mli lɛ mli ŋmeii lɛ, ehe miihia ni abɔ mɔdɛŋ waa koni afee ŋmeii ni yɔɔ teŋgbɛ lɛ jogbaŋŋ koni akɛba nɔnyɛɛ ni baa shi kɛ kɔɔyɔɔ ni ji carbon dioxide ni buaa ehe naa yɛ teŋgbɛ ŋmeii lɛ amli lɛ shi. Enɛɛmɛi enyɔ lɛ fɛɛ baanyɛ aha tsɔne ni akɛtswaa adafitswaa lɛ mli agbala. Ewa hu akɛ aaafee ŋmeii bibii ni damɔ shi amɛ diɛŋtsɛ amɛhe lɛ yɛ gbɛ ni da nɔ. Nɔ ni tamɔɔɔ enɛ lɛ, gbɛjianɔtoo hee ni atsɔɔ lɛ ji zero-gap MEA gbɛjianɔtoo ni bɛ flow chamber loo layer ni yɔɔ teŋgbɛ. Kɛ akɛto electrochemical cells krokomɛi ni yɔɔ lɛ ahe lɛ, gbɛjianɔtoo ni atsɔɔ lɛ yɛ srɔto yɛ gbɛ ni ji akɛ, ehaa anyɛɔ afee formic acid tɛ̃ɛ yɛ gbɛ ni anyɛɔ akwɛɔ nɔ, hewalɛ ni tsuɔ nii jogbaŋŋ, ni nɔ ko nɔ ko bɛ mli.
Kɛha hydrogen sutsakemɔ ni tsiɔ naa lɛ, mɔdɛŋbɔɔ ni da ni akɛbaa CO2 shi lɛ kɛ MEA kɛ AEM membrane gbɛjianɔtoi ni akɛ electrolytes ni fa babaoo ni yɔɔ molar mli lɛ ebɔ he (tamɔ, 1-10 M KOH) koni ekɛfee alkaline shihilɛi yɛ cathode lɛ nɔ (tamɔ bɔ ni atsɔɔ yɛ mfoniri 2a lɛ mli lɛ). Yɛ nɛkɛ gbɛjianɔtoi nɛɛ amli lɛ, formate ions ni afee yɛ cathode lɛ mli lɛ tsɔɔ membrane lɛ mli akɛ charge ni ehiii, no sɛɛ lɛ KCOOH feɔ ni ejɛɔ gbɛjianɔtoo lɛ mli kɛtsɔɔ anodic KOH stream lɛ nɔ. Eyɛ mli akɛ formate FE kɛ cell voltage lɛ hi shishijee mli taakɛ atsɔɔ yɛ mfoniri 2b lɛ mli lɛ moŋ, shi shifimɔ kaa lɛ ha FE lɛ nɔ ba shi aaafee 30% yɛ ŋmɛlɛtswai 10 pɛ mli (Mfoniri S1a–c). Esa akɛ akadi akɛ 1 M KOH anolyte ni akɛtsuɔ nii lɛ he hiaa waa koni akɛba anodic voltage ni fe nine yɛ alkaline oxygen sutsakemɔ hetoo (OER) gbɛjianɔtoi amli37 ni anyɛ ana ion nine shɛɔ nɔ yɛ cathode catalyst saatso lɛ mli33. Kɛji akɛ anolyte lɛ mli nibii ni yɔɔ mli lɛ ba shi kɛyashɛ 0.1 M KOH lɛ, tsɛŋemɔ hela lɛ mli hewalɛ kɛ formic acid oksideshin (formic acid ni laajeɔ) lɛ fɛɛ yaa hiɛ (Mfoniri S1d), ni tsɔɔ bɔ ni zero-sum jarayeli lɛ ji. Akɛ mass balance lɛ fɛɛ tsu nii kɛkwɛ bɔ ni formate oxidation lɛ yaa hiɛ ehaa lɛ mli; kɛha saji krokomɛi lɛ, kwɛmɔ “Gbɛi” lɛ fã lɛ. Akɛ MEA kɛ CEM membrane configurations kome tsuɔ nii kɛtsɔɔ nitsumɔ lɛ hu he nii, ni atsɔɔ nɔ ni jɛ mli ba lɛ yɛ mfoniri S1f,g lɛ mli. FE formate ni abua naa kɛjɛɔ katod lɛ mli lɛ ji >60% yɛ 200 mA/cm2 yɛ kaa lɛ shishijee mli, shi efite oya yɛ ŋmɛlɛtswai enyɔ mli yɛ katod ŋmei ni abua naa ni awie he kɛtsɔ hiɛ lɛ hewɔ (Mfoniri S11).
MEA ni bɛ nɔ ko nɔ ko kɛ CO2R yɛ katod lɛ nɔ, hydrogen oksideshin nifeemɔ (HOR) loo OER yɛ anode lɛ nɔ, kɛ AEM membrane kome ni yɔɔ teŋ lɛ he mfoniri. b FE kɛ cell voltage kɛha nɛkɛ gbɛjianɔtoo nɛɛ kɛ 1 M KOH kɛ OER ni hoɔ yɛ anode lɛ nɔ. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔ ni yɔɔ susumɔi srɔtoi etɛ mli. yɛ FE kɛ gbɛjianɔtoo lɛ mli tsɔne ni haa H2 kɛ HOR yɔɔ anode lɛ nɔ lɛ. Akɛ sui srɔtoi tsuɔ nii koni akɛyoo srɔtofeemɔ ni yɔɔ formate kɛ formic acid ni afeɔ lɛ teŋ. d MEA he mfoniri ni BPM tsake kɛtee hiɛ yɛ teŋgbɛ. FE kɛ batri mli hewalɛ kɛ be ni yɔɔ 200 mA/cm2 kɛtsɔ gbɛjianɔtoo nɛɛ nɔ. f Mfoniri ni tsɔɔ hiɛ-kɛ-sɛɛ BPM MEA yɛ kaa kuku ko sɛɛ.
Bɔni afee ni afee formic acid lɛ, akɛ hydrogen haa Pt-on-carbon (Pt/C) ni haa tsɔne lɛ tsuɔ nii yɛ anode lɛ mli lɛ. Taakɛ atsɔɔ yɛ mfoniri 2d lɛ mli lɛ, akwɛ BPM ni yaa hiɛ ni jieɔ protons yɛ anode lɛ mli lɛ mli momo koni anyɛ ana formic acid feemɔ. BPM tuning unit lɛ fite yɛ minitii 40 ni etsu nii yɛ 200 mA/cm2 mli lɛ sɛɛ, ni voltage ni fa fe 5 V fata he (Mfoniri 2e). Yɛ kaa lɛ sɛɛ lɛ, ana delamination ni yɔɔ faŋŋ yɛ CEM/AEM lɛ teŋgbɛ. Kɛfata formate he lɛ, anions tamɔ carbonate, bicarbonate kɛ hydroxide hu baanyɛ atsɔ AEM membrane lɛ mli ni amɛkɛ protons ni yɔɔ CEM/AEM teŋgbɛ lɛ afee ekome ni amɛfee CO2 gas kɛ nu ni ji nu, ni no kɛ BPM shwiemɔ baa (Mfoniri 2f) kɛ , yɛ naagbee lɛ, ekɛ tsɛŋemɔ hela lɛ fiteɔ.
Kɛjɛ nitsumɔ kɛ shigbeemɔ gbɛjianɔtoi ni yɔɔ ŋwɛi gbɛjianɔtoo lɛ mli lɛ nɔ lɛ, atsɔɔ MEA tsumaa he gbɛjianɔtoo hee ko mli taakɛ atsɔɔ yɛ mfoniri 1c lɛ mli lɛ, ni atsɔɔ mli fitsofitso yɛ mfoniri 3a38 lɛ mli. Yɛ biɛ lɛ, PCEM fã lɛ haa gbɛ kɛhaa formic acid kɛ anions lɛ fãmɔ kɛjɛɔ CEM/AEM fã lɛ mli, ni no haa nɔ ni abua naa lɛ baa shi. Yɛ nakai beaŋ nɔŋŋ lɛ, PCEM teŋgbɛ gbɛ lɛ kudɔɔ formic acid kɛyaa diffusion medium kɛ flow field lɛ mli, ni ehaa formic acid oxidation ni baanyɛ aba lɛ baa shi. Atsɔɔ nɔ ni jɛɔ polarization mli baa kɛtsɔ AEMs ni 80, 40 kɛ 25 mm yɔɔ mli lɛ nɔ yɛ mfoniri 3b lɛ mli. Taakɛ akpaa gbɛ lɛ, eyɛ mli akɛ tsɔne lɛ mli hewalɛ fɛɛ yaa hiɛ kɛ AEM lɛ mli tsɔne lɛ yaa hiɛ moŋ, shi AEM ni mli wa lɛ ni akɛtsuɔ nii lɛ tsiɔ formic acid lɛ sɛɛgbɛ gbɛfaŋnɔ naa, ni no haa cathode pH lɛ yaa hiɛ ni ehaa H2 lɛ baa shi (Mfoniri 3c–e).
a Nɔkwɛmɔnɔ ni tsɔɔ MEA gbɛjianɔtoo kɛ AEM kɛ CEM ni atswa kɛ formic acid gbɛfaa gbɛi srɔtoi. b Cell voltage yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei srɔtoi kɛ AEM tsɔnei srɔtoi. yɛ EE mli yɛ ŋmɛnɛŋmɛnɛ beaŋ ŋmɔlɔi srɔtoi ni AEM ŋmɔlɔ ji 80 μm (d) 40 μm, e) 25 μm. Tɔmɔ bars damɔ shi kɛha sɛɛkuu ni asusu kɛjɛ nɔkwɛmɔnii sɔrɔtoi etɛ mli. f Nɔ ni jɛɔ mli baa ji formic acid mlibotemɔ kɛ pH sɛɛnamɔ yɛ CEM/AEM teŋgbɛ yɛ AEM ŋmɔlɔi srɔtoi amli. f PC kɛ pH yɛ katod layer ni yɔɔ katalis lɛ mli lɛ mli kɛ AEM sini mli ŋmɔlɔi srɔtoi. g Formic acid mli nibii ni yɔɔ mli lɛ mlijaa enyɔ kɛ CEM/AEM sɛɛkpeemɔ kɛ ŋmei.
Mfoniri S2 tsɔɔ bɔ ni formic acid mlibotemɔ kɛ pH mlijaa yɛ MEA ŋmɔlɔ mli kɛtsɔ Poisson-Nernst-Planck nibii ni bɛ naagbee lɛ ahe mfonirifeemɔ nɔ. Ebɛ naakpɛɛ akɛ anaa formic acid ni fa fe fɛɛ, ni ji 0.23 mol/L lɛ yɛ CEM/AEM sɛɛgbɛ, ejaakɛ formic acid lɛ ji nɔ ni afeɔ yɛ sɛɛgbɛ nɛɛ. Formic acid ni yɔɔ AEM lɛ mli lɛ baa shi oya be mli ni AEM lɛ mli tsɔi lɛ yaa hiɛ lɛ, ni tsɔɔ akɛ shitee-kɛ-woo ni da kɛha mass transfer kɛ formic acid ni hoɔ fioo yɛ sɛɛgbɛ gbɛfaŋ lɛ hewɔ. f kɛ g tsɔɔ pH kɛ formic acid sɛɛnamɔi ni yɔɔ cathode catalyst saatso lɛ mli ni sɛɛgbɛ shweremɔ kɛ formic acid mlibotemɔ ni yɔɔ fãi enyɔ mli lɛ mlijaa kɛbaa lɛ, yɛ gbɛ kome nɔ. Babaoo ni AEM membrane lɛ mli shwieɔ shi lɛ, babaoo ni formic acid ni yɔɔ katod lɛ masɛi lɛ fa babaoo, ni katod lɛ pH lɛ bafeɔ acidic. No hewɔ lɛ, eyɛ mli akɛ AEM membranes ni mli wa lɛ haa ohmic laajemɔi babaoo baa moŋ, shi amɛhe hiaa waa koni atsĩ formic acid lɛ sɛɛ gbɛ kɛya cathode lɛ naa ni aha FE formic acid gbɛjianɔtoo lɛ hetsemɔ ni nɔ kwɔ lɛ aya hiɛ. Yɛ naagbee lɛ, AEM ŋmɔlɔ ni yaa hiɛ kɛyashɛɔ 80 μm lɛ ha FE >75% kɛha formic acid yɛ <2 V kɛ 300 mA/cm2 kɛha 25 cm2 ŋmɔlɔ kpokpaa.
Bɔni afee ni aka bɔ ni nɛkɛ PECM-based tsumaa nɛɛ damɔ shi shiŋŋ ehaa lɛ, akwɛ batri lɛ mli la lɛ nɔ yɛ 200 mA/cm2 ŋmɛlɛtswai 55 sɔŋŋ. Atsɔɔ nɔ ni jɛ mli ba lɛ fɛɛ yɛ mfoniri 4 lɛ mli, ni nɔ ni jɛ mli ba kɛjɛ klɛŋklɛŋ ŋmɛlɛtswai 3 lɛ mli lɛ ji nɔ ni ajie lɛ kpo yɛ mfoniri S3 lɛ mli. Kɛ akɛ Pt/C anodic catalyst lɛ tsu nii lɛ, tsɛŋemɔ hela lɛ mli la lɛ tee hiɛ waa yɛ klɛŋklɛŋ minitii 30 lɛ mli (Mfoniri S3a). Yɛ be kakadaŋŋ mli lɛ, tsɔne ni haa tsɛŋemɔ hela lɛ mli la lɛ tee nɔ ehi shi nɔ ni miihe ashɛ nɔ ni yaa nɔ daa lɛ, ni ekɛ 0.6 mV/h ni fiteɔ nii lɛ haa (Mfoniri 4a). Yɛ kaa lɛ shishijee mli lɛ, PV ni ji formic acid ni abua naa yɛ anode lɛ nɔ lɛ ji 76.5% ni PV ni ji hydrogen ni abua naa yɛ cathode lɛ nɔ lɛ ji 19.2%. Yɛ klɛŋklɛŋ ŋmɛlɛtswaa ni akɛka lɛ sɛɛ lɛ, hydrogen FE lɛ ba shi kɛyashɛ 13.8%, ni tsɔɔ akɛ formate halamɔ etee hiɛ. Shi, ŋmɛlɛtswaa kome mli lɛ, tsɔne ni haa hulu tsoɔ ni ji 62.7% lɛ tee hiɛ kɛjɛ nɔ ni miihe ashɛ zero yɛ kaa lɛ shishijee mli kɛtee 17.0%. No sɛɛ lɛ, FE ni ji H2, CO, formic acid kɛ bɔ ni anodic oxidation ni ji formic acid lɛ yaa nɔ ehaa lɛ tee nɔ ehi shi yɛ kaa lɛ mli. Ekolɛ, formic acid oxidation ni yaa hiɛ yɛ klɛŋklɛŋ ŋmɛlɛtswaa lɛ mli lɛ baanyɛ ajɛ formic acid ni abua naa yɛ PCEM/AEM sɛɛgbɛ lɛ hewɔ. Beni formic acid lɛ mli nibii ni yɔɔ mli lɛ yaa hiɛ lɛ, jeee akɛ ejɛɔ tsɔne lɛ mli ŋmeii lɛ amli kɛkɛ, shi moŋ egbɛɔ eshwaa kɛtsɔɔ FEM lɛ diɛŋtsɛ mli ni eboteɔ Pt/C anode layer lɛ mli. Akɛni formic acid ji nu ni yɔɔ 60°C hewɔ lɛ, enaabuamɔ baanyɛ ekɛ naagbai aba ni ekɛ oksideshin ni hi fe hydrogen aba.
a Hewalɛ ni yɔɔ tsɔne lɛ mli lɛ kɛ be (200 mA/cm2, 60 °C). Nɔ ni akɛwo mli lɛ tsɔɔ optical microscope mfoniri ni tsɔɔ MEA ni EM ni mli efo mli lɛ fã ko ni afo mli. Skel bar: 300 μm. b PE kɛ formic acid he tsemɔ akɛ be nitsumɔ yɛ 200 mA/cm2 ni akɛ Pt/C anode tsuɔ nii.
Akɛ nano-X-ray computed tomography (nano-CT) tsu nii kɛtsɔɔ bɔ ni nɔkwɛmɔnii lɛ yɔɔ ha yɛ kaa lɛ shishijee mli (BOT) yɛ hesaamɔ be mli kɛ kaa lɛ naagbee (EOT) yɛ ŋmɛlɛtswai 55 ni akɛkaa shifimɔ lɛ sɛɛ, taakɛ atsɔɔ yɛ mfoniri 5 a lɛ mli lɛ. EOT nɔkwɛmɔnɔ lɛ yɛ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ dalɛ ni da ni elɛɛmɔ ji 1207 nm kɛ akɛto 930 nm he kɛha BOT. Atsɔɔ mfoniri ni yɔɔ ŋwɛigbɛ ni yɔɔ duŋ mli ni akɛkwɛɔ nibii bibii ni yɔɔ ŋwɛigbɛ (HAADF-STEM) kɛ hewalɛ ni gbɛɔ eshwaa X-ray spectroscopy (EDS) lɛ mli hetooi yɛ mfoniri 5b lɛ mli. Yɛ be mli ni BOT tsɔne lɛ mli tsɔne lɛ mli nibii bibii lɛ ateŋ babaoo kɛ agbɛnɛ hu agglomerates wuji komɛi yɔɔ mli lɛ, yɛ EOT fã lɛ mli lɛ, abaanyɛ aja tsɔne lɛ mli awo kpokpai sɔrɔtoi enyɔ mli: eko yɛ tsɔne mli nibii bibii ni wa ni sa kadimɔ waa, ni ekroko lɛ hu yɛ kpokpai ni yɔɔ ŋmeii babaoo. Nibii bibii ni yɔɔ mli lɛ ayibɔ. EDS mfoniri lɛ tsɔɔ akɛ, nibii bibii wuji ni wa lɛ amli eyi obɔ kɛ Bi, ekolɛ dade Bi, ni hei ni ŋmeii yɔɔ lɛ hu yɛ kɔɔyɔɔ ni haa wala yibii lɛ fa babaoo. Kɛji akɛ tsɔne lɛ tsu nii yɛ 200 mA/cm2 lɛ, hewalɛ ni ehiii ni yɔɔ katod lɛ mli lɛ baaha Bi2O3 lɛ aba shi, taakɛ in situ X-ray absorption spectroscopy hetooi ni awie he yɛ shishigbɛ nɛɛ yeɔ he odase lɛ. HAADF-STEM kɛ EDS mapping hetooi lɛ tsɔɔ akɛ Bi2O3 tsɔɔ shigbeemɔ gbɛjianɔtoo ko mli, ni no haa amɛfiteɔ kɔɔyɔɔ ni haa wala lɛ ni amɛbua amɛhe naa amɛfeɔ dade bibii wuji. X-ray diffraction patterns ni yɔɔ BOT kɛ EOT katod lɛ mli lɛ maa EDS saji lɛ ashishitsɔɔmɔ lɛ nɔ mi (Mfoniri 5c): kristalo Bi2O3 pɛ ji nɔ ni ana yɛ BOT katod lɛ mli, ni ana kristalo bimetal yɛ EOT katod lɛ mli. Kɛha bɔ ni katod hewalɛ tsuɔ nii ehaa yɛ Bi2O3 katod katalis lɛ oksideshin shihilɛ lɛ shishi lɛ, atsake hulutsoo lɛ kɛjɛ kpokpaa nɔ hewalɛ ni agbele naa (+0.3 V vs RHE) kɛyashi -1.5 V (vs RHE). Ana akɛ Bi2O3 fa lɛ jeɔ shishi ebaa shi yɛ -0.85 V kɛ akɛto RHE he, ni line yɛŋ lɛ mli hewalɛ ni baa shi yɛ spectrum lɛ naa lɛ tsɔɔ akɛ dade Bi baa shi kɛyashɛɔ 90% yɛ RHE mli yɛ -1.1. V kɛ RHE (Mfoniri 5d). Ekɔɔɔ he eko gbɛ ni atsɔɔ nɔ atsuɔ he nii lɛ, formate ni yɔɔ katod lɛ mli lɛ fɛɛ tsakeee, taakɛ atsɔɔ kɛjɛɔ H2 kɛ CO FE kɛ formic acid feemɔ mli lɛ, yɛ tsakemɔi ni he hiaa yɛ katod lɛ mli, nɔ ni haa oksideshin shihilɛ, kɛ mikrokristalin gbɛjianɔtoo lɛ fɛɛ sɛɛ.
a Nibii ni haa mɔ tsui nyɔɔ emli lɛ ahe gbɛjianɔtoo ni yɔɔ fãi etɛ kɛ nibii ni haa mɔ tsui nyɔɔ emli lɛ amli nibii ni anáa kɛtsɔ nano-X-ray CT nɔ lɛ mlijaa. Skel bar: 10 μm. b Yitso 2: HAADF-STEM mfonirii ni kɔɔ katod ni ji BOT kɛ EOT nibii ni haa mɔ tsui nyɔɔ emli lɛ ahe. Skel bar: 1 μm. 2: HADF-STEM kɛ EDX mfonirii ni ajie lɛ kpo yɛ EOT tsɔne ni haa mɔ tsui nyɔɔ emli lɛ mli lɛ. Skel bar: 100 nm. c X-ray tsɔɔmɔi ni kɔɔ BOT kɛ EOT katod nɔkwɛmɔnii lɛ ahe. d Yɛ he ni eyɔɔ lɛ, X-ray ni jieɔ Bi2O3 tsɔne ni yɔɔ 0.1 M KOH mli lɛ mli lɛ ji hewalɛ nitsumɔ (0.8 V kɛyashi -1.5 V vs. RHE).
Kɛha hegbɛi ni yɔɔ ni baaha hewalɛ nitsumɔ aya hiɛ kɛtsɔ formic acid oxidation ni tsiɔ naa lɛ nɔ lɛ, akɛ H2 reference electrode tsu nii koni akɛyoo nɔ ni voltage ni laajeɔ lɛ yeɔ ebuaa39. Yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei ni shɛɛɛ 500 mA/cm2 lɛ, katod hewalɛ lɛ hiɔ shi yɛ -1.25 V shishi. asid. Yɛ nɔ ni yaa nɔ blɛoo lɛ hewɔ lɛ, kɛ akɛto HOR41 he lɛ, formic acid oxidation nifeemɔ bibioo ni yɔɔ anode lɛ mli lɛ baanyɛ aha anodic hewalɛ lɛ aya hiɛ waa. Nɔ ni jɛ mli ba lɛ tsɔɔ akɛ, kɛ́ atsĩ formic acid anodic oxidation lɛ naa kwraa lɛ, ebaanyɛ ejie nɔ ni miihe ashɛ 500 mV ni fe nine lɛ.
Kɛha nɛkɛ akɔntaabuu nɛɛ kaa lɛ, atsake bɔ ni nu ni ji deionized (DI) lɛ hoɔ yɛ anode lɛ mli lɛ mli koni akɛba formic acid ni hoɔ lɛ mli lɛ shi. 6b kɛ c tsɔɔ FE, formic acid mlibotemɔ, kɛ tsɔne mli hewalɛ akɛ DI flux nitsumɔ yɛ anode lɛ nɔ yɛ 200 mA/cm2. Beni nu ni ajie lɛ kpo lɛ mli hoɔ lɛ yaa hiɛ kɛjɛɔ 3.3 mL/min kɛyaa 25 mL/min lɛ, formic acid ni yɔɔ anode lɛ mli lɛ baa shi kɛjɛɔ 0.27 mol/L kɛyaa 0.08 mol/L. Kɛ akɛto he lɛ, kɛtsɔ sandwitsi gbɛjianɔtoo ni Xia kɛ ekrokomɛi kɛba lɛ nɔ. 30 Aná fɔmik asid ni falɛ ji 1.8 mol/L yɛ 200 mA/cm2. Nibii ni yɔɔ mli lɛ ni aba shi lɛ haa FE ni yɔɔ formic acid lɛ mli lɛ fɛɛ yaa hiɛ ni ehaa FE ni yɔɔ H2 lɛ nɔ baa shi be mli ni cathode pH lɛ bafeɔ alkaline babaoo yɛ formic acid lɛ sɛɛgbɛ gbɛfaŋnɔ ni baa shi lɛ hewɔ. Formic acid ni baa shi yɛ DI ni hoɔ lɛ hu jieɔ formic acid oxidation, ni no ha tsɔne lɛ mli hewalɛ ni baa shi fe 1.7 V yɛ 200 mA/cm2 lɛ ba. Batri mli latsaa hu saa nitsumɔ fɛɛ he, ni atsɔɔ nɔ ni jɛɔ mli baa lɛ yɛ mfoniri S10 lɛ mli. Shi kɛlɛ, PCEM-ni damɔ tsumaa nɔ lɛ baanyɛ aha hewalɛ nitsumɔ aya hiɛ jogbaŋŋ yɛ formic acid oxidation tsimɔ mli, kɛji kɛtsɔ anodic catalysts ni hydrogen halamɔ ni yaa hiɛ kɛyaa formic acid nɔ loo kɛtsɔ tsɔne nitsumɔ nɔ.
a Nibii ni haa mɔ tsui nyɔɔ emli ni ji H2 electrode ni tsuɔ nii yɛ 60 °C, Pt/C anode kɛ 80 μm AEM lɛ mligbalamɔ. b FE kɛ formic acid ni abua naa yɛ 200 mA/cm2 kɛtsɔ anodic deionized nu ni hoɔ srɔtoi lɛ nɔ. c Kɛ́ anode lɛ bua formic acid lɛ naa yɛ srɔtoi amli lɛ, tsɔne lɛ mli hewalɛ ji 200 mA/cm2. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔ ni yɔɔ susumɔi srɔtoi etɛ mli. d Nihɔɔmɔ jara ni baa shi fe fɛɛ ni aja mli kɛtsɔ nitsumɔ nɔ yɛ nu ni mli ewo muji srɔtoi ni akɛ maŋ nitsumɔhei amli srawa hewalɛ jara ni ji US$0.068/kWh kɛ US$4.5/kg hydrogen tsuɔ nii. (*: Asusuɔ akɛ formic acid ni yɔɔ anode lɛ mli lɛ ji 10 M FA, maŋ lɛ mli sarawa hewalɛ jara ji $0.068/kWh, ni hydrogen ji $4.5/kg. **: Asusuɔ akɛ formic acid ni baa shi fe fɛɛ lɛ ji anoderic. FA ni yɔɔ anode lɛ mli lɛ ji 1, the M3. $0.03/kWh, ni ŋwɛi ŋta lɛ damɔ shi kɛha jara ni ji 85 wt% FA lɛ.
Afee techno-economic analysis (TEA) koni ana shika ni baa shi fe fɛɛ ni akɛhɔ̃ɔ fuel assemblies lɛ yɛ nitsumɔ shihilɛi srɔtoi amli, taakɛ atsɔɔ yɛ mfoniri 5d lɛ mli lɛ. Abaanyɛ ana gbɛi kɛ sɛɛgbɛ saji kɛha TEA yɛ SI lɛ mli. Kɛji akɛ LC ni yɔɔ anode exhaust lɛ mli lɛ fa babaoo lɛ, yɛ cell voltage ni fa lɛ fɛɛ sɛɛ lɛ, fuel kpee lɛ he nyɔmɔwoo fɛɛ baa shi yɛ mligbalamɔ he nyɔmɔwoo ni baa shi lɛ hewɔ. Kɛji akɛ abaanyɛ ajie anodic oxidation ni ji formic acid lɛ shi kɛtsɔ tsɔne ni haa tsɔne lɛ tsuɔ nii loo electrode he ŋaalee nɔ lɛ, tsɔne ni haa tsɔne lɛ mli hewalɛ ni baa shi (1.66 V) kɛ FA ni fa babaoo ni yɔɔ nu ni hoɔ lɛ mli (10 M) lɛ ni akɛaafee ekome lɛ baaha tsɔne ni akɛfeɔ tsɔne ni akɛfeɔ tsɔne lɛ mli FA lɛ he nyɔmɔwoo lɛ aba shi kɛyashɛ 0.74 US dollars/kg (ni damɔ tsɔne nɔ). jara) dɔlai 0.068/kWh kɛ dɔlai 4.5/kg haidrojin42. Kɛfata he lɛ, kɛ akɛ wɔsɛɛ be mli jara ni atsɔɔ akɛ abaanyɛ afee srawa hewalɛ ni anyɛɔ atsakeɔ lɛ ni ji $0.03/kWh kɛ hydrogen ni ji $2.3/kg fata he lɛ, FA nu fɔŋ ni ato he gbɛjianɔ lɛ baa shi kɛyashɛɔ akpekpei 1.3, ni nɔ ni jɛɔ mli baa ji naagbee jara ni atsɔɔ akɛ afee lɛ ji US$0.66/kg43. Akɛ enɛ toɔ jara ni yɔɔ amrɔ nɛɛ he. No hewɔ lɛ, wɔsɛɛ be mli mɔdɛŋbɔɔ ni akɛjwɛŋmɔ maa electrode nibii kɛ gbɛjianɔtoi anɔ lɛ baanyɛ aha anodization aba shi babaoo yɛ be mli ni eŋmɛɔ gbɛ ni nitsumɔ yɛ cell voltages ni baa shi lɛ nɔ koni ekɛ LC ni fa babaoo aba.
Yɛ kukufoo mli lɛ, wɔkase zero-gap MEA gbɛjianɔtoi babaoo kɛha CO2 shibaa kɛyaa formic acid nɔ ni wɔkɛ gbɛjianɔtoo ko ni yɔɔ hiɛ-kɛ-sɛɛ-kɛ-sɛɛ bipolar membrane ni perforated cation tsakemɔ membrane (PECM) fata he lɛ he susumɔ ba koni ekɛha membrane mass transfer interface lɛ aya hiɛ kɛha formic acid ni jɛɔ mli baa lɛ. . Nɛkɛ gbɛjianɔtoo nɛɛ haa >96% formic acid yɛ 0.25 M (yɛ anode DI ni hoɔ 3.3 mL/min mli). Yɛ DI ni hoɔ oya (25 mL/min) lɛ mli lɛ, nɛkɛ gbɛjianɔtoo nɛɛ ha ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni ji >80% FE ni ji 200 mA/cm2 yɛ 1.7 V ni akɛ 25 cm2 cell area tsuɔ nii lɛ. Yɛ anodic DI mlijaa (10 mL/min) mli lɛ, PECM gbɛjianɔtoo lɛ hiɛɔ hewalɛ ni yɔɔ shiŋŋ kɛ formic acid FE ni nɔ kwɔ mli kɛha ŋmɛlɛtswai 55 ni akɛkaa yɛ 200 mA/cm2. Abaanyɛ aha shifimɔ ni nɔ kwɔ kɛ halamɔ ni jɛɔ jarayeli mli nibii ni haa mɔ tsui nyɔɔ emli kɛ polymeric membrane nibii amli lɛ aya hiɛ kɛtsɔ amɛ ni akɛ electrocatalysts ni hi jogbaŋŋ lɛ baafata he lɛ nɔ. Nitsumɔ ni nyiɛ sɛɛ lɛ baakɔ shihilɛi ni akɛtsuɔ nii lɛ ahe tsakemɔ, anode catalyst halamɔ, kɛ MEA gbɛjianɔtoo lɛ he koni akɛba formic acid oxidation shi, ni no baaha nu ni hoɔ babaoo yɛ cell voltages ni baa shi lɛ mli aba. Gbɛ ni yɔɔ mlɛo ni atsɔɔ nɔ akɛ carbon dioxide tsuɔ nii kɛhaa formic acid ni ajie lɛ kpo yɛ biɛ lɛ jieɔ anolyte kɛ catholyte tsũi, sandwich mli nibii, kɛ nibii krɛdɛɛi ahe hiamɔ lɛ kɛyaa, ni no haa wala yibii lɛ ahewalɛ yaa hiɛ ni ehaa gbɛjianɔtoo lɛ mli nibii ni mli wawai lɛ baa shi, ni ehaa efeɔ mlɛo akɛ aaaya hiɛ. Gbɛjianɔtoo ni atsɔɔ lɛ haa gbɛjianɔtoo kɛha CO2 tsakemɔ nitsumɔhei ni baanyɛ atsu nii yɛ ŋaa kɛ shika gbɛfaŋ lɛ ahe nitsumɔ wɔsɛɛ.
Ja akɛɛ gbɛ kroko nɔ lɛ, akɛ tsofafeemɔ mli nibii kɛ tsofai ni akɛwoɔ mli lɛ fɛɛ tsu nii bɔ ni aná lɛ. Akɛ bismuth oxide catalyst (Bi2O3, 80 nm) lɛ he nii kɛjɛ U.S. Nibii Amlipɛimɔ Nanomaterials, Inc. 18.2 Ω, Milli–Q® Sɛɛnamɔ A10 nu hetsemɔ gbɛjianɔtoo) lɛ he Omnisolv® gbɛi ni ji N-propanol (nPA) lɛ kɛjɛ Millipore Sigma dɛŋ. ACS he odaseyeli ni ji methanol kɛ acetone lɛ heɔ kɛjɛɔ VWR tsofafeemɔ nitsumɔhe BDH® kɛ Fisher tsofafeemɔ nitsumɔhe lɛ. Akɛ polymer powder lɛ futu acetone kɛ methanol ni akɛfutu mli lɛ mli yɛ 1:1 mli yɛ shwiili mli koni ana polymer ni gbɛɔ eshwaa ni 6.5 wt.% yɔɔ mli. 20g Bi2O3, nu ni mli tse waa, nPA kɛ ionomer ni gbɛɔ eshwaa lɛ ni akɛfutuɔ 30ml tsɛnsi mli lɛ nɔ. Nɔ ni yɔɔ mli lɛ ji 30 wt.% ni haa mɔ tsui nyɔɔ emli, ionomer kɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ mlijaa 0.02 kɛ dãa kɛ nu mlijaa 2:3 (40 wt.% nPA). Dani abaafutu lɛ, akɛ Glen Mills 5mm zirconia ni akɛshwieɔ nii lɛ 70g fataa he. Akɛ nɔkwɛmɔnii lɛ wo FisherbrandTM dijitaal tɔ rola nɔ yɛ 80 rpm mli ŋmɛlɛtswai 26 sɔŋŋ. Ha ink lɛ ahi shi minitii 20 dani okɛwo nɔ. Akɛ Bi2O3 ink wo Qualtech tsɔne ko ni tsuɔ nii diɛŋtsɛ (QPI-AFA6800) nɔ kɛtsɔ 1/2 ′′ x 16 ′′ laboratorio waya ni akɛwoɔ mli lɛ nɔ (RD Specialties – 60 mil diameter) yɛ 22°C nɔ. 5 mL ni ji katalitik ink lɛ wo 7.5 x 8 inch Sigraacet 39 BB carbon gas shweremɔ tsɔne (fuel cell ni akɛtoɔ) mli kɛtsɔ tso ni akɛwoɔ mli lɛ nɔ yɛ oyaiyeli ni ato he gbɛjianɔ ni ji 55 mm/sec nɔ. Okɛ electrodes ni akɛwo mli nɛɛ awo flɔnɔɔ mli ni oha egbi yɛ 80 °C. Atsɔɔ tso ni akɛwoɔ mli lɛ he gbɛjianɔtoo kɛ GDE ni akɛwoɔ mli lɛ he mfonirii yɛ mfoniri S4a kɛ b lɛ mli. X-ray la ni tsoɔ (XRF) nibii (Fischerscope® XDV-SDD, Fischer-Technology Inc. USA) ma nɔ mi akɛ GDE ni akɛwoɔ mli lɛ ji 3.0 mg Bi2O3/cm2.
Kɛha tsɔnei ni akɛfee tsɔnei ni yɔɔ anion tsakemɔ tsɔnei (AEM) kɛ CEM ni mli ewo muji. Akɛ Nafion NC700 (Chemours, USA) ni ŋmɛlɛtswaa ni ji 15 μm lɛ tsu nii akɛ CEM ŋtayaa. Akɛ anodic catalyst lɛ shwie FEM lɛ nɔ tɛ̃ɛ kɛ ionomer kɛ carbon mlijaa 0.83 kɛ he ni eha he ni ji 25 cm2. 10E50E, TANAKA dade ni jara wa) ni 0.25 mg Pt/cm2 ni akɛwoɔ mli lɛ tsu nii akɛ nɔ ni haa anode lɛ yaa hiɛ. Akɛ Nafion D2020 (Ion Hewalɛ, U.S.A.) tsu nii akɛ ionomer kɛha anode fã ni haa tsɔne lɛ tsuɔ nii lɛ. Akɛ CEM perforation lɛ tsuɔ nii kɛtsɔ linei ni kɛ amɛhe kpãa gbee ni afoɔ yɛ CEM sini lɛ nɔ yɛ 3mm teŋgbɛ lɛ nɔ. Atsɔɔ bɔ ni afeɔ afoɔ ŋmeii lɛ amli fitsofitso yɛ mfoniri S12b kɛ c lɛ mli. Kɛtsɔ X-ray computed tomography nɔ lɛ, ama nɔ mi akɛ ŋwɛi ŋta ni yɔɔ ŋta lɛ mli lɛ ji 32.6 μm, taakɛ atsɔɔ yɛ mfoniri S12d kɛ e lɛ mli lɛ. Yɛ be mli ni abuaa tsɛŋemɔ helai anaa lɛ, akɛ CEM tsɔne ni akɛ tsɔne ni haa tsɛŋemɔ hela lɛ ebɔ he lɛ wo Toray wolo ni dalɛ ji 25 cm2 (5 wt% PTFE ni akɛtsu nii, Fuel Cell Store, USA) nɔ. Akɛ AEM tsɔne ko (PiperION, Versogen, USA) ni elɛɛmɔ ji 25, 40 loo 80 μm wo CEM lɛ nɔ, ni no sɛɛ lɛ akɛwo GDE katod lɛ nɔ. Afo AEM tsɔne lɛ mli 7.5 × 7.5 cm koni ekɛha tsɔne ni hoɔ lɛ fɛɛ nɔ, ni akɛwo 1 M potassium hydroxide mli nyɔɔŋ kome dani abua naa. Anode kɛ cathode fɛɛ kɛ PTFE spacers ni mli wa bɔ ni sa ni baanyɛ ashɛ GDE ni hi fe fɛɛ ni ji 18% lɛ tsuɔ nii. Atsɔɔ bɔ ni afeɔ abuaa batri lɛ mli fitsofitso yɛ mfoniri S12a lɛ mli.
Yɛ kaa beaŋ lɛ, akwɛ tsɛŋemɔ hela ni abua naa lɛ nɔ yɛ 60 °C (30, 60, kɛ 80 °C kɛha hulutsoo he nikasemɔi) kɛ 0.8 L/min ni ji hydrogen gas ni akɛhaa anode lɛ kɛ 2 L/min ni ji carbon dioxide ni akɛhaa cathode lɛ. 100% hulutsoo kɛ 259 kPa absolute cathodic hewalɛ. Yɛ be mli ni nitsumɔ lɛ yaa nɔ lɛ, akɛ katod la ni hoɔ lɛ futuɔ 1 M KOH solution lɛ mli yɛ 2 mL/min mli koni ekɛwo katod catalyst saatso lɛ kɛ ionic conduction lɛ nitsumɔ he hewalɛ. Akɛ anode gas ni hoɔ kɛ nu ni mli ewo muji lɛ futuɔ mli yɛ 10 ml/min mli koni ajie formic acid ni yɔɔ anode lɛ nɔ lɛ. Atsɔɔ tsɔne lɛ mli nibii ni akɛwoɔ mli kɛ nibii ni ajieɔ kɛjɛɔ mli lɛ amli fitsofitso yɛ mfoniri S5 lɛ mli. Katod kɔɔyɔɔ ni ajieɔ lɛ mli lɛ yɛ CO2 ni ekɛ CO kɛ H2 baa. Ajieɔ nu lɛ mli lasu lɛ kɛtsɔɔ tsɔne ko ni haa hulutsoo baa shi yɛ 2°C lɛ nɔ. Abaabua gas ni eshwɛ lɛ naa koni akɛpɛi gas be mli. Anode lɛ mli nu lɛ hu baatsɔ tsɔne ko ni haa nu lɛ mli tsɔɔ lɛ mli koni ekɛgbala nu lɛ kɛjɛ gas lɛ mli. Abaabua nu fɔŋ lɛ naa yɛ tsɛnsii ni mli tse amli ni akɛ nu mli chronometry baakwɛ mli koni ana bɔ ni formic acid ni jɛɔ mli baa lɛ fa ha. Akɛ Garmy potentiostat (ni ji 30K, Gamry, U.S.A.) lɛ tsu nii kɛka tsɔne ni haa hulu tsoɔ waa lɛ mli. Dani abaasusu ŋwɛi ŋta ni ji 2.5 mA/cm2 lɛ he lɛ, akwɛɔ wala yibii lɛ amli shii ejwɛ yɛ 0 kɛyashi 250 mA/cm2 kɛtsɔ linear voltammetry ni skan rate ji 2.5 mA/cm2 nɔ. Akɛ polarization curves lɛ tsu nii yɛ galvanostatic gbɛ nɔ ni akɛ cell lɛ hiɛ ŋmɛnɛŋmɛnɛ beaŋ density ko mli minitii 4 dani ajie cathode gas kɛ anolyte nu lɛ he nɔkwɛmɔnɔ.
Wɔkɛ hydrogen tsɔɔmɔ electrode ni yɔɔ MEA lɛ mli lɛ tsuɔ nii koni wɔkɛgbala cathode kɛ anodic hewalɛi lɛ amli. Atsɔɔ bɔ ni tsɔne ni akɛkwɛɔ nibii amli lɛ yɔɔ ha lɛ mli yɛ mfoniri S6a lɛ mli. Akɛ Nafion tsɔne ko (Nafion 211, IonPower, USA) tsu nii akɛ ionic tsɔne ni akɛtsaa MEA tsɔne lɛ kɛ tsɔne ni akɛkwɛɔ nii lɛ nɔ. Akɛ Nafion strip lɛ naagbee kome fata 1 cm2 gas diffusion electrode (GDE) ni akɛ 0.25 mg Pt/cm2 (50 wt% Pt/C, TEC10E50E, TANAKA Dade ni Jara) ni akɛshwie 29BC carbon wolo (Fuel USA Store) nɔ lɛ he. ). Akɛ polyetheretherketone (PEEK) tsɔne krɛdɛɛ ko tsuɔ nii koni akɛtsi gas naa ni ekwɛ koni GDE kɛ Nafion tsɔnei lɛ ateŋ tsakpaa kpakpa aba, ni akɛ tsɔne ni akɛkwɛɔ nibii amli lɛ atsa fuel cell tsɔne lɛ nɔ. Nafion strip lɛ naagbee kroko lɛ kɛ CEM batri lɛ naagbee ni jeɔ kpo lɛ kpãa gbee. Nɔkwɛmɔnɔ S6b tsɔɔ ŋwɛi fã ni akɛtsɔɔ ŋwɛi ŋta ni akɛ MEA lɛ ebɔ he lɛ.
Beni kɔɔyɔɔ ni ajieɔ lɛ kpo lɛ tsɔ tsɔne ni haa kɔɔyɔɔ lɛ mli tsɔɔ kɛ kɔɔyɔɔ-nu mligbalamɔ mli lɛ sɛɛ lɛ, ajieɔ kɔɔyɔɔ lɛ he nɔkwɛmɔnii kɛjɛɔ katod lɛ mli. Akɛ 4900 Micro GC (10 μm molecular sieve, Agilent) tsu nii kɛpɛi kɔɔyɔɔ ni abua naa lɛ mli kɛ hoo lɛ shii etɛ. Akɛ nɔkwɛmɔnii lɛ wo aluminum foil gas nɔkwɛmɔnɔ kotokui ni bɛ hewalɛ ni ji SupelTM (Sigma-Aldrich) lɛ amli kɛha be pɔtɛɛ ko (sɛkɛndii 30) ni akɛ niji wo microgas chromatograph lɛ mli yɛ ŋmɛlɛtswai enyɔ mli kɛjɛ be mli ni abua naa lɛ. Akɛ tsofa ni akɛwoɔ mɔ mli lɛ mli latsaa lɛ to 110°C. Akɛ argon (Matheson Gas-Matheson Purity) tsu nii akɛ kɔɔyɔɔ ni akɛwoɔ mli lɛ mli, ni ajie kɔɔyɔɔ ni mli edɔ (105 °C) ni mli edɔ (28 psi) 10 m MS5A ŋwɛitsu lɛ nɔ. Akɛ tsɔne ni akɛwoɔ tsɔne mli ni haa hulu tsoɔ waa (TCD) lɛ tsuɔ nii kɛnaa nɛkɛ tsakpaai nɛɛ. Atsɔɔ GC kromatogram kɛ CO kɛ H2 ŋwɛi ŋta yɛ mfoniri S7 mli. 120 sɛkɛndii) ni akɛ 0.22 μm PTFE syringe filter tsu nii kɛshwie 2 mL tsɛnsii amli. 1260 Infinity II bioinert nu mli nibii ni yɔɔ tsɛnsii lɛ amli lɛ tsu nii kɛpɛi mli, ni akɛ 20 μl ni ji nɔkwɛmɔnɔ lɛ wo mli kɛtsɔ autosampler (G5668A) ni 4 mM sulfuric acid (H2SO4) ni akɛyaa he fɛɛ he lɛ tsuɔ nii yɛ mli lɛ nɔ. ) yɛ 0.6 ml/min (pɔmp ni ji ejwɛ G5654A) mli. Akɛ nibii ni akɛtsuɔ nii lɛ mli gbala yɛ tsɔne ko ni mli edɔ (35°C, tsɔne ni akɛwoɔ tsɔne mli ni akɛwoɔ tsɔne mli lɛ mli) ni tsɔne ni akɛwoɔ tsɔne mli ni ji Micro-Guard Cation H lɛ tsɔɔ hiɛ lɛ nɔ. Akɛ tsɔne ko ni akɛtaoɔ nibii amli (DAD) tsu nii kɛna formic acid. yɛ ŋshɔkei ni ji 210 nm kɛ ŋshɔkei ni ji 4 nm lɛ mli. Atsɔɔ HPL kromatogram kɛ formic acid shishitoo mla ni akɛtoɔ he lɛ yɛ mfoniri S7 lɛ mli.
Akɛ equation ni nyiɛ sɛɛ nɛɛ buɔ gas nibii ni jɛɔ mli baa (CO kɛ H2) FE lɛ he akɔntaa, ni akɛ gas equation ni hi jogbaŋŋ lɛ buɔ gas moles lɛ fɛɛ he akɔntaa:
Amɛteŋ ekomɛi ji: \({n}_{i}\): ɛlɛktrɔn ayibɔ ni yɔɔ ɛlɛktrɔnik nifeemɔ mli. \(F\): Faraday nɔ ni tsakeee. \({C}_{i}\): HPLC nu mli nibii ni yɔɔ mli lɛ mli. \(V\): nu mli nɔkwɛmɔnɔ ni abua naa yɛ be pɔtɛɛ ko mli t. \(j\): ŋmɛnɛŋmɛnɛ beaŋ tsɔne. \(A\): Elɛktrɔd lɛ jiomɛtri he (25 cm2). \(t\): nɔkwɛmɔnɔ be. \(P\): nɔnyɛɛ ni yeɔ emuu. \({x}_{i}\): Gas mlijaa oha mlijaa ni GC tsɔɔ. \(R\): kɔɔyɔɔ ni tsakeee. \(T\): dɔlɛ.
Akɛ plasma atomik nibii ni ajieɔ kɛjɛɔ mli lɛ (ICP-OES) tsu nii kɛsusu bɔ ni anodik kations lɛ fa ha lɛ he. Cations ni baanyɛ atsɔ mli loo egbɛ eshwa anode lɛ mli lɛ ekomɛi ji Ti, Pt, Bi kɛ K. Kɛ ajie K lɛ, cations krokomɛi lɛ fɛɛ yɛ husu ni akɛnaa lɛ shishi. Feemɔ ions yɛ tsabaa lɛ mli ni eshiɔ anode lɛ koni ekɛ protons loo cations krokomɛi afee ekome. No hewɔ lɛ, abaanyɛ abu formic acid lɛ he tsemɔ he akɔntaa akɛ
Formate/FA nifeemɔ damɔ shi kɛha FA ni afee yɛ kWh ni akɛ MEA gbɛjianɔtoo pɔtɛɛ ko tsuɔ nii yɛ mli lɛ mli, yɛ mol/kWh mli. Akɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ mli tsɔne lɛ, tsɔne lɛ mli hewalɛ kɛ Faraday nitsumɔ mli hewalɛ ni yɔɔ nitsumɔ shihilɛi pɔtɛɛ komɛi amli lɛ buɔ he akɔntaa.
Buu formic acid ni yɔɔ anode lɛ mli lɛ falɛ he akɔntaa yɛ bɔ ni tsɔne lɛ fɛɛ yɔɔ ha lɛ nɔ. Nibii etɛ ni kɛ amɛhe wuɔ ta lɛ baa yɛ katod lɛ mli: hydrogen sutsakemɔ, CO2 ni baa shi kɛyaa CO mli, kɛ CO2 ni baa shi kɛyaa formic acid mli. Akɛni wɔyɛ formic acid oksideshin gbɛjianɔtoo yɛ Anton hewɔ lɛ, abaanyɛ aja formic acid FE lɛ mli awo fãi enyɔ: formic acid ni abua naa kɛ formic acid oksideshin. Abaanyɛ aŋma mass balance lɛ fɛɛ akɛ:
Wɔkɛ GC tsu nii ni wɔkɛna bɔ ni formic acid, hydrogen, kɛ CO ni HPLC buaa naa lɛ fa ha. Esa akɛ akadi akɛ, abua formic acid lɛ babaoo naa kɛjɛ anode lɛ mli kɛtsɔ gbɛjianɔtoo ni atsɔɔ yɛ Supplementary Figure S5 lɛ nɔ. Formate ni abua naa kɛjɛɔ cathode tsu lɛ mli lɛ he ehiaaa, aaafee shishitoo mlai enyɔ ni baa shi, ni eshɛɛɛ 0.5% yɛ SC lɛ fɛɛ mli.
Gbɛfaa gbɛjianɔtoo ni yaa nɔ ni akɛtsuɔ nii yɛ biɛ lɛ damɔ nitsumɔ ni eho yɛ gbɛjianɔtoi ni tamɔ nakai nɔŋŋ nɔ34. Akɛ Poisson-Nerst-Planck (PNP) equation gbɛjianɔtoo ni akɛfata he lɛ tsuɔ nii koni akɛna nu mli nibii ni yɔɔ mli lɛ kɛ tsɔne ni haa hulu kpɛɔ lɛ mli hewalɛ ni yɔɔ tsɔne ni akɛtswaa la kɛ tsɔne ni haa hulu kpɛɔ lɛ mli. Akɛ equation ni yɔɔ shishi lɛ he susumɔ fitsofitso kɛ jiomɛtri nɔkwɛmɔnɔ lɛ haa yɛ SI lɛ mli.
Gbɛjianɔtoo nɛɛ tsɔɔ bɔ ni nu mli nibii kpaanyɔ (\({{{{{{\rm{C}}}}}}}}{{{{{\rm{O}}}}}}}}_{2 \rm{O}}}}}}}_{2 \abɛku ({{{{{\rm{\rm{aq}^}}}}}\ninejurɔ)}\), \(r{{{}}}}}\ninejurɔ)}\), \(r{{}}}{ \ ({{{{\rm{O}}}}}}{{{{{\rm{\rm{H}}}}}}^{-}\), \({{{{{{ \rm{ HCO}}}}}}}_{3}^{-}\), \({{{{\rm{CO}}}}}}_{{\rm{CO}}}}}}_ ({{{\rm{HCOOH}}}}}}\), \({{{{\rm{HCOO}}}}}}}}^{- }\) kɛ \({{{{{\rm{K}}}}}}^{+_}\)), anostatik hewalɛ yɛ ionik kudɔmɔ mli kɛ katodik ɛlɛktrɔn ni tsɔɔ tsɔne mli. Elɛktrostatik hewalɛi yɛ fãi amli (\({\phi }_{A}\) kɛ \({\phi }_{C}\) yɛ gbɛ kome nɔ). Yɛ no najiaŋ lɛ, tsɔne ni haa hulu kpɛɔ yɛ maŋ lɛ mli lɛ loo charge mlijaa nitsumɔi lɛ eko kwraa bɛ mli, atsuɔ ŋwɛi charge kpokpaa lɛ he nii tɛ̃ɛ kɛtsɔ Poisson equation lɛ nɔ; Nɛkɛ gbɛ nɛɛ haa wɔfeɔ Donnan sɛɛkuu lɛ he mfoniri tɛ̃ɛ yɛ CEM|AEM, CEM|Pore, kɛ AEM|Pore teŋgbɛ. Kɛfata he lɛ, akɛ porous electrode theory (PET) tsuɔ nii kɛtsɔɔ bɔ ni charge lɛ yaa nɔ yɛ anodic kɛ cathodic fãi ni yɔɔ tsɔne ni haa tsɔne lɛ tsuɔ nii lɛ mli lɛ mli. Kɛyashi niŋmalɔi lɛ anilee naa lɛ, nitsumɔ nɛɛ damɔ shi kɛha klɛŋklɛŋ nitsumɔ ni akɛ PET tsuɔ nii yɛ gbɛjianɔtoi ni yɔɔ ŋwɛi charge kpokpai babaoo lɛ amli.
Akɛ Zeiss Xradia 800 Ultra ni 8.0 keV X-ray jɛɛhe yɔɔ mli lɛ ka GDE BOT kɛ EOT katod nɔkwɛmɔnii lɛ akwɛ, kɛ mfoniri ni akɛfutuɔ nii. Abua mfonirii 901 naa kɛjɛ -90° kɛyashi 90° ni ajie lɛ kpo yɛ sɛkɛndii 50 mli. Akɛ sɛɛgbɛtsɔɔmɔ filta ni voxel dalɛ ji 64 nm tsu nii kɛtswa ekoŋŋ. Akɛ mlai ni aŋmala krɛdɛɛ ko tsu nii kɛpɛi mligbalamɔ kɛ fãji bibii lɛ amlijaa mli.
Electron microscopic sui lɛ biɔ ni akɛ MEAs ni akaa lɛ awo epoxy resin mli koni akɛsaa he kɛha ultrathin fãi ni akɛ ojarawatɛi tsuɔ nii yɛ mli lɛ. Afo MEA lɛ eko fɛɛ eko mli fã ni tsɔɔ ŋwɛigbɛ lɛ mli kɛyashɛ 50 kɛyashi 75 nm. Akɛ Talos F200X tsɔne ni akɛkwɛɔ nibii bibii amli (Thermo Fisher Scientific) tsu nii kɛsusu tsɔne ni akɛkwɛɔ nibii bibii amli (STEM) kɛ hewalɛ ni gbɛɔ eshwaa X-ray nibii bibii ni akɛkwɛɔ nii amli (EDS) lɛ he. Akɛ EDS Super-X gbɛjianɔtoo ko ni yɔɔ SDD nibii 4 ni samflɛ bɛ mli lɛ ewo mikroskopu lɛ mli, ni etsuɔ ​​nii yɛ 200 kV mli.
Akɛ powda X-ray difraktomita (PXRD) lɛ tsu nii yɛ Bruker Advance D8 powda X-ray difraktomita ni Ni-filtered Cu Kα radiation tsuɔ nii yɛ 40 kV kɛ 40 mA nɔ lɛ nɔ. Skanning he lɛ jeɔ shishi kɛjɛɔ 10° kɛyashi 60°, gbɛ lɛ dalɛ ji 0.005°, ni data lɛ he oyaiyeli lɛ ji sɛkɛndi kome yɛ gbɛ fɛɛ gbɛ nɔ.
Asusu RAS spectrum ni yɔɔ Bi2O3 Bi L3 catalyst lɛ naa lɛ he akɛ eji nyɛmɔ nitsumɔ kɛtsɔ shia mli wala yibii ni akɛtsuɔ nii lɛ nɔ. 156.3 μL ionomer mli nu (6.68%) ni akɛ 1 M KOH, nu (157 μL) kɛ isopropyl dãa (104 μL) futu mli lɛ tsu nii kɛfee Bi2O3 ni haa mɔ tsui nyɔɔ emli lɛ he nii koni anyɛ ana ionomer ni akɛwoɔ mli lɛ. Nɔ ni haa nɔ ko yaa hiɛ lɛ ji 0.4. Akɛ niŋmaatsei lɛ wo graphene woji lɛ anɔ yɛ hei ni yɔɔ koŋtɛi ejwɛ (10×4 mm) kɛyashi Bi2O3 nibii ni haa mɔ tsui nyɔɔ emli lɛ shɛɔ 0.5 mg/cm2. Akɛ Kapton woɔ graphene wolo lɛ fã ni eshwɛ lɛ nɔ koni ekɛjie nɛkɛ hei nɛɛ kɛjɛ electrolyte lɛ he. Akɛ graphene wolo ni akɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ wo PTFEs enyɔ ateŋ ni akɛ skru fĩ wala yibii lɛ gbɔmɔtso lɛ he (PEEK), Mfoniri S8. Hg/HgO (1 M NaOH) ji nɔ ni akɛkwɛɔ nibii amli, ni carbon wolo ji nɔ ni akɛkwɛɔ nibii amli. Akɛ platinum waya ni akɛwo hydrogen ni eyi obɔ kɛ 0.1 M KOH mli lɛ tsu nii kɛsusu Hg/HgO tsɔne ni akɛkwɛɔ nii lɛ he koni akɛtsake hewalɛi fɛɛ ni asusu lɛ awo hydrogen tsɔne ni anyɛɔ atsakeɔ (RHE) lɛ mli. Akɛ XRD spectra lɛ tsu nii kɛtsɔ Bi2O3/graphene wolo ni tsuɔ nii ni akɛwo 0.1 M KOH mli, ni edɔ kɛyashɛɔ 30 °C lɛ he hewalɛ ni akwɛɔ nɔ lɛ nɔ. Electrolyte lɛ bɔleɔ batri lɛ mli, ni electrolyte lɛ botemɔ he lɛ yɛ cell lɛ shishigbɛ, ni electrolyte lɛ kpojiemɔ lɛ hu yɛ ŋwɛigbɛ koni ekwɛ akɛ electrolyte lɛ kɛ catalyst layer lɛ kpeɔ kɛ́ ŋmeii ba. Akɛ CH Instruments 760e potentiostat tsu nii koni akɛkudɔ tsɔne ni tsuɔ nii lɛ hewalɛ. 100, -200, -300, -400, -500, -800, -850, -900, -1000, -1100, -1500 kɛ +700 mV ni damɔ RHE nɔ. Atsake iR nyɛmɔi lɛ fɛɛ.
13424 eV kɛha Bi dade) X-ray ni ŋmɛɔ nii jogbaŋŋ (XAFS) lɛ he niiamlipɛimɔ yɛ gbɛ 10-ID, Photon Jɛɛhe ni Etee Hiɛ (APS), Argonne Maŋ Fluorescence Laboratory lɛ nɔ. Maŋ Nɔkwɛmɔnɔ Susumɔ He. Akɛ Si(111) monochromator ni yɔɔ kristalo enyɔ ni akɛ nitrogen ni mli edɔ ewo mli lɛ tsu nii koni akɛto X-ray hewalɛ lɛ he gbɛjianɔ, ni akɛ ashwishwɛ ni akɛ rhodium ehà nɔ lɛ tsu nii koni akɛha harmonic ni yɔɔ mli lɛ aba shi. Akɛ skan hewalɛi lɛ srɔtoi kɛjɛ 13200 kɛyashi 14400 eV, ni akɛ 5 × 5 silicon PIN diode gbɛjianɔtoo ni filta loo Soller slits bɛ mli lɛ tsu nii kɛsusu la ni tsoɔ lɛ he. 13271.90 eV kɛtsɔɔ Pt foil lɛ L2 naagbee lɛ nɔ. Yɛ bɔ ni electrochemical cell lɛ mli wa ha lɛ hewɔ lɛ, anyɛɛɛ asusu spectrum ni yɔɔ shishitoo mla lɛ mli lɛ he yɛ be kome mli. No hewɔ lɛ, tsakemɔ ni abuɔ he akɔntaa yɛ X-ray hewalɛ ni baa lɛ mli lɛ ji ±0.015 eV ni damɔ susumɔi ni afɔɔ feemɔ yɛ kaa lɛ mli fɛɛ lɛ nɔ. Bi2O3 ŋtayaa lɛ mli ŋtayaa lɛ haa hulutsoo lɛ diɛŋtsɛ shwieɔ ehe yɛ gbɛ ko nɔ; electrodes lɛ hiɛɔ he ko ni yɔɔ shiŋŋ yɛ incident beam kɛ detector lɛ he, ni no haa skan fɛɛ skan lɛ feɔ ekome. Akɛ XAFS spectrum ni bɛŋkɛ ŋmɔ lɛ tsu nii koni akɛna bɔ ni bismuth lɛ mli oksideshin shihilɛ kɛ tsofafeemɔ su lɛ yɔɔ ha lɛ kɛtsɔ XANES kpokpaa ni ji Bi kɛ Bi2O3 shishitoo mlai lɛ ni akɛtoɔ he lɛ nɔ kɛtsɔ Athena tsɔne lɛ mli linear combination fitting algorithm (version 0.9.26) lɛ nɔ. kɛtsɔ kood IFEFFIT 44 nɔ.
Nibii ni fiɔ yibɔi ni yɔɔ sane nɛɛ mli lɛ asɛɛ kɛ nikasemɔ nɛɛ naagbee wiemɔi krokomɛi lɛ yɛ woloŋmalɔ ni kɛ lɛ kpãa gbee lɛ ŋɔɔ kɛji abi ni jwɛŋmɔ yɔɔ mli.
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