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Okukyendeeza aha nshaho y‘amashanyarazi kuza omu formic acid n‘omuringo ogurikuraganisa gw‘okutunguura okukoresa kwa kaboni kandi gwine obushoboorozi bw‘okukoresibwa nk‘omuringo gw‘okubiikamu amaizi g‘omuyaga. Omu murimo ogu, enkora y‘okuteerana kw‘amashanyarazi g‘omubiri ogutarimu rubaju rwona neekorwa ahabw‘okuteerana kw‘amashanyarazi g‘omubiri oburikworeka asidi ya formic kuruga omu carbon dioxide. Entunguuka y’omutaano omu bya tekinologiya n’okuhindura ebiri omu nkora y’okuhindura ebiri omu nkora y’okuhindura ebiriisa, ebirikukoresibwa omu nkora y’okuhindura ebiriisa ebiri omu maisho, nibibaasisa formic acid erikubaho aha rubaju rw’entuura y’omubiri kuhindurwa kurabira omu mwanya gw’okusheeshasheesha ogwa anodic omu bipimo by’ahansi nka 0.25 M. Hatariho okwongyeraho ebiriisa bya battery anodexi aisting components the ledecept cation the sandwich components. ebikoreso n’enkora ezirikukira kubaho omu nkora y’amajuta n’okukoresa amashanyarazi g’amaizi, ekirikubaasisa okuhindura omu bwangu kuza omu kutunguura n’okuguza. Omu kahuri ka 25 cm2, enkora y‘okuhindura ebiri omu kation erimu ebitobo neeha >75% y‘obushoboorozi bwa Faraday ahabwa formic acid ahari <2 V na 300 mA/cm2. Ekikuru munonga, okukyebera okuhamire kw‘eshaaha 55 ahari 200 mA/cm2 kukooreka okuhamire kwa Faraday n‘amaani g‘obutafaari. Okushwijuma kwa tekinologiya n‘eby‘entasya nikukoresibwa kworeka emiringo y‘okuhikiiriza oburinganiza bw‘esente n‘emiringo y‘okukora formic acid eriho hati.
Okukyendeeza aha nkora y’amashanyarazi kuruga omu carbon dioxide kuza omu formic acid orikukoresa amashanyarazi agarikugarukaho kworekwa ngu nikukyendeeza aha sente z’okukora ebintu kuhika ahari 75%1 waagyeragyeranisa n’emiringo y’obuhangwa erikukoresa amajuta g’ebishaka. Nkoku kirikworekwa omu bihandiiko2,3, formic acid eine emiringo mingi y’okugikozesa, kuruga aha muringo murungi kandi ogw’eby’entaasya gw’okubiika n’okutwara amaizi g’omubiri kuhika aha by’okurya by’okukoresa omu by’emibazi4,5 nari eby’obuhangwa6. Formic acid nangwa ekamanyirwa nk’ekintu ekirikukoresibwa omu kuhindura amajuta g’enyonyi agatarikuhwaho barikukoresa enkora y’okuhindura eby’okurya7,8. Omu kutunguuka kw’eby’entaasya ya formic acid1,9, emirimo mingi y’okucondooza etaire omutima aha kutunguura okutoorana kw’ebintu ebirikureetaho 10,11,12,13,14,15,16. Kwonka, okuteeraho kwingi nikugumizamu kuta omutima aha butafaari bukye bwa H nari obutafaari oburikugyendera omu maizi oburikukorera aha nkora y‘amaani makye (<50 mA/cm2). Okukyendeeza aha sente, okuhikiiriza eby‘obushuubuzi n‘okwongyera aha kuza omu katare okurikukuratiraho, okukyendeeza aha nkora y‘amashanyarazi (CO2R) kushemerire kukorwa aha nkora y‘amashanyarazi (≥200 mA/cm2) n‘oburungi bwa Faraday Tech (FE)17 obwo barikutunguura okukoresa eby‘okukoresa eby‘amashanyarazi n‘ebicweka bya battery futer a CO2. eby‘okukoresa kutwara omugisha gw‘eby‘entasya y‘omutindo18. Okwongyera ahari ekyo, okwongyera aha mugasho gw’okukora n’okwetantara okwongyera kukora eby’okurya ebiri ahansi, formic acid eshemerire kukoresibwa nk’ekintu ky’aha muheru omu mwanya gw’okukoresa eminyoro ya formate19.
Omu rubaju oru, okuteeraho okuhererukireyo kukozirwe kukora eby’okukoresa eby’okukoresa omu by’amakorero ebirikukora aha CO2R formate/formic acid ebirikwegamira aha kujanjaaza omuyaga (GDE). Okushwijuma okuhikire okwakozirwe Fernandez-Caso na bagyenzi be.20 nikufunza enkora zoona z‘obutafaari bw‘amashanyarazi ahabw‘okugumizamu kukyendeeza CO2 kuhika aha formic acid/formate. Omu kutwariza hamwe, enkora zoona eziriho nizibaasa kubaganisibwamu emiringo eshatu emikuru: 1. Katoliiti ezirikugyendera omu maizi19,21,22,23,24,25,26,27, 2. Ekibumbe kimwe (ekibumbe ky’okuhindura kation (CEM)28, ekibumbe ky’okuhindura anion (AEMfi)29 na 3. ebicweka by‘okusharaho eby‘enkora ezi nibyorekwa omu kishushani 1a Ahabw‘okutebeekanisa kw‘okusheesheka kw‘ekyoma ky‘okusheeshasheesha nikihangwa ahagati y‘ekibunu ky‘okusheeshasheesha n‘okusheeshasheesha kw‘ekikwato ky‘okusheeshasheesha kya GDE Nikikoresibwa kuhangaho emihanda y‘okusheeshasheesha kw‘okusheeshasheesha kw‘okusheeshasheesha kw‘ekicweka ky‘okutegyeka eky‘okutooranamu33. ekozesiibwe Chen na bagyenzi be.Okukozesa katodi ya SnO2 aha rubaju rwa kaboni orurimu orubaju rwa katoliiti orurikwingana mm 1.27, kuhika ahari 90% FE 35 ahari 500 mA/cm2 kikahikirizibwa Okuteerana kw’orubaju rwa katoliiti orurikwingana n’orubaju rwa katoliiti orurikugaruka enyima n’ekipande ky’okuhingisa ekirikugaruka enyima (reverse-biased transfer voltage) VPM membrane. okukoresa gye amaani ga 15% Okutunguura okukoresa gye amaani, Li na bagyenzi be, barikukoresa enkora emwe eya CEM, bakatunga FE 29 eya 93.3% aha nkora y‘obucweka bw‘amaani eya 51.7 mA/cm2 aha nkora ya sin current Diaz-Sainz. mA/cm2. Kwonka, emiringo yoona ekareetaho formate okukira ekintu ekirikukunda, formic acid Okwongyerera aha byetaago by‘okukora ebindi, omu nkora za CEM, formats nka KCOOH nizibaasa kurahuka kwerundaana omu mwanya gwa GDE n‘okusheesheka, ekirikureetaho okuzibira entambura n‘okuremwa kw‘obutafaari bwanyima.
Okugyeragyeranisa eby‘okukoresa bishatu ebirikukirayo kumanywa eby‘okuhindura CO2R kuza omu formate/formic acid n‘enkora y‘okwombeka erikuteekateekwaho omu kucondooza oku. b Okugyeragyeranisa omubaro gwona ogw‘obwire obu n‘ebirikuruga omu formate/formic acid ahabw‘enkora ya catholyte, enkora ya sandwich, enkora ya CEM emwe omu bihandiiko (eyorekwa omu kipande ky‘okwongyeraho S1) n‘emirimo yeitu. Obumanyiso obukingire nibworeka okukora kw’omubazi gwa formate, kandi obubonero obugumire nibworeka okukora kwa formic acid. *Okutebekanisa nikworekwa orikukoresa haidrojeni aha anode. c Okutebekanisa kwa MEA okwa zero-gap orikukoresa ekicweka ky‘omubiri ekirimu ebiriisa bibiri ebiine ebiina ebirikukora omu muringo gw‘okuhindura ebiri omu maisho.
Okuzibira okuhangwa kwa fomati, Proietto na bagyenzi be. 32 bakakozesa omuringo gw’okuteeraho okushwijuma ogutarikubaganisibwamu ogu amaizi agarimu deionized garikugyenderamu kurabira omu nkora y’omugati. Enkora neebaasa kuhika >70% CE omu nkora y‘obuhango bwa 50–80 mA/cm2. Omu muringo nigwo gumwe, Yang na bagyenzi be. 14 bakaha enteekateeka y‘okukoresa ekicweka ky‘amashanyarazi ekigumire ahagati ya CEM na AEM kutunguura okukora kwa formic acid. Yang na bagyenzi be.31,36 bakatunga 91.3% FE omu kacweka ka 5 cm2 ahari 200 mA/cm2, bakareetaho omubazi gwa 6.35 wt% gw‘omubazi gwa asidi ya formiki. Xia n’abandi. Okukozesa enkora erikushushana, 83% okuhindura kwa carbon dioxide (CO2) kuza omu formic acid FE kukahikirizibwa ahari 200 mA/cm2, kandi okugumaho kw‘enkora kukagyezibwa kumara eshaaha 100 edakiika 30. N‘obu ebyarugamu aha rulengo rukye biraabe nibiraganisa, okweyongyera kw‘omuhendo n‘okugumizamu kw‘ebintu ebirikuhindura ion ebirimu obucupa nibireetera kigumire kugyeragyeranisa enkora z‘omugati kuhika aha nkora mpango (nk‘eky‘okureeberaho, 1000 cm2).
Kureeba omu maisho ebirikuruga omu nkora zitari zimwe na zimwe, tukahandiika aha nkora z‘okukora formate/formic acid ahari kWh ahabw‘enkora zoona ezaagambirweho enyima kandi twazihandiika omu kishushani 1b. Nikireebeka gye aha ngu enkora yoona erimu katoliti nari interlayer neija kuhika aha mutwe gw’okukora kwayo aha nkora y’amaani makye kandi ekyerere aha nkora y’amaani maingi, ahu ekikomo kya ohmic kirikubaasa kumanyisa amaani g’obutafaari. Ekindi, n‘obu enkora ya CEM erikukoresa amaani marungi eraabe neeha okukora kwa molar formic acid okurikukirayo ahari kWh, okweyongyera kw‘omunyugunyu nikubaasa kureetera okusiisikara kw‘okukora okwa juba aha nkora y‘amaani g‘amaani.
Okukyendeeza aha miringo y‘okuremwa eyaagambirweho enyima, tukakora ekibiina ky‘eby‘amashanyarazi (MEA) ekirimu BPM erimu ebicweka by‘omumaisho ebirikuhakanisa n‘ekicweka ky‘okuhindura cation (PCEM) ekirimu ebitobo. Enyombeka y‘okwombeka neeyorekwa omu kishushani 1c. Haidrojeni (H2) neetaaha omu anode kureetaho purotoni kurabira omu nkora ya haidrojeni (HOR). Omuringo gwa PCEM nigutaaha omu nkora ya BPM kubaasa kwikiriza ions za formate ezirikuruga omu katodi kuraba omu AEM, zikwataniise na purotoni kuhanga asidi ya formic aha nkoragana ya BPM n’omu nshonda z’omugati za CEM, reero zirugyemu kurabira omu anode ya GDE n’omu mwanya gw’okusheesheka. . Okukozesa enkora egi, tukatunga >75% FE ya formic acid ahari <2 V na 300 mA/cm2 ahabw‘omwanya gw‘obutafaari bwa 25 cm2. Ekikuru munonga, enkora egi neekoresa ebicweka ebirikushangwa omu katare n’eby’okukoresa eby’okukoresa omu kuhanga amajuta n’eby’okukoresa omu maizi, ekirikubaasisa obwire bw’okutunguuka omu bwangu. Entebekanisa za katoliiti zirimu ebishengye by‘okugyenderamu bya katoliiti ebirikubaasa kureetera obutaikirizana bwa pressure ahagati y‘ebicweka bya gaasi n‘amaizi, namunonga omu nkora z‘obutafaari obuhango. Aha nkora za sandwich eziine emiringo y‘okusheeshasheesha kw‘amaizi, okuteeraho kwingi nikwetengyesa kutunguura omutindo gw‘ahagati ogurimu obutafaari kukyendeeza aha kugwa kwa pressure n‘okuteerana kwa carbon dioxide omu mutindo gw‘ahagati. Ebi byombi nibibaasa kureetera okugaaniira kw’esimu kutabura. Kandi nikigumire kureetaho ebicweka by’omubiri ebikye ebirikwemerera byonka aha rurengo rwingi. Okutaana n‘ekyo, enkora ensya etebekanisiibwe n‘enkora ya zero-gap MEA etarimu ekishengye ky‘okusheesheka nari omutindo gw‘ahagati. Okugyeragyeranisa n’obutafaari obundi oburiho obw’amashanyarazi, enkora etebekanisiibwe n’ey’omutaano ahabw’okugira ngu neebaasisa okuteerana butoosha kwa formic acid omu nkora erikubaasa kugyezesibwa, erikukoresa amaani makye, kandi erimu zero-gap.
Okuzibira okuhinduka kwa haidrojeni, okuteeraho kw‘okukyendeeza CO2 aha rurengo rwahaiguru kukoreise enkora ya MEA na AEM membrane omu kugaita n‘ebiriisa by‘amashanyarazi ebirimu ebiriisa bingi (nk‘eky‘okureeberaho, 1-10 M KOH) kuhangaho embeera z‘alkaline aha katodi (nk‘oku kirikworekwa omu kishushani 2a). Omu ntebeekanisa ezi, ions za formate ezirikuhangwa aha katodi niziraba omu membrane nk’ebika ebiine eshagama mbi, reero KCOOH neehangwa kandi eruga omu nkora kurabira omu mugyera gwa anodic KOH. N‘obu formate FE na cell voltage byabaire biri birungi omu kubanza nk‘oku kirikworekwa omu kishushani 2b, okukyebera okugumaho kukarugamu okukyendeeza kwa FE kwa 30% omu shaaha 10 zonka (ekishushani S1a–c). Nikimanyisa ngu okukozesa 1 M KOH anolyte ni kikuru munonga kukyendeeza aha nkora y‘okuhindura oxygen (OER)37 n‘okuhikiiriza okuhikirizibwa kwa ion omu kitanda ky‘okuhindura cathode33. Okuteerana kwa anolyte kwakyendeera kuhika ahari 0.1 M KOH, bombi amaani g‘obutafaari n‘okuhindura kwa formic acid (okufeerwa kwa formic acid) nibyeyongyera (ekishushani S1d), ekirikworeka okushuubuza kwa zero-sum. Ekipimo ky’okuhindura formate oxidation kikakyeberwa barikukoresa omubaro gw’oburemeezi bwona; okumanya ebirikukiraho, reeba ekicweka “Emiringo.” Okukora okurikukoresa MEA n‘enkora y‘omubiri emwe eya CEM nayo ekakyeberwa, kandi ebyarugamu nibyorekwa omu kishushani S1f,g. FE formate eyashohoziibwe kuruga omu katodi ekaba eri >60% ahari 200 mA/cm2 aha kutandika kw’okukyebera, kwonka ekasheenyagurika juba omu shaaha ibiri ahabw’okuteerana kw’omunyugunyu gwa katodi ogwagambirweho enyima (ekishushani S11).
Ekishushani kya zero-gap MEA erimu CO2R aha katodi, okugarukamu kw‘okuhindura kw‘amaizi (HOR) nari OER aha anode, n‘ekibunu kimwe kya AEM ahagati. b FE n‘amaani g‘obutafaari ahabw‘okutebeekanisa oku na 1 M KOH na OER ebirikugyendera aha anode. Enshobi z‘emiti nizijwekyera okutaana kw‘omutindo gw‘ebipimo bishatu ebitarikushushana. omu FE n‘amaani g‘obutafaari bw‘omubiri na H2 na HOR aha anode. Erangi zitari zimwe na zimwe nizikoresibwa kutaanisaho okukora kwa formate na formic acid. d Ekishushani ky‘okureeberaho kya MEA na BPM ehindukire omu maisho ahagati. FE n‘amaani ga battery n‘obwire ahari 200 mA/cm2 orikukoresa enkora egi. f Ekishushani ky‘okusharaho eky‘omu maisho BPM MEA bwanyima y‘okugyezibwa okukye.
Okubaasa kureetaho asidi ya formiki, haidrojeni neeheebwa ekirungo kya Pt-aha-kaboni (Pt/C) aha anode. Nkoku kirikworekwa omu kishushani 2d, BPM erikuta omu maisho erikureetaho purotoni aha anode ekacondoozibwaho enyima kubaasa kutunga okukora kwa formic acid. Ekikwato ky‘okuhindura BPM kikaremwa bwanyima y‘okukora edakiika 40 aha nkora ya 200 mA/cm2, kirikuhererukayo n‘okutunguuka kw‘amaani g‘okurenga ahari 5 V (Fig. 2e). Bwanyima y‘okukyebera, okusheesheka okurikureebwa kukareebeka aha nkoragana ya CEM/AEM. Oyihireho formate, anions nka carbonate, bicarbonate na hydroxide nazo nizibaasa kuraba omu nkora ya AEM kandi zikwatagane na purotoni aha nkoragana ya CEM/AEM kureetaho omuyaga gwa CO2 n’amaizi g’amaizi, ekirikureetaho okusheesheka kwa BPM (ekishushani 2f) kandi , aha muheru nikireetaho okuremwa kw’obutafaari.
Okurugirira aha nkora y‘okukora n‘okuremwa kw‘enkora y‘ahaiguru, enkora nsya ya MEA neeteekateekwaho nk‘oku erikworekwa omu kishushani 1c kandi neeshoboororwa omu bwijwire omu kishushani 3a38. Aha, omutindo gwa PCEM niguha omuhanda gw’okufuruka kwa formic acid na anions kuruga omu nkora ya CEM/AEM, obwo nigukyendeeza aha kuteerana kw’ekintu. Omu bwire nibwo bumwe, omuhanda gwa PCEM ogw‘omugati niguhabura formic acid omu mwanya gw‘okujanjaara n‘okusheesheka, ekirikukyendeeza aha kubaasa kw‘okuhinduka kwa formic acid. Ebirugire omu kucondooza kwa polarization barikukoresa AEMs eziine obuhango bwa mm 80, 40 na 25 nibyorekwa omu kishushani 3b. Nk‘oku kirikuteekateekwaho, n‘obu amaani g‘obutafaari goona garaabe nigayeyongyera n‘okweyongyera kw‘obuhango bwa AEM, okukoresa AEM erimu obuhango nikuzibira okujanjaara kw‘enyima kwa formic acid, obwo nikwongera pH ya katodi n‘okukyendeeza aha kureetaho H2 (Fig. 3c–e).
a Eky‘okureeberaho ky‘omutindo gwa MEA na AEM na CEM erimu ebitobo n‘emihanda y‘okutwara formic acid etari emwe n‘emwe. b Amashanyarazi g‘obutafaari aha nkora zitari zimwe na zimwe n‘obuhango bwa AEM obutari bumwe na bumwe. omu EE aha nkora zitari zimwe na zimwe z‘obwire obu n‘obuhango bwa AEM bwa 80 μm (d) 40 μm, e) 25 μm. Enshobi z‘emibaro nizijwekyera okutaana kw‘omutindo okupimirwe kuruga omu sampo ishatu z‘omutaano. f Ebirugire omu kugyeragyeranisa eby‘okutaho formic acid n‘omuhendo gwa pH aha nkoragana ya CEM/AEM aha nkora ya AEM etari emwe n‘emwe. f PC na pH omu nkora ya katodi ey’ekirungo ky’ebintu ebiine obuhango bwa firimu ya AEM etari emwe n’emwe. g Okugabanisa kw‘ebicweka bibiri eby‘okuteerana kwa formic acid n‘okutaho CEM/AEM n‘okusheenya.
Ekishushani S2 nikyoreka okugabwa kw‘okutaho ebiriisa bya formic acid na pH omu nkora ya MEA yoona orikukoresa enkora ya Poisson-Nernst-Planck ey‘ebintu ebiine obugarukiro. Tikirikutangaaza kureeba ngu omubaro gw’ekiriisa kya formic acid ogurikukirayo, 0.23 mol/L, nigureebeka aha nkoragana ya CEM/AEM, ahabw’okuba formic acid neehangwa aha nkoragana egi. Okuteerana kwa formic acid kurabira omu AEM nikukyendeera juba munonga nk‘oku obuhango bwa AEM burikweyongyera, ekirikworeka okuzibira kwingi okutwarwa kw‘ebintu bingi n‘okukyendeeza aha kusheeshasheesha kwa formic acid ahabw‘okujanjaara kw‘enyima. Ebishushani 3 f na g nibyoreka omuhendo gwa pH na formic acid omu kitanda kya cathode catalyst ekirikureetwaho okujanjaara kw’omugongo n’okugabwa kw’ebicweka bibiri eby’okuteerana kwa formic acid, nk’oku biri. Oku omubiri gwa AEM gurikukyendeera, nikwo n’okuteerana kwa formic acid kurikweyongyera haihi n’ekirungo kya katodi, kandi pH ya katodi neehinduka asidi. Nahabwekyo, n’obu obutafaari bwa AEM obuhango buraabe niburugamu okufeerwa kw’ohmic kwingi, nibukora munonga omu kuzibira okugaruka kujanjaara kwa formic acid kuza omu cathode n’okutunguura obushemeire bw’ahaiguru obw’enkora ya FE formic acid. Eky‘aha muheru, okwongyera aha buhango bwa AEM kuhika ahari 80 μm kikarugamu FE >75% ahabwa formic acid ahari <2 V na 300 mA/cm2 ahabw‘omwanya gw‘obutafaari bwa 25 cm2.
Okugyezaho okuhama kw’omutindo ogu ogurikwegamira ahari PECM, amashanyarazi ga battery gakaguma gari aha 200 mA/cm2 kumara eshaaha 55. Ebirugiremu byona nibyorekwa omu kishushani 4, n‘ebirugire omu shaaha 3 z‘okubanza nibyorekwa omu kishushani S3. Ku barikukoresa Pt/C anodic catalyst, amaani g‘obutafaari gakeeyongyera munonga omu dakiika 30 z‘okubanza (ekishushani S3a). Omu bwire buraingwa, amaani g‘obutafaari gakaguma haihi nk‘oku gari, gakaha omubaro gw‘okusheenya 0.6 mV/h (Fig. 4a). Omu kutandika kw’okukyebera, PV ya formic acid eyaabaire eteeraine aha anode ekaba eri 76.5% kandi PV ya hydrogen eyaabaire eteeraine aha cathode ekaba eri 19.2%. Bwanyima y’eshaaha y’okubanza y’okukyebera, FE ya haidrojeni ekagwa kuhika ahari 13.8%, ekirikworeka okutoorana kwa formate okutunguukire. Kwonka omubaro gw’okuhindura ebiriisa bya formic acid omu nkora gukeyongyera kuhika ahari 62.7% omu shaaha 1, kandi omubaro gw’okuhindura ebiriisa bya anodic formic acid gukeeyongyera kuruga haihi ahari zero aha kutandika kw’okukyebera kuhika ahari 17.0%. Okurugirira ahari ekyo, FE ya H2, CO, formic acid n’omubaro gw’okuhindura anodic oxidation ya formic acid bikaguma bigumire omu bwire bw’okugyezesa. Okwongyera aha kuhinduka kwa formic acid omu shaaha y‘okubanza nikubaasa kuba nikureetwaho okuteerana kwa formic acid aha nkoragana ya PCEM/AEM. Okuteerana kwa formic acid ku kurikweyongyera, tikurikuruga omu kusheeshasheesha kw’ekibunu kyonka, kureka nikujanjaara kurabira omu FEM ahabwayo kandi kutaaha omu Pt/C anode layer. Ahabw’okugira ngu formic acid n’amaizi aha 60°C, okuteerana kwayo nikubaasa kureetera oburemeezi omu kuhingisa obuhango kandi kirugyemu okukunda okuhinduka kw’okwotsya okukira haidrojeni.
a Amashanyarazi g‘obutafaari n‘obwire (200 mA/cm2, 60 °C). Ekicweka ky‘omunda nikyoreka ekishushani kya optical microscope eky‘ekicweka ky‘okusharaho ekya MEA ekirimu EM erimu ebitobo. Omubaro gw’okupima: 300 μm. b Obushemeire bwa PE na formic acid nk‘omurimo gw‘obwire ahari 200 mA/cm2 orikukoresa anode ya Pt/C.
Enkora y‘eby‘okureeberaho aha kutandika kw‘okukyebera (BOT) omu bwire bw‘okutebeekanisa n‘aha muheru gw‘okukyebera (EOT) bwanyima y‘eshaha 55 z‘okukyebera okuhamire ekamanyirwa aha kukoresa nano-X-ray computed tomography (nano-CT), nk‘oku kirikworekwa omu kishushani 5 a. Eky‘okureeberaho kya EOT kiine obuhango bw‘ebicweka by‘omubiri ebihango ebiine oburaingwa bwa 1207 nm kugyeragyeranisa na 930 nm ahabwa BOT. Ebishushani by‘okukyebera eby‘omumwanya gw‘omwirima eby‘omumwanya gw‘ahaiguru (HAADF-STEM) n‘ebirugire omu kucondooza kw‘okujanjaaza amaani (EDS) nibyorekwa omu kishushani 5b. N‘obu omutindo gw‘okureetaho BOT guraabe gurimu obucweka obukye bw‘okureetaho obucweka bw‘omubiri oburikukira obwingi hamwe n‘ebicweka bimwe ebihango ebirikuteerana, omu nkora ya EOT omutindo gw‘okureetaho okuhinduka nigubaasa kubaganisibwamu ebicweka bibiri eby‘omutaano: kimwe kiine obucweka bw‘omubiri obugumire munonga kandi ekindi kiine ebicweka by‘omubiri ebiine obucupa bwingi. Omubaro gw’ebicweka ebikye. Ekishushani kya EDS nikyoreka ngu obucweka obuhango obugumire burimu Bi nyingi, nikibaasa kuba kiri eky’ekyoma Bi, kandi emyanya erimu obucupa erimu oxygen nyingi. Obutafaari bwaba nibukora aha 200 mA/cm2, obushoboorozi obubi bwa katodi nibwija kureetera okukyendeeza kwa Bi2O3, nk’oku kirikworekwa omu byarugamu omu kucondooza kwa in situ X-ray absorption spectroscopy ebigambirweho ahaifo. Ebirugire omu kucondooza kwa maapu ya HAADF-STEM na EDS nibyoreka ngu Bi2O3 neehingura omu nkora y’okukyendeeza, ekirikugireetera kufeerwa oxygen kandi ekateerana omu bicweka by’ekyoma ebihango. Enkora ya X-ray diffraction ya katodi za BOT na EOT neehamya okushoboorora kw’ebihandiiko bya EDS (Fig. 5c): Bi2O3 yonka ey’ekibiriiti ekashangwa omu katodi ya BOT, kandi bimetal ey’ekibiriiti ekashangwa omu katodi ya EOT. Okwetegyereza oku obushoboorozi bwa katodi burikukora aha mbeera y’okuhindura ebiriisa bya Bi2O3, ebirikuba biriho bikahindurwa kuruga aha bushoborozi bw’okutambura okukingire (+0.3 V vs RHE) kuhika ahari -1.5 V (vs RHE). Nikireebeka ngu omurundi gwa Bi2O3 nigutandika kukyendeera ahari -0.85 V kugyeragyeranisa na RHE, kandi okukyendeera kw’amaani g’omurongooti ogurikwera omu kicweka ky’aha rubaju rw’ekishushani nikyoreka ngu Bi ey’ekyoma neekyendeera kuhika ahari 90% ya RHE ahari -1.1. V aha RHE (ekishushani 5d). Hatariho kugyendera aha nkora, okutoorana kwa formate kwona aha katodi omu bwijwire tikurikuhinduka, nk’oku kirikushoboororwa kuruga omu H2 na CO FE n’okukora kwa formic acid, n’obu haraabe hariho empindahinduka mpango omu nkora ya katodi, embeera y’okuhindura ebiriisa, n’omutindo gwa microcrystalline.
a Omuringo gw’ebicweka bishatu eby’omubiri gw’ekicweka ky’omubiri n’okugabwa kw’ebicweka by’omubiri ebitungirwe barikukoresa nano-X-ray CT. Omubaro gw’okupima: 10 μm. b Ahaiguru 2: Ebishushani bya HAADF-STEM eby‘ebicweka bya katodi eby‘ebikwato bya BOT na EOT. Omubaro gw’okupima: 1 μm. Ahansi 2: Ebishushani bya HADF-STEM na EDX ebihango eby‘omutindo gwa katodi gw‘ekirungo kya EOT. Omubaro gw’okupima: 100 nm. c Emitwarize y‘okutambura kwa X-ray ey‘eby‘okureeberaho bya katodi ya BOT na EOT. d Omu mwanya X-ray okunywanisa kw‘eby‘okurya bya Bi2O3 omu 0.1 M KOH nk‘omurimo gw‘obushoboorozi (0.8 V kuhika -1.5 V vs. RHE).
Kubaasa kumanya gye emigisha eriho ey‘okutunguura okukoresa gye amaani orikuzibira okuhinduka kwa formic acid, H2 reference electrode ekakoresibwa kumanya ekirikureetaho okufeerwa kw‘amaani39. Aha nkora y‘obwire obu eri ahansi ya 500 mA/cm2, obushoboorozi bwa katodi nibuguma ahansi ya -1.25 V. Obushoboorozi bwa anodi nibubaganisibwamu ebicweka bibiri ebikuru: oburemeezi bw‘okuhindura obw‘obwire obu HOR n‘obuhango bw‘amaani oburengire obw‘okuteekateeka HOR 40 oburikuteberezibwa ahabw‘okupimwa enyimaho equmic ahabw‘ekicweka kya Bulter-V, . asidi. Ahabw’okugira ngu enkora y’okugarukamu neekora mpora munonga waagyeragyeranisa na HOR41, omubaro mukye gw’okugarukamu kwa formic acid oxidation aha anode nigubaasa kurugamu okweyongyera kw’amaani omu bushoborozi bwa anode. Ebirugiremu nibyoreka ngu okuzibira okuhikire kw‘okuhindura kwa formic acid anodic oxidation nikubaasa kwihaho haihi 500 mV y‘amaani g‘okurenga.
Okugyezaho okutebereza oku, omubaro gw’okusheesheka kw’amaizi agarimu deionized (DI) aha ntandikiro ya anode gukahindurwa kukyendeeza aha kusheesheka kw’amaizi agarikuruga omu formic acid. Ebishushani 6b na c nibyoreka FE, okuteerana kwa formic acid, n‘amaani g‘obutafaari nk‘omurimo gwa DI flux aha anode ahari 200 mA/cm2. Omubaro gw‘okusheeshasheesha kw‘amaizi agarimu deionized ku gwabaire nigweyongyera kuruga ahari 3.3 mL/min kuhika ahari 25 mL/min, okuteerana kwa formic acid aha anode kukakyendeera kuruga ahari 0.27 mol/L kuhika ahari 0.08 mol/L. Omu kugyeragyeranisa, okukoresa omutindo gwa sandwich ogwateirweho Xia na bagyenzi be. 30 omubaro gw’ekiriisa kya formiki ogwa 1.8 mol/L gukatunga 200 mA/cm2. Okukyendeeza aha kuteekateeka nikutunguura FE yoona eya formic acid kandi nikikyendeeza FE ya H2 nk‘oku pH ya katodi erikweyongyera kuba alkaline ahabw‘okukyendeeza aha kujanjaara kwa formic acid omu mugongo. Okukyendeeza aha nkora ya formic acid aha nkora ya DI erikukirayo nakyo kikaba nikiihaho okuhinduka kwa formic acid, ekyarugiremu amaani g‘obutafaari goona agabaire gari ahansi ya 1.7 V ahari 200 mA/cm2. Ebiriisa bya battery nabyo nibikwata aha kukora kwona, kandi ebyarugamu nibyorekwa omu kishushani S10. Kwonka, ebyombeko ebirikwegamira ahari PCEM nibibaasa kutunguura munonga okukoresa gye amaani omu kuzibira okuhinduka kwa formic acid, yaaba kurabira omu kukoresa anodic catalysts eziine okutoorana kwa hydrogen okurungi kuza omu formic acid nari kurabira omu kukora kw’ebikwato.
a Okuhendagura kw‘amaani g‘obutafaari orikukoresa obutafaari bw‘okureeberaho H2 electrode erikukora aha 60 °C, Pt/C anode na 80 μm AEM. b FE na formic acid ebirundainwe ahari 200 mA/cm2 barikukoresa emihendo y‘okusheesheka etari emwe n‘emwe y‘amaizi agatarimu anodic deionized. c Anode ku erikuteerana formic acid omu bipimo bitarikushushana, amaani g’obutafaari ni 200 mA/cm2. Enshobi z‘emibaro nizijwekyera okutaana kw‘omutindo gw‘ebipimo bishatu ebitarikushushana. d Omuhendo gw‘okuguza oguri ahansi munonga ogucwekirwemu ahabw‘okukora aha mihendo y‘okusheeshasheesha kw‘amaizi agatari gamwe na gamwe orikukoresa emihendo y‘amashanyarazi g‘omu ihanga ey‘amakorero eya US$0.068/kWh na US$4.5/kg haidrojeni. (*: Embeera y’okukyendeeza aha nkora ya formic acid aha anode neeteekateekwaho kuba 10 M FA, omuhendo gw’amashanyarazi g’amakorero omu ihanga ryona ni $0.068/kWh, kandi haidrojeni ni $4.5/kg. **: Embeera y’okukyendeeza aha nkora ya formic acid neeteekateekwaho kuba edede anode. Omuhendo gwa FA aha anode ni 1, thelect3. $0.03/kWh, kandi omurongooti ogurimu obutonyezi nigujwekyera omuhendo gw’akatare gwa 85 wt% FA.
Okushwijuma kwa tekinologiya n‘eby‘entasya (TEA) kukakorwa kutunga omuhendo mukye gw‘okuguza eby‘okuteerana by‘amajuta ahansi y‘embeera z‘okukora zitari zimwe na zimwe, nk‘oku kirikworekwa omu kishushani 5d. Emiringo n‘ebihandiiko by‘enyima ebya TEA nibibaasa kushangwa omu SI. LC concentration omu anode exhaust yaaba eri ahaiguru, n‘obu cell voltage eraabe eri ahaiguru, omuhendo gwona ogw‘okuteerana amajuta nigukyendeera ahabw‘okukyendeeza aha sente z‘okwahukana. Ku kiraabe ngu anodic oxidation ya formic acid neebaasa kukyendeezibwa kurabira omu kutunguura catalyst nari tekinologiya ya electrode, okuteerana kw’amaani g’obutafaari obukye (1.66 V) n’okutaho FA kwingi omu maizi agarikuruga omu maizi (10 M) kukaba nikwija kukyendeeza aha sente z’okukora FA y’amashanyarazi kuhika ahari 0.74 US dollars/kg (okurugiirira aha mashanyarazi). omuhendo) $0.068/kWh na $4.5/kiro y’amaizi42. Ekindi, ku kirikugambwaho n‘omuhendo gw‘omumaisho ogurikuteekateekwaho ogw‘amashanyarazi agarikugarukaho ogwa $0.03/kWh na haidrojeni gwa $2.3/kg, ekigyendererwa ky‘amaizi g‘ebishaka ekya FA nikikyendeera kuhika ahari miriyooni 1.3, ekirikureetaho omuhendo gw‘okukora ogurikuteekateekwaho ogw‘aha muheru ni US$0.66/kg43. Eki nikigyeragyeranisibwa n’emihendo y’akatare eriho hati. Nahabwekyo, okuteeraho kw’omumaisho okutaire omutima aha bintu by’amashanyarazi n’enkora nikubaasa kwongyera kukyendeeza aha anodization obwo kurikwikiriza okukora aha voltages z’obutafaari obukye kureetaho LC concentrations z’ahaiguru.
Omu bugufu, tukashoma aha mitwarize mingi ya zero-gap MEA ahabw‘okukyendeeza CO2 kuhika ahari formic acid kandi twateekateeka aha nkora erimu ekicweka ky‘omubiri ekirikureeba omu maisho ekirimu ekicweka ky‘omubiri ekirikuhindura cation (PECM) ekirimu ebitobo kuhwera omu nkora y‘okuhingisa oburemeezi bw‘omubiri ahabw‘ekirungo kya formic acid ekirikurugamu. . Entebekanisa egi neereetaho >96% ya asidi ya formic aha bipimo ebirikuhika ahari 0.25 M (aha nkora y‘okusheeshasheesha kwa anode DI eya 3.3 mL/min). Aha mibaro y‘okusheeshasheesha kwa DI eri ahaiguru (25 mL/min), enkora egi ekaha oburemeezi bw‘obwire obu >80% FE ya 200 mA/cm2 ahari 1.7 V orikukoresa omwanya gw‘obutafaari bwa 25 cm2. Omu mibaro ya anodic DI ey‘omutindo gw‘ahaiguru (10 mL/min), enkora ya PECM ekaguma n‘amaani g‘amaani n‘embeera z‘ahaiguru za formic acid FE kumara eshaaha 55 z‘okugyezibwa ahari 200 mA/cm2. Okuhama n’okutoorana kw’ahaiguru okurikuhikirizibwa ebikwato ebirikuguzibwa n’ebintu bya polymeric membrane nibibaasa kwongyerwamu amaani orikubigaita n’ebikwato by’amashanyarazi ebihikire. Omurimo ogurikukurataho nigwija kuta omutima aha kuhindura embeera z‘okukora, okutoorana anode catalyst, n‘omutindo gwa MEA kukyendeeza aha kuhindura kwa formic acid oxidation, ekirikureetaho okusheeshasheesha okurikukirayo aha nkora y‘obutafaari bw‘ahansi. Enkora eyorobi ey‘okukoresa carbon dioxide ahabwa formic acid erikworekwa aha neemaraho okwetenga kw‘ebishengye bya anolyte na catholyte, ebicweka bya sandwich, n‘ebintu by‘omutaano, obwo nikwo kwongyera aha maani g‘obutafaari n‘okukyendeeza aha kugumizamu kw‘enkora, ekirikureetera kyanguha kutunguuka. Entebekanisa etebekanisiibwe neeha omuhanda gw’okutunguura eby’obuhangwa n’eby’entaasya omu biro by’omumaisho eby’okuhindura CO2.
Okwihaho kyaba kitagambirwe, ebintu byona eby‘omutindo gw‘eby‘emibazi n‘ebirungo bikakoresibwa nk‘oku byatungirwe. Ekirungo ky’okureetaho ebiriisa (Bi2O3, 80 nm) kikagurwa kuruga omu kitongore ky’okucondooza ekya US, Inc. N-propanol (nPA) ey’omuringo gwa Omnisolv® n’amaizi agarikwera munonga (18.2 Ω, enkora y’okushemeza amaizi eya Milli–Q® Advantage A10) bikagurwa kuruga omu kampuni ya Millipore Sigma. Methanol na asetoni eziine orusa rwa ACS nizigurwa kuruga omu kampuni za VWR BDH® na Fisher Chemical, nk’oku zirikukuratana. Empunu ya polimeri ekataburwa n’omutaano gwa acetone na methanol omu nkora ya 1:1 omu buremeezi kutunga okujanjaara kwa polimeri okurimu 6.5 wt.%. Tebeekanisa erangi y’okureetaho ebiriisa orikutabura 20g Bi2O3, amaizi marungi munonga, nPA n’okujanjaara kwa ionomer omu nsaka ya miriyoni 30. Ekirungo eki kikaba kirimu 30 wt.% y’ekirungo, omubaro gw’oburemeezi bwa ionomer n’ekirungo kya 0.02 n’omubaro gw’oburemeezi bw’omwonyo n’amaizi 2:3 (40 wt.% nPA). Batakatabwire, 70g y’ebintu by’okushenda ebya Glen Mills 5mm zirconia bikateebwa omu ntamu. Sampuli zikateebwa aha rubaaho rwa FisherbrandTM rwa dijitali aha 80 rpm kumara eshaaha 26. Reka erangi esitame kumara edakiika 20 otakagiteekaho. Erangi ya Bi2O3 ekateebwa aha kikwato kya Qualtech ekirikukoresibwa kyonka (QPI-AFA6800) barikukoresa 1/2′′ x 16′′ okugaruzaho waya z’okukyebera (RD Specialties – oburaingwa bwa miriyooni 60) ahari 22°C. 5 mL y‘erangi y‘okureetaho okuhinduka ekateebwa aha kikwato ky‘okujanjaaza omuyaga gwa kaboni Sigraacet 39 BB ekya inci 7.5 x 8 (okubiika amajuta) kurabira omu kuteekaho enkoni aha sipiidi etarikuhinduka eya 55 mm/sec. Hindurira ebikwato ebi ebiine erangi omu furiigi kandi obyomye aha 80 °C. Omuringo gw‘okujwara enkoni n‘ebishushani by‘okujwara GDE nibyorekwa omu bishushani S4a na b. Ekikwato ky’okukyebera ebiri omu itaka (XRF) kikahamya ngu okutaho GDE eyaabaire erimu 3.0 mg Bi2O3/cm2.
Aha nkora y‘ebicweka by‘omubiri ebirimu ebicweka by‘omubiri ebirikuhindura anion (AEM) na CEM erimu ebitobo. Nafion NC700 (Chemours, USA) erimu obuhango bw’eiziina bwa 15 μm ekakoresibwa nk’omutindo gwa CEM. Ekirungo kya anodic kikafuuhirirwa butunu aha FEM n’omubaro gwa ionomer na carbon ogwa 0.83 n’omwanya gw’okukingira ogwa 25 cm2. Platinum erikushagikwa erimu omwanya muhango gw’ahaiguru (50 wt.% Pt/C, TEC 10E50E, ekyoma ky’omuhendo kya TANAKA) erimu omutwaro gwa 0.25 mg Pt/cm2 ekakoresibwa nk’ekintu ekirikureetaho anode. Nafion D2020 (Ion Power, USA) ekakoresibwa nk’ekintu ekirikureetaho okuteerana kw’eby’okurya. Okusheenya kwa CEM nikukorwa omu kushara emiringo erikushushana aha firimu ya CEM aha bwire bwa 3mm. Ebirikukwata aha nkora y‘okusheenya nibyorekwa omu bishushani S12b na c. Okukozesa X-ray computed tomography, kikahamibwa ngu omwanya gw’okusheenya gukaba guri 32.6 μm, nk’oku kirikworekwa omu kishushani S12d na e. Omu bwire bw‘okuteerana obutafaari, ekipande kya CEM ekirimu ebitobo ekirimu ekirikureetaho okuhinduka kikateebwa aha rupapura rwa Toray orwa cm2 25 (5 wt% PTFE eyajanjabirwe, Fuel Cell Store, USA). Ekipande kya AEM (PiperION, Versogen, USA) ekiine oburaingwa bwa 25, 40 nari 80 μm kikateebwa ahaiguru ya CEM reero bwanyima aha katodi ya GDE. Ekipande kya AEM kikatemwa omu bicweka bya sentimita 7.5 × 7.5 kukingaho omusiri gwona ogw’okusheesheka kandi kyateebwa omu kiro kyona omu 1 M potassium hydroxide solution kitakateeraine. Anode na cathode zombi nizikoresa ebikwato bya PTFE ebiine obuhango oburikumara kubaasa kutunga okunyigirizibwa kwa GDE okuhikire okwa 18%. Ebirikukwata aha nkora y‘okuteerana battery nibyorekwa omu kishushani S12a.
Omu kugyezibwa, obutafaari obuteeraine bukaguma buri aha 60 °C (30, 60, na 80 °C ahabw’okucondooza okurikurugiirira aha bwire bw’obwire) n’omuyaga gwa haidrojeni 0.8 L/min ogwaheebwa anode na 2 L/min gwa carbon dioxide ogwaheebwa katodi. Emigyera y’omuyaga yoona eya anodic na cathodic ekaba erimu obutagatsi aha 100% y’obutagatsi oburikugyeragyeranisibwa n’obutagatsi bwa 259 kPa obuhikire. Omu bwire bw‘okukora, omugyera gwa gaasi ya katodi gukatabura n‘omubazi gwa 1 M KOH aha rurengo rwa 2 mL/min kutunguura okukoresa ekitanda ky‘okureetaho katodi n‘okutwara ionic. Tabura omugyera gwa gaasi ya anode n‘amaizi agatarimu ioni aha sipiidi ya miriyoni 10/edakiika kwihaho formic acid aha anode. Ebirikukwata aha bikwatiraine n‘ebikwato ebirikutaaha n‘ebirikurugamu nibyorekwa omu kishushani S5. Omuyaga ogurikuruga omu katodi gurimu CO2 kandi nigureetaho CO na H2. Omuyaga gw’amaizi nigwihwaho kurabira omu kikwato ekirikuhindura obutagatsi (ekintu ekirikuhindura obutagatsi bw’obwire bukye ahari 2°C). Gaasi esigaireho neija kurundaanwa kukyeberwa obwire bwa gaasi. Okutambura kwa anode nakwo nikwija kuraba omu condenser kutaanisa amaizi na gaasi. Amaizi g’ebishaka nigaija kurundaanwa omu bidomora ebishemeire kandi gakyeberwe barikukoresa liquid chronometry kubaasa kumanya obuhango bwa formic acid erikurugamu. Okukyebera kw’amashanyarazi kukakorwa barikukoresa ekikwato kya Garmy (enamba y’okureeberaho 30K, Gamry, USA). Batakapimire omubaro gw’okuteerana, obutafaari bukaba butebeekanisiibwe emirundi 4 omu nkora kuruga ahari 0 kuhika ahari 250 mA/cm2 barikukoresa linear voltammetry n’omubaro gw’okukyebera ogwa 2.5 mA/cm2. Polarization curves zikatunga omu muringo gwa galvanostatic n’obutafaari obukwatsirwe aha nkora y’amaani emwe kumara edakiika 4 batakatandikireho sampo y’omuyaga gwa katodi n’amaizi ga anolyte.
Nitukoresa ekikwato ky’okureeberaho eky’amaizi omu MEA kutaanisa obushoboorozi bwa katodi n’obwa anodi. Omuringo gw‘okukoresa ekiriisa ky‘okureeberaho nigworeka omu kishushani S6a. Ekirungo kya Nafion (Nafion 211, IonPower, USA) kikakozesebwa nk’orubaju rw’okugaita ekicweka kya MEA n’ekikwato ky’okureeberaho. Enshonga emwe y‘omubaro gwa Nafion ekaba ekwataniise n‘ekikwato ky‘okujanjaaza omuyaga (GDE) kya cm2 1 ekirimu 0.25 mg Pt/cm2 (50 wt% Pt/C, TEC10E50E, eby‘ekyoma by‘omuhendo bya TANAKA) ekyateirwe aha mpapura za kaboni eza 29BC (Fuel USA Cell). ). Ekikwato ky’omutaano ekya polyetheretherketone (PEEK) nikikoresibwa kukingaho gaasi n’okureeba ngu hariho okukwatagana kurungi ahagati y’ebicweka bya GDE na Nafion, n’okutaho ekikwato ky’okureeberaho n’ekikwato ky’amajuta. Omuheru ogundi ogw’omurongooti gwa Nafion nigukwatanisa n’orubaju orurikuruga aheeru rwa battery ya CEM. Ekishushani S6b nikyoreka ekicweka ky‘okusharaho eky‘okureeberaho ky‘eby‘okureeberaho ebiine akakwate na MEA.
Bwanyima y’omuyaga ogurikuruga omu itaka kuraba omu kikwato ekirikutaanisa gaasi n’amaizi, sampo za gaasi nizitwarwa kuruga omu katodi. Gaasi eyaarundainwe ekakyeberwa haakiri emirundi eshatu barikukoresa ekikwato kya 4900 Micro GC (ekikwato ky‘okukyebera 10 μm, Agilent). Sampuli zikatorotoorwaho omu nshaho z‘okushoroora gaasi z‘ekyoma z‘aluminiyamu ezitarikukora SupelTM (Sigma-Aldrich) kumara obwire obutebeekanisiibwe (sekondi 30) kandi zikateebwa omu ngaro omu nkora ya microgas chromatograph omu shaaha ibiri kuruga obu zashoroozibwa. Ebiriisa by’okuteera omubazi bikateebwa ahari 110°C. Kaboni (CO) na haidrojeni (H2) bikataanisibwa aha nkora y’okwotsya (105 °C) erimu omuhimbo (28 psi) 10 m MS5A enyomyo barikukoresa argon (Matheson Gas-Matheson Purity) nk’omuyaga ogurikutwara. Enkwatanisa ezi nizimanyirwa aha kukoresa ekikwato ekirimu ebirikumanyisa oku obutagatsi burikukora (TCD). Ebishushani bya GC n‘ebikwato by‘okupima CO na H2 nibyorekwa omu kishushani S7. Sampuli z‘amaizi ga formic acid zikatorotoorwaho kuruga omu anode kumara obwire obutebeekanisiibwe (sekondi 120) kandi zasendwa barikukoresa ekishwijumwa ky‘empiira kya 0.22 μm PTFE omu bikopo bya 2 mL. Ebintu by’amaizi ebiri omu bikopo bikakyeberwa barikukoresa enkora ya Agilent 1260 Infinity II bioinert ey’amaani g’okukyebera amaizi (HPLC), omu 20 μl y’eky’okureeberaho kyateebwamu kurabira omu nkora y’okukyebera (G5668A) erimu omurundi gw’okugyendera aha 4 mM sulfuric acid (H2SO4). ) aha nkora y‘okusheeshasheesha 0.6 ml/edakiika (pampu y‘ebicweka bina G5654A). Ebintu bikataanisibwa aha nkora y‘okurinda (35°C, omukyebe gw‘enyomyo G7116A) Aminex HPX-87H 300 × 7.8 mm (Bio-Rad) erikubanza n‘enyomyo y‘okurinda eya Micro-Guard Cation H. Formic acid ekakyeberwa barikukoresa ekikwato ky’okukyebera ebiri omu nkora (DAD). aha rubaju rw’omuyaga rwa 210 nm n’oburaingwa bw’omuyaga bwa 4 nm. Ekishushani kya HPL n‘omutindo gw‘okugyeragyeranisa ogwa formic acid nibyorekwa omu kishushani S7.
Ebirugire omu gaasi (CO na H2) FE nibibarwa barikukoresa enkora egi, kandi omubaro gwona ogwa mole za gaasi nigubarwa barikukoresa enkora ya gaasi ehikire:
Omuri ebyo: \({n}_{i}\): omubaro gw’ebicweka by’omubiri ebiri omu nkora y’amashanyarazi. \(F\): Ekirikugumaho ekya Faraday. \({C}_{i}\): Okuteerana kw’ebintu by’amaizi bya HPLC. \(V\): omubaro gw’eky’okureeberaho ky’amaizi ekirundainwe omu bwire obutebeekanisiibwe t. \(j\): oburemeezi bw’obwire obu. \(A\): Omwanya gw’eby’obuhangwa (25 cm2). \(t\): obwire bw’okutooranamu. \(P\): okugyemeserezibwa okuhikire. \({x}_{i}\): Ebicweka 10 ahari igana ebya gaasi ebirikumanyirwa ahari GC. \(R\): omuyaga ogutarikuhinduka. \(T\): obutagatsi.
Okuteerana kw’ebicweka by’omubiri ebirikwetwa anodic cations kukakyeberwa barikukoresa eby’okureeberaho by’okukyebera ebiri omu plasma (ICP-OES). Kationi ezirikubaasa kusheesheka nari kujanjaara omu anode harimu Ti, Pt, Bi na K. Okwihaho K, kationi ezindi zoona zikaba ziri ahansi y’ekikomo ky’okukyebera. Okukora ayoni omu nshonga kureka anode kukwatanisa na purotoni nari ebindi kationi. Nahabwekyo, obushemeire bwa formic acid nibubaasa kubarwa nka .
Okukora Formate/FA nikujwekyera omuhendo gwa FA ogurikukorwa ahari buri kWh y‘amashanyarazi agarikukoresibwa barikukoresa enkora ya MEA emwe, omu mol/kWh. Nikibarwa kurugiirira aha nkora y‘amaani, amaani g‘obutafaari n‘oburungi bwa Faraday ahansi y‘embeera z‘okukora ezitari zimwe na zimwe.
Barira omuhendo gwa formic acid oguri omu anode kurugiirira aha nkora yoona ey’oburemeezi. Ebintu bishatu ebirikurwanira nibibaho aha katodi: okuhinduka kwa haidrojeni, okukyendeeza CO2 kuba CO, n’okukyendeeza CO2 kuba formic acid. Ahabw‘okugira ngu twine omuringo gw‘okuhindura ebiriisa bya formic acid omu Anton, formic acid FE neebaasa kubaganisibwamu ebicweka bibiri: okuteerana asidi ya formic n‘okuhindura ebiriisa bya formic acid. Omubaro gwona ogw’oburemeezi nigubaasa kuhandiikwa ngu:
Twakozesa GC kugyeragyeranisa omuhendo gwa formic acid, hydrogen, na CO ezaabaire zirundainwe omu HPLC. Nikimanyisa ngu ebicweka ebikuru ebya formic acid bikatorotoorwaho kuruga omu anode barikukoresa enkora erikworekwa omu kishushani ky‘okwongyeraho S5. Omuhendo gwa formate ogurikushoroozibwa kuruga omu kishengye kya katodi tiguri muhango, niguhika aha nkora ibiri z’obuhango obukye, kandi niguhika ahansi ya 0.5% y’omubaro gwona ogwa SC.
Enkora y‘entambura erikugumizamu erikukoresibwa aha neerugiirira aha mirimo eyabandize aha nkora ezirikushushana34. Enkora y’okuteerana ey’okugyeragyeranisa kwa Poisson-Nerst-Planck (PNP) neekoresibwa kumanyisa okuteerana kw’amaizi n’obushoboorozi bw’amashanyarazi omu mitwe y’okutwara eby’amashanyarazi n’eby’amashanyarazi. Okureeba omu bwijwire eby‘okureeberaho ebiri ahansi y‘eby‘okureeberaho n‘eby‘okureeberaho bya geometry nibiheebwa omu SI.
Enkora egi neemanyisa okuteerana kw’ebintu munaana ebiri omu maizi (\({{{{{{\rm{C}}}}}}}}{{{{{\rm{O}}}}}}}}_{2 \rm{O}}}}}}}}{2 \aharubaju rwa bumosho ({{{{{\rm{aq}^}}}}\buryo)}\ ), \(r \ ({{{{\rm{O}}}}}}{{{{{\rm{H}}}}}^{-}\), \({{{{{\rm{ HCO}}}}}}}_{3}^{-}\), \({{{{\rm{CO}}}}}}_{{\rm{CO}}}}}} ({{{\rm{HCOOH}}}}}}\), \({{{{\rm{HCOO}}}}}}}}^{- }\) na \({{{{{\rm{K}}}}}}^{+}\)), obushoboorozi bw'amashanyarazi omu nkora y'okutwara amashanyarazi (\(\){phi) okutwara ekiriisa kya katodi. Obushoboorozi bw‘amashanyarazi omu mitendekyere (\({\phi }_{A}\) na \({\phi }_{C}\) nk‘oku biri). Omu mwanya gw’ekyo, tihariho obutafaari bw’amashanyarazi obw’omu kicweka nari emirimo y’okugabanisa eshagama erikuhikirizibwa, ekicweka ky’eshagama y’omu mwanya nikishoboororwa butunu barikukoresa ekibaro kya Poisson; Enkora egi neetubaasisa kugyeragyeranisa butoosha ebirugire omu kugaruka enyima kwa Donnan aha nkora ya CEM|AEM, CEM|Pore, na AEM|Pore. Okwongyera ahari ekyo, enteekateeka ya porous electrode theory (PET) neekoresibwa kushoboorora okutwarwa kw’eshagama omu nkora ya anodic na cathodic ey’ekintu ekirikureetaho okuhinduka. Okurugiirira aha kumanya kw‘abahandiiki, omurimo ogu nigujwekyera okukoresa kwa PET okwabandize omu nkora eziine ebicweka by‘okushashura eby‘omu mwanya bingi.
Sampuli za katodi za GDE BOT na EOT zikakyeberwa barikukoresa Zeiss Xradia 800 Ultra erimu 8.0 keV X-ray entandikwa, okunywanisa n‘emiringo y‘omusiri muhango, n‘okuteerana ebishushani1. Ebishushani 901 bikatorotoorwaho kuruga ahari -90° kuhika ahari 90° n’obwire bw’okubishohoza bwa sekondi 50. Okugaruka kwombeka kukakorwa barikukoresa ekicweka ky’okushwijuma eky’okureeberaho ky’enyima ekiine obuhango bwa voxel bwa 64 nm. Okushwijuma okugabanisa n‘okugabanisa obuhango bw‘ebicweka kukakorwa barikukoresa koodi ehandiikirwe omu muringo gw‘omutaano.
Okucondooza okurikukoresibwa Electron microscopic nikutwariramu okuta MEAs z‘okugyezesa omu epoxy resin omu kutebeekanisa okusharaho okukye munonga n‘omusyo gwa diamond. Ekicweka ky’okusharaho kya buri MEA kikasharaho kuhika aha 50 kuhika 75 nm. Ekikwato ky’okupima ebiri omu nkora ya Talos F200X (Thermo Fisher Scientific) kikakoresibwa omu kupima ebiri omu nkora ya Talos F200X (STEM) n’okupima ebirikujanjaaza amaani (EDS). Microscope egi eine enkora ya EDS Super-X erimu ebikwato 4 ebirikumanyisa SDD ebitariho dirisa kandi neekora aha 200 kV.
Ebishushani by‘okukyebera eby‘obucupa (PXRD) bikatunga aha kikwato ky‘okukyebera eby‘obucupa ekya Bruker Advance D8 ekiine omushana gwa Cu Kα ogurikushwijumwa Ni ogurikukorera aha 40 kV na 40 mA. Omubaro gw’okukyebera niguruga ahari 10° kuhika ahari 60°, obuhango bw’eitembezo ni 0.005°, kandi omuvuyo gw’okutunga amakuru ni sekondi 1 ahari buri itembezo.
Ekishushani kya RAS aha rubaju rw’ekirungo kya Bi2O3 Bi L3 kikapimwa nk’omurimo gw’obushoboorozi barikukoresa akatafaari akakozirwe omu ka. Erangi ya Bi2O3 ekatebeekanisibwa barikukoresa 26.1 mg Bi2O3 erimu 156.3 μL y’omubazi gw’okuteerana (6.68%) kandi ekakyeberwa na 1 M KOH, amaizi (157 μL) n’omwengye gwa isopropyl (104 μL) kutunga erangi y’okuteerana. Omubaro gw’ebintu ebirikureetaho okuhinduka ni 0.4. Erangi ekateebwa aha mpapura za graphene omu bicweka by’enkokora (10×4 mm) kuhitsya obu okuremeera kw’ekirungo kya Bi2O3 kwahikire ahari 0.5 mg/cm2. Ekipande kya graphene ekisigaireho nikiteebwaho Kapton kubaasa kutaanisa emyanya egi kuruga omu nkora y’amashanyarazi. Orupapura rwa graphene orurimu ekiriisa kya catalyst rukateebwa ahagati ya PTFE ibiri kandi rwahamibwa aha mubiri gw’obutafaari (PEEK) n’ebikwato by’okuteera, ekishushani S8. Hg/HgO (1 M NaOH) ekakora nk’ekikwato ky’okureeberaho, kandi orupapura rwa kaboni rukakora nk’ekikwato ky’okubara. Ekikwato ky‘okureeberaho ekya Hg/HgO kikagyezesibwa barikukoresa waya ya platinum eyaabaire erimu 0.1 M KOH erimu haidrojeni kuhindura obushoboorozi bwona obupimirwe kuza omu nkora y‘okukoresa haidrojeni erikugaruka enyima (RHE). Ebishushani bya XRD bikatunga okureeberera obushoboorozi bw’ekintu ekirikukorera aha rupapura rwa Bi2O3/graphene ekibiikire omu 0.1 M KOH, ekirikwotsya kuhika ahari 30 °C. Amashanyarazi nigazengyerera omu battery, ahu amashanyarazi garikutaaha ahansi y’ekicweka ky’omubiri kandi ahu garikuruga ahaiguru kureeba ngu amashanyarazi gakwatagana n’ekicweka ky’omubiri ekirikureetaho okuhinduka (catalyst layer) ebicupuri byabaho. Ekikwato kya CH Instruments 760e potentiostat kikakozesebwa okutegyeka obushoboorozi bw‘eby‘amashanyarazi ebirikukora. Omukuratana gw‘obushoboorozi gukaba guri obushoboorozi bw‘okutambura okukingire: -100, -200, -300, -400, -500, -800, -850, -900, -1000, -1100, -1500 na +700 mV kurugiirira ahari RHE. Obushoboorozi bwa iR bwona bukahindurwa.
Bi L3 edge (~13424 eV ahabw’ekyoma kya Bi) Okukyebera okurikukwata aha nkora ya X-ray (XAFS) kukakorwa aha muhanda 10-ID, Enshonga y’okukyebera ebiri omu itaka (APS), ekitongore ky’okucondooza eky’omu ihanga ekya Argonne. Ekitongore ky’eihanga eky’okupima eky’okureeberaho. Ekikwato ky’erangi ibiri ekya Si(111) monochromator ekifukiiziibwe n’amaizi ga nitrogen kikakoresibwa kuhindura amaani ga X-ray, kandi endabirwamu erimu rhodium ekakoresibwa kukyendeeza aha biri omu harmonic. Amaani g’okukyebera gakaba nigahinduka kuruga ahari 13200 kuhika ahari 14400 eV, kandi okujwara kw’omushana kukapimwa barikukoresa 5 × 5 silicon PIN diode array etaine bishwijumwa nari ebicweka bya Soller. Amaani g’okuraba zero ag’ekirugiremu kya kabiri nigagyezesibwa ahari 13271.90 eV kurabira omu rubaju rwa L2 orwa Pt foil. Ahabw’obuhango bw’ekicweka ky’amashanyarazi, kikaba kitarikubaasika kupima omurundi gumwe spectrum y’omutindo gw’okureeberaho. Nahabwekyo, empindahinduka ebariirwe kuruga omu kukyebera kuza omu kukyebera omu maani g‘eby‘okureeberaho bya X-ray ni ±0.015 eV kurugiirira aha kupima okurikugarukagaruka omu kucondooza kwona. Obuhango bw’ekicweka kya Bi2O3 nibureetaho okwenywanisa kw’okujwara kw’omushana; ebikwato by‘amashanyarazi nibiguma biine omutindo oguhamire kugyeragyeranisa n‘omushana gw‘ebintu ebirikubaho n‘ekikwato ekirikumanyisa, ekirikureetera ebishushani byona kuba nk‘ebirikushushana. Eby’okureeberaho bya XAFS eby’omumwanya oguri haihi bikakoresibwa kumanyisa embeera y’okwotsya n’omuringo gw’eby’obuhangwa bya bismuth barikugyeragyeranisa n’ekicweka kya XANES eky’omutindo gwa Bi na Bi2O3 barikukoresa enkora y’okuteerana ey’omutindo gw’okuteerana ey’omuringo gumwe eya puroguraamu ya Athena (omuringo 0.9.26). omu koodi IFEFIIT 44.
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