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He huarahi whai hua te whakaiti hikohiko o te hauhā waro ki te waikawa formic hei whakapai ake i te whakamahinga o te hauhā waro, ā, he pea ka whakamahia hei reo rokiroki hauwai. I roto i tēnei mahi, ka whakawhanakehia he hoahoa huihuinga hiko kiriuhi kore-āputa mō te hanga hikohiko tika o te waikawa formic mai i te hauhā waro. Ko tētahi whanaketanga hangarau matua ko te kiriuhi whakawhiti cation kua pokaia, e, ina whakamahia i roto i te whirihoranga kiriuhi bipolar kua whakahāngai whakamua, ka taea te neke i te waikawa formic i hangaia i te atanga kiriuhi mā roto i te mara rere anodic i roto i ngā kukū iti iho i te 0.25 M. Me te kore he wāhanga hanawiti tāpiri i waenga i te anode me te cathode, ko te whāinga o te ariā he whakamahi i ngā rauemi pākahiko me ngā hoahoa e kitea ana i roto i ngā pūtau wahie me te electrolysis hauwai, e taea ai te whakawhiti tere ki te tauine-ake me te hokohoko. I roto i te pūtau 25 cm2, ko te whirihoranga kiriuhi whakawhiti cation kua pokaia e whakarato ana i te pai o Faraday >75% mō te waikawa formic i te <2 V me te 300 mA/cm2. Ko te mea nui ake, i whakaatuhia e te whakamātautau pumau 55-haora i te 200 mA/cm2 te pai o Faraday me te ngaohiko pūtau. E whakamahia ana te tātari hangarau-ōhanga hei whakaatu i ngā huarahi hei whakatutuki i te ōritetanga o ngā utu me ngā tikanga whakaputa waikawa formic o nāianei.
Kua whakaatuhia te whakaiti hikohiko o te hauhā waro ki te waikawa formic mā te whakamahi i te hiko whakahou hei whakaiti i ngā utu whakaputa tae atu ki te 75%1 ki te whakataurite ki ngā tikanga tuku iho e hangai ana ki te wahie pūmua. E ai ki ngā tuhinga2,3, he whānui ngā whakamahinga o te waikawa formic, mai i te huarahi whai hua me te ōhanga mō te penapena me te kawe i te hauwai ki te rauemi whāngai mō te umanga matū4,5, te umanga koiora rānei6. Kua tautuhia te waikawa formic hei rauemi whāngai mō te hurihanga i muri mai ki ngā takawaenga wahie jet pumau mā te whakamahi i te hangarau pākia7,8. I te whanaketanga o te ōhanga waikawa formic1,9, he maha ngā mahi rangahau kua arotahi ki te arotau i te whiriwhiringa whakatere10,11,12,13,14,15,16. Heoi, he maha tonu ngā mahi e arotahi ana ki ngā pūtau-H iti, ki ngā pūtau rere wai rānei e mahi ana i ngā kiato iti o te iahiko (<50 mA/cm2). Hei whakaiti i ngā utu, hei whakatutuki i te hokohoko me te whakanui ake i te urunga ki te mākete i muri mai, me mahi te whakaiti i te hauhā waro hiko (CO2R) i ngā kiato au teitei (≥200 mA/cm2) me te whai huatanga Faraday (FE)17 me te whakanui ake i te whakamahinga rauemi me te whakamahi i ngā wāhanga pākahiko mai i te Hangarau. Mā ngā pūtau wahie me te hiko wai ka taea e ngā taputapu CO2R te whakamahi i ngā ōhanga tauine18. Hei tāpiri, hei whakanui ake i te whai huatanga o te whakaputa me te karo i te tukatuka atu i raro iho, me whakamahi te waikawa formic hei hua whakamutunga kaua ki ngā tote formate19.
I tēnei huarahi, kua whakapau kaha tata nei ki te whakawhanake i ngā taputapu hiko tohatoha hau (GDE) CO2R e hāngai ana ki te hanganga/waikawa formic. E whakarāpopoto ana tētahi arotake whānui nā Fernandez-Caso et al.20 i ngā whirihoranga pūtau hiko katoa mō te whakahekenga tonu o te CO2 ki te waikawa formic/formate. I te nuinga o te wā, ka taea te wehewehe i ngā whirihoranga katoa o nāianei ki ngā wāhanga matua e toru: 1. Ngā katote rere-ā-roto19,21,22,23,24,25,26,27, 2. Kiriuhi kotahi (kiriuhi whakawhiti kationi (CEM)28, kiriuhi whakawhiti anion rānei (AEM)29 me te 3. Whirihoranga hanawiti15,30,31,32. Ko ngā wāhanga whakawhiti māmā o ēnei whirihoranga e whakaaturia ana i te Pikitia 1a. Mō te whirihoranga rere o te katote, ka hangaia he rūma electrolyte i waenganui i te kiriuhi me te katote o te GDE. Ka whakamahia te katote rere-ā-roto hei hanga i ngā awa katote i roto i te paparanga katote o te whakakorikori33, ahakoa kei te tautohetia tōna hiahia mō te whakahaere i te whiriwhiringa formate34. Heoi, i whakamahia tēnei whirihoranga e Chen et al. Mā te whakamahi i te katote SnO2 i runga i te papa waro me te paparanga katote matotoru 1.27 mm, tae atu ki te 90% FE 35 i te 500 mA/cm2 i tutuki. Ko te whakakotahitanga o te matotoru Ko te paparanga katote me te kiriuhi bipolar whakamuri (BPM) e whakawhāiti ana i te whakawhiti katote ka whakarato i te ngaohiko whakahaere o te 6 V me te whai huatanga pūngao o te 15%. Hei whakapai ake i te whai huatanga pūngao, mā te whakamahi i te whirihoranga CEM kotahi, i tutuki i a Li et al. te FE 29 o te 93.3% i te kiato iahiko haurua o te 51.7 mA/cm2. I whakamahia e Diaz-Sainz et al.28 he mīhini tātari me te kiriuhi CEM kotahi i te kiato iahiko o te 45 mA/cm2. Heoi, i whakaputahia e ngā tikanga katoa te formate kaua ko te hua pai, te waikawa formic. Haunga ngā whakaritenga tukatuka tāpiri, i roto i ngā whirihoranga CEM, ka taea e ngā hōputu pēnei i te KCOOH te kohikohi tere i roto i te GDE me te mara rere, ka puta he here kawe me te korenga o te pūtau i te mutunga.
Te whakataurite i ngā whirihoranga taputapu hurihanga CO2R tino kitea e toru ki te waikawa formate/formic me te hoahoanga kua whakaarohia i roto i tēnei rangahau. b Te whakataurite i te au katoa me te hua waikawa formate/formic mō ngā whirihoranga catholyte, ngā whirihoranga hanawiti, ngā whirihoranga CEM kotahi i roto i ngā tuhinga (e whakaaturia ana i roto i te Ripanga Tāpiri S1) me tā mātou mahi. Ko ngā tohu tuwhera e tohu ana i te whakaputanga o te otinga formate, ā, ko ngā tohu totoka e tohu ana i te whakaputanga o te waikawa formic. *Te whirihoranga e whakaaturia ana mā te whakamahi i te hauwai i te anode. c Te whirihoranga MEA kore-āputa mā te whakamahi i te kiriuhi bipolar hiato me te paparanga whakawhiti cation poka e mahi ana i te aratau whakamuri.
Hei ārai i te hanganga o te whakatakotoranga, i whakamahia e Proietto me ētahi atu 32 tētahi whirihoranga pēhi tātari kore-wehewehe e rere ai te wai whakakore-ion mā roto i te paparanga. Ka taea e te pūnaha te whakatutuki i te >70% CE i roto i te awhe kiato o te iahiko o te 50–80 mA/cm2. Waihoki, i whakaarohia e Yang me ētahi atu 14 te whakamahinga o tētahi paparanga irahiko totoka i waenganui i te CEM me te AEM hei whakatairanga i te hanganga o te waikawa formic. I tutuki i a Yang me ētahi atu 91.3% FE i roto i tētahi pūtau 5 cm2 i te 200 mA/cm2, ka puta he otinga waikawa formic 6.35 wt%. Mā te whakamahi i tētahi whirihoranga ōrite, i tutuki te 83% o te huringa o te hauhā waro (CO2) ki te waikawa formic FE i te 200 mA/cm2, ā, i whakamatautauria te pakari o te pūnaha mō te 100 hāora 30 meneti. Ahakoa he pai ngā hua iti, ko te pikinga o te utu me te uaua o ngā kapia whakawhiti katote porous ka uaua ki te whakarahi i ngā whirihoranga paparanga ki ngā pūnaha nui ake (hei tauira, 1000 cm2).
Hei tiro i te pānga kupenga o ngā hoahoa rerekē, i tātaitia e mātou te hanga waikawa formate/formic mō ia kWh mō ngā pūnaha katoa i whakahuatia i mua ake nei, ā, i tuhia ki te Pikitia 1b. E mārama ana i konei ko tētahi pūnaha kei roto he catholyte, he paparanga rānei ka eke ki te taumata teitei o tana mahi i ngā kiato iahiko iti, ā, ka heke i ngā kiato iahiko teitei ake, ka taea e te rohe ohmic te whakatau i te ngaohiko pūtau. Heoi anō, ahakoa ko te whirihoranga CEM whai hua-pūngao e whakarato ana i te hanga waikawa formic molar teitei rawa atu mō ia kWh, ka taea e te kohikohinga tote te arahi ki te hekenga tere o te mahi i ngā kiato iahiko teitei.
Hei whakaiti i ngā momo rahunga i kōrerotia i mua, i whakawhanakehia e mātou he huihuinga irahiko kiriuhi (MEA) kei roto he BPM whakahāngai whakamua me te kiriuhi whakawhiti kationi kua pokaia (PCEM). Kei te whakaatuhia te hoahoa i te Pikitia 1c. Ka whakaurua te hauwai (H2) ki roto i te anode hei whakaputa i ngā porotana mā te tauhohenga whakahāngai hauwai (HOR). Ka whakaurua he paparanga PCEM ki roto i te pūnaha BPM hei tuku i ngā katote formate i hangaia i te katote kia haere mā te AEM, ka honoa ki ngā porotana hei hanga waikawa formic i te atanga BPM me ngā pore interstitial o te CEM, kātahi ka puta mā te anode GDE me te mara rere. . Mā te whakamahi i tēnei whirihoranga, i tutuki i a mātou te >75% FE o te waikawa formic i te <2 V me te 300 mA/cm2 mō te rohe pūtau 25 cm2. Ko te mea nui, ka whakamahia e te hoahoa ngā wāhanga me ngā hoahoa taputapu e wātea ana i te hokohoko mō ngā tipu hiko pūtau wahie me te wai, e taea ai te wā tere ki te tauine. Kei roto i ngā whirihoranga katote ngā rūma rere katote ka taea te whakaputa i te kore taurite o te pēhanga i waenga i ngā āhua hau me te wai, inā koa i roto i ngā whirihoranga pūtau nui ake. Mō ngā hanganga hanawiti he paparanga pūwero o te rere o te wai, me whakapau kaha nui ki te arotau i te paparanga waenga pūwero hei whakaiti i te hekenga pēhanga me te kohikohinga o te hauhā waro i roto i te paparanga waenga. Ka taea e ēnei e rua te whakararuraru i ngā whakawhitiwhitinga pūkoro. He uaua hoki ki te whakaputa i ngā paparanga pūwero angiangi tū motuhake i runga i te tauine nui. He rerekē, ko te whirihoranga hou kua whakaarohia he whirihoranga MEA kore-āputa kāore he rūma rere, he paparanga waenga rānei. Ki te whakatauritea ki ētahi atu pūtau hikohiko o nāianei, he ahurei te whirihoranga kua whakaarohia nā te mea ka taea te hanga tika i te waikawa formic i roto i te whirihoranga tauine, whai hua-pūngao, kore-āputa.
Hei pehi i te whanaketanga o te hauwai, kua whakamahia e ngā mahi whakaiti CO2 nui ngā whirihoranga membrane MEA me AEM me te whakakotahitanga me ngā electrolytes kukū molar teitei (hei tauira, 1-10 M KOH) hei waihanga i ngā āhuatanga kawakore i te cathode (e whakaaturia ana i te Pikitia 2a). I roto i ēnei whirihoranga, ka haere ngā katote formate i hangaia i te cathode mā roto i te membrane hei momo utu kino, kātahi ka hangaia te KCOOH ka puta i te pūnaha mā te awa KOH anodic. Ahakoa i pai te FE formate me te ngaohiko pūtau i te tīmatanga e whakaaturia ana i te Pikitia 2b, i hua ake i te whakamātautau pumau he whakahekenga o te FE tata ki te 30% i roto i te 10 h noa iho (Pikitia S1a–c). Me mōhio ko te whakamahinga o te 1 M KOH anolyte he mea nui hei whakaiti i te ngaohiko anodic i roto i ngā pūnaha tauhohenga whanaketanga hāora kawakore (OER)37 me te whakatutuki i te urunga katote i roto i te moenga whakakorikori cathode33. Ina whakaitihia te kukū o te anolyte ki te 0.1 M KOH, ka piki ake te ngaohiko pūtau me te waikura waikawa formic (te ngaronga o te waikawa formic) (Pikitia S1d), e whakaatu ana i te taurite kore-tapeke. I aromatawaihia te nui o te waikura formate mā te whakamahi i te toenga papatipu whānui; mō ētahi atu taipitopito, tirohia te wāhanga "Ngā Tikanga". I akohia hoki te mahi mā te whakamahi i ngā whirihoranga membrane MEA me te CEM kotahi, ā, kei te Pikitia S1f,g ngā hua. Ko te FE formate i kohia mai i te cathode he >60% i te 200 mA/cm2 i te tīmatanga o te whakamātautau, engari i tere te pakaru i roto i ngā haora e rua nā te kohikohinga tote cathode i kōrerohia i mua (Pikitia S11).
He hoahoa o te MEA kore-āputa me te CO2R i te katote, te tauhohenga waikura hauwai (HOR) te OER rānei i te anode, me te kiriuhi AEM kotahi i waenganui. b Ko te FE me te ngaohiko pūtau mō tēnei whirihoranga me te 1 M KOH me te OER e rere ana i te anode. Ko ngā pae hapa e tohu ana i te paerewa rerekētanga o ngā inenga rerekē e toru. i roto i te FE me te ngaohiko pūtau pūnaha me te H2 me te HOR i te anode. Ka whakamahia ngā tae rerekē hei wehewehe i te hanga waikawa formate me te formic. d He hoahoa hoahoa o te MEA me te BPM kua nekehia whakamua ki waenganui. Ko te FE me te ngaohiko pākahiko ki te wā i te 200 mA/cm2 mā te whakamahi i tēnei whirihoranga. f He whakaahua whakawhiti-wāhanga o te BPM MEA kua whakahāngai whakamua i muri i te whakamātautau poto.
Hei whakaputa waikawa formic, ka tukuna te hauwai ki tētahi whakakorikori Pt-on-carbon (Pt/C) i te anode. E ai ki te Whakaahua 2d, kua rangahaua i mua tētahi pūtorino whakaputa BPM whakahāngai-mua i te anode hei whakatutuki i te whakaputanga waikawa formic. I rahua te waeine whakatikatika BPM i muri i te 40 meneti o te mahi i te iahiko o te 200 mA/cm2, me te pikinga ngaohiko neke atu i te 5 V (Pikitia 2e). Whai muri i te whakamātautau, i kitea he wehewehenga mārama i te atanga CEM/AEM. Haunga te formate, ka taea hoki e ngā anion pēnei i te carbonate, te bicarbonate me te hydroxide te haere mā roto i te membrane AEM ka tauhohe ki ngā pūtorino i te atanga CEM/AEM hei whakaputa hau CO2 me te wai wai, ka hua ake te wehewehenga BPM (Pikitia 2f) ā, i te mutunga ka hua ake te rahunga o te pūtau.
I runga i ngā tikanga mahi me te rahunga o te whirihoranga i runga ake nei, ka whakaarohia he hoahoa MEA hou e whakaaturia ana i te Pikitia 1c, ā, ka whakamāramahia i te Pikitia 3a38. I konei, ka whakaratohia e te paparanga PCEM he ara mō te hekenga o te waikawa formic me ngā anion mai i te atanga CEM/AEM, ā, ka whakaitihia te kohikohinga o te matū. I taua wā anō, ka arahina e te ara interstitial PCEM te waikawa formic ki roto i te reo horapa me te mara rere, ka whakaitihia te tūponotanga o te waikura waikawa formic. Ko ngā hua polarization e whakamahi ana i ngā AEM me ngā matotoru o te 80, 40 me te 25 mm e whakaaturia ana i te Pikitia 3b. E ai ki te tumanako, ahakoa ka piki ake te ngaohiko pūtau whānui me te piki haere o te matotoru o te AEM, mā te whakamahi i te AEM matotoru ake ka ārai i te horapa whakamuri o te waikawa formic, ā, ka piki ake te pH cathode me te whakaiti i te hanga H2 (Pikitia 3c–e).
a He whakaahua o te hanganga MEA me te AEM me te CEM pokaia me ngā ara kawe waikawa formic rerekē. b Te ngaohiko pūtau i ngā kiato iahiko rerekē me ngā matotoru AEM rerekē. i roto i te EE i ngā kiato iahiko rerekē me te matotoru AEM o te 80 μm (d) 40 μm, e) 25 μm. Ko ngā pae hapa e tohu ana i te paerewa rerekētanga i inehia mai i ngā tauira motuhake e toru. f Ngā hua whakatauira o te kukū waikawa formic me te uara pH i te atanga CEM/AEM i ngā matotoru AEM rerekē. f PC me te pH i roto i te paparanga cathode o te whakakorikori me ngā matotoru kiriata AEM rerekē. g Te tohatoha rua-ahu o te kukū waikawa formic me te atanga CEM/AEM me te pokaia.
E whakaatu ana te Pikitia S2 i te tohatoha o te kukū waikawa formic me te pH puta noa i te matotoru MEA mā te whakamahi i te whakatauira huānga mutunga kore Poisson-Nernst-Planck. Kāore i te miharo ko te kukū teitei rawa o te waikawa formic, 0.23 mol/L, ka kitea i te atanga CEM/AEM, nā te mea ka hangaia te waikawa formic i tēnei atanga. Ka tere ake te heke o te kukū o te waikawa formic mā roto i te AEM i te pikinga o te matotoru o te AEM, e tohu ana i te ātete nui ake ki te whakawhiti papatipu me te iti ake o te rere o te waikawa formic nā te horapa whakamuri. E whakaatu ana ngā Pikitia 3 f me g i ngā uara pH me te waikawa formic i roto i te moenga whakakorikori cathode i puta mai i te horapa whakamuri me te tohatoha rua-ahu o te kukū waikawa formic. Ko te angiangi o te membrane AEM, ko te teitei ake o te kukū o te waikawa formic tata ki te cathode, ā, ka waikawa te pH o te cathode. Nō reira, ahakoa he nui ake ngā mate ohmic i puta mai i ngā membrane AEM matotoru, he mea nui ēnei hei aukati i te horapa whakamuri o te waikawa formic ki te cathode me te whakanui ake i te parakore teitei o te pūnaha waikawa formic FE. Hei whakamutunga, ko te whakanui ake i te matotoru o te AEM ki te 80 μm i hua ake ai he FE >75% mō te waikawa formic i te <2 V me te 300 mA/cm2 mō te horahanga pūtau 25 cm2.
Hei whakamātautau i te pumau o tēnei hoahoa PECM, i puritia te iahiko pākahiko ki te 200 mA/cm2 mō ngā hāora 55. Kei te Pikitia 4 ngā hua whānui, me ngā hua mai i ngā hāora tuatahi e 3 kua tohua ki te Pikitia S3. I te whakamahinga o te whakakorikori anodic Pt/C, i piki tere te ngaohiko pūtau i roto i ngā meneti 30 tuatahi (Pikitia S3a). I roto i te wā roa, i noho tonu te ngaohiko pūtau, me te tere whakahekenga o te 0.6 mV/h (Pikitia 4a). I te tīmatanga o te whakamātautau, ko te PV o te waikawa formic i kohia i te anode he 76.5%, ā, ko te PV o te hauwai i kohia i te cathode he 19.2%. I muri i te hāora tuatahi o te whakamātautau, i heke te hauwai FE ki te 13.8%, e tohu ana i te pai ake o te whiriwhiringa formate. Heoi, i heke te tere waikura o te waikawa formic i roto i te pūnaha ki te 62.7% i roto i te 1 hāora, ā, i piki te tere waikura o te waikawa formic anodic mai i te tata kore i te tīmatanga o te whakamātautau ki te 17.0%. I muri mai, i noho pumau tonu te FE o te H2, te CO, te waikawa formic me te tere o te whakapūngao anodic o te waikawa formic i te wā o te whakamātautau. Ko te pikinga o te whakapūngao waikawa formic i te haora tuatahi pea nā te kohikohinga o te waikawa formic i te atanga PCEM/AEM. I te pikinga o te kukū o te waikawa formic, ehara i te mea ka puta noa i te poka o te kiriuhi, engari ka horapa hoki i roto i te FEM tonu ka tomo ki te paparanga anode Pt/C. I te mea he wai te waikawa formic i te 60°C, ka taea e tōna kohikohinga te whakararu i te whakawhiti papatipu me te hua ake he whakapūngao pai ake i te hauwai.
a Te ngaohiko pūtau ki te wā (200 mA/cm2, 60 °C). E whakaatu ana te whakaurunga i tētahi whakaahua karuārai whatu o tētahi wāhanga whakawhiti o tētahi MEA me tētahi EM kua pokaia. Pae tauine: 300 µm. b Te parakore o te PE me te waikawa formic hei mahi a te wā i te 200 mA/cm2 mā te whakamahi i tētahi anode Pt/C.
I whakaahuahia te āhua o ngā tauira i te tīmatanga o te whakamātautau (BOT) i te wā whakarite me te mutunga o te whakamātautau (EOT) i muri i te 55 hāora o te whakamātautau pumau mā te whakamahi i te nano-X-ray computed tomography (nano-CT), e whakaaturia ana i te Pikitia 5 a. He nui ake te rahi o te matūriki whakakorikori o te tauira EOT me te diameter o te 1207 nm ki te 930 nm mō te BOT. Kei te Pikitia 5b ngā ​​whakaahua o te karu hiko whakawhiti matawai pōuri-pouri teitei-koki (HAADF-STEM) me ngā hua o te mātakitaki hihi-X marara-pūngao (EDS). Ahakoa kei roto i te paparanga whakakorikori BOT te nuinga o ngā matūriki whakakorikori iti me ētahi kohikohinga nui ake, i te wāhanga EOT ka taea te wehewehe i te paparanga whakakorikori kia rua ngā rohe motuhake: tētahi he nui ake ngā matūriki totoka, ko tētahi he nui ake ngā rohe porous. Te maha o ngā matūriki iti ake. E whakaatu ana te whakaahua EDS he nui te Bi i roto i ngā matūriki totoka nui, tera pea he konganuku te Bi, ā, he nui te hāora i roto i ngā rohe porous. Ina whakahaerehia te pūtau i te 200 mA/cm2, ka whakaitihia te Bi2O3 e te pūmanawa kino o te katote, e whakaatuhia ana e ngā hua o te tirotiro mimiti hihi-X in situ kua kōrerohia i raro nei. E whakaatu ana ngā hua mahere HAADF-STEM me te EDS ka pāngia te Bi2O3 e te tukanga whakaiti, ka ngaro te hāora, ka huihui hei matūriki whakarewa nui ake. Ko ngā tauira diffraction hihi-X o ngā katote BOT me EOT e whakaū ana i te whakamaoritanga o ngā raraunga EDS (Pikitia 5c): ko te Bi2O3 tioata anake i kitea i roto i te katote BOT, ā, i kitea te bimetal tioata i roto i te katote EOT. Hei mārama ki te pānga o te pūmanawa katote ki te āhua waikura o te whakakorikori katote Bi2O3, i rerekē te pāmahana mai i te pūmanawa ara iahiko tuwhera (+0.3 V vs RHE) ki te -1.5 V (vs RHE). E kitea ana ka tīmata te whakahekenga o te wāhanga Bi2O3 i te -0.85 V e pā ana ki te RHE, ā, ko te whakahekenga o te kaha o te rārangi mā i te rohe taha o te whānuitanga e tohu ana kua whakahekehia te Bi whakarewa ki te 90% o te RHE i te -1.1. V e pā ana ki te RHE (Pikitia 5d). Ahakoa te tikanga, ko te whiriwhiringa whānui o te formate i te cathode kāore i rerekē, e ai ki te H2 me te CO FE me te hanganga waikawa formic, ahakoa ngā huringa nui o te āhua o te cathode, te āhua o te waikura o te whakakorikori, me te hanganga moroiti-kiriata.
a Hanganga toru-ahu o te paparanga whakatere me te tohatoha o ngā matūriki whakatere i whiwhi mā te whakamahi i te nano-X-ray CT. Pae tauine: 10 µm. b Runga 2: Ngā whakaahua HAADF-STEM o ngā paparanga katote o ngā whakatere BOT me EOT. Pae tauine: 1 µm. Raro 2: Ngā whakaahua HADF-STEM me EDX kua whakanuia o te paparanga katote o te whakatere EOT. Pae tauine: 100 nm. c Ngā tauira whakarara hihi-X o ngā tauira katote BOT me EOT. d Ngā ira mimiti hihi-X in situ o te irahiko Bi2O3 i roto i te 0.1 M KOH hei pānga o te pūmanawa (0.8 V ki te -1.5 V vs. RHE).
Hei whakatau i ngā whai wāhitanga e wātea ana hei whakapai ake i te whai huatanga o te pūngao mā te aukati i te waikura waikawa formic, i whakamahia he hiko tohutoro H2 hei tautuhi i te takoha o te ngaronga ngaohiko39. I ngā kiato o ia au i raro i te 500 mA/cm2, ka noho tonu te pūmanawa katote i raro i te -1.25 V. E rua ngā wāhanga matua o te pūmanawa anodic: te kiato o ia au whakawhiti HOR me te ngaohiko nui ariā HOR 40 i matapaetia e te whārite Bulter-Volmer i inehia i mua, ā, ko te toenga wāhanga nā te waikura waikawa formic. Nā te puhoi rawa o te tauhohenga ki te whakataurite ki te HOR41, ko te tere iti o te tauhohenga waikura waikawa formic i te anode ka hua ake he pikinga nui o te pūmanawa anodic. E whakaatu ana ngā hua ka taea e te aukati katoa i te waikura waikawa formic te whakakore i te ngaohiko nui tata ki te 500 mV.
Hei whakamātautau i tēnei whakatau tata, i whakarerekētia te tere rere o te wai whakakore iona (DI) i te tomokanga o te anode hei whakaiti i te kukū o te waikawa formic para. E whakaatu ana ngā Pikitia 6b me te c i te FE, te kukū waikawa formic, me te ngaohiko pūtau hei mahi a te rere DI i te anode i te 200 mA/cm2. I te pikinga o te tere rere o te wai whakakore iona mai i te 3.3 mL/min ki te 25 mL/min, i heke te kukū waikawa formic i te anode mai i te 0.27 mol/L ki te 0.08 mol/L. Hei whakataurite, mā te whakamahi i te hanganga hanawiti i whakaarohia e Xia et al. 30 i whiwhihia he kukū waikawa formic o te 1.8 mol/L i te 200 mA/cm2. Mā te whakaiti i te kukū ka whakapai ake i te FE whānui o te waikawa formic, ā, ka whakaiti i te FE o te H2 i te mea ka nui ake te kawakore o te pH cathode nā te hekenga o te horapa o te waikawa formic. Nā te whakaiti i te kukū o te waikawa formic i te rere DI mōrahi i tata whakakorea te waikura waikawa formic, ka hua ake he ngaohiko pūtau katoa i raro iho i te 1.7 V i te 200 mA/cm2. Ka pā hoki te pāmahana pākahiko ki te mahi whānui, ā, e whakaaturia ana ngā hua i te Pikitia S10. Heoi, ka taea e ngā hoahoa e hangai ana ki te PCEM te whakapai ake i te whai huatanga o te pūngao ki te aukati i te waikura waikawa formic, ahakoa mā te whakamahi i ngā whakakorikori anodic me te whiriwhiringa hauwai pai ake ki te waikawa formic, mā te whakahaere taputapu rānei.
a Te wetewete i te ngaohiko pūtau mā te whakamahi i te hiko tohutoro pūtau H2 e mahi ana i te 60 °C, te anode Pt/C me te 80 µm AEM. b Ngā kukū FE me te waikawa formic i kohia i te 200 mA/cm2 mā te whakamahi i ngā tere rere rerekē o te wai whakakore ionized anodic. c Ina kohia e te anode te waikawa formic i ngā kukū rerekē, ko te ngaohiko pūtau he 200 mA/cm2. Ko ngā pae hapa e tohu ana i te paerewa rerekē o ngā inenga rerekē e toru. d Te utu hoko iti rawa e wehea ana e te mahi i ngā tere rere wai whakakore ionized rerekē mā te whakamahi i ngā utu hiko toharite ā-motu o te US$0.068/kWh me te US$4.5/kg hauwai. (*: Ko te āhua waikura iti rawa o te waikawa formic i te anode e kiia ana ko te 10 M FA, ko te utu hiko ahumahi toharite ā-motu ko te $0.068/kWh, ā, ko te hauwai ko te $4.5/kg. **: Ko te āhua waikura iti rawa e kiia ana ko te waikawa formic. Ko te kukū o te FA i te anode ko te 1.3 M anode, ko te utu hiko ā muri ake nei e tumanakohia ana ko te $0.03/kWh, ā, ko te rārangi iraira e tohu ana i te utu mākete o te 85 wt% FA.
I whakahaerehia he tātaritanga hangarau-ōhanga (TEA) hei whiwhi i te utu hoko iti rawa o ngā huihuinga wahie i raro i ngā āhuatanga whakahaere maha, e whakaaturia ana i te Pikitia 5d. Kei roto i te SI ngā tikanga me ngā raraunga papamuri mō TEA. Ina teitei ake te kukū LC i roto i te putanga hau anode, ahakoa te teitei ake o te ngaohiko pūtau, ka whakaitihia te utu whānui o te huihuinga wahie nā te whakaiti i te utu wehenga. Mena ka taea te whakaiti i te waikura anodic o te waikawa formic mā te whakawhanake i te whakakorikori, i te hangarau hiko rānei, mā te whakakotahitanga o te ngaohiko pūtau iti ake (1.66 V) me te kukū FA teitei ake i roto i te para (10 M) ka whakaitihia te utu o te hanga FA hikohiko ki te 0.74 tāra US/kg (i runga i te hiko). utu) $0.068/kWh me te $4.5/kg hauwai42. Heoi anō, ina honoa ki te utu ā-muri e matapaetia ana mō te hiko whakahou o te $0.03/kWh me te hauwai o te $2.3/kg, ka whakaitihia te whāinga waipara FA ki te 1.3 miriona, ka hua ake ko te utu whakaputa whakamutunga e matapaetia ana ko te US$0.66/kg43. He rite tēnei ki ngā utu mākete o nāianei. Nō reira, ko ngā mahi ā-muri e arotahi ana ki ngā rauemi me ngā hanganga hiko ka taea te whakaiti ake i te anodization me te tuku i te mahi i ngā ngaohiko pūtau iti ake kia puta ai he kukū LC teitei ake.
Hei whakarāpopototanga, kua akohia e mātou ētahi hanganga MEA kore-āputa mō te whakaiti CO2 ki te waikawa formic, ā, kua whakaarohia he hanganga kei roto he kiriuhi bipolar whakamuri-whakamua tae atu ki te kiriuhi whakawhiti cation kua pokaia (PECM) hei whakahaere i te atanga whakawhiti papatipu kiriuhi mō te waikawa formic ka puta. . Ka whakaputahia e tēnei whirihoranga te >96% waikawa formic i ngā kukū tae atu ki te 0.25 M (i te tere rere DI anode o te 3.3 mL/min). I ngā tere rere DI teitei ake (25 mL/min), i whakaratohia e tēnei whirihoranga he mātotoru iahiko o te >80% FE o te 200 mA/cm2 i te 1.7 V mā te whakamahi i te horahanga pūtau 25 cm2. I ngā tere DI anodic ngawari (10 mL/min), i pupuri te whirihoranga PECM i te ngaohiko pumau me ngā taumata FE waikawa formic teitei mō te 55 hāora o te whakamātautau i te 200 mA/cm2. Ka taea te whakarei ake i te pumau me te whiriwhiringa teitei i tutukihia e ngā whakakorikori e wātea ana i te hokohoko me ngā rauemi kiriuhi polymeric mā te whakakotahi i a rātou me ngā whakakorikori hiko kua arotauhia. Ka arotahi ngā mahi e whai ake nei ki te whakarerekē i ngā āhuatanga whakahaere, te whiriwhiringa o te whakakorikori anode, me te hanganga MEA hei whakaiti i te waikura waikawa formic, ka hua ake he parahanga kukū ake i ngā ngaohiko pūtau iti ake. Mā te huarahi māmā ki te whakamahi i te hauhā waro mō te waikawa formic e whakaaturia ana i konei ka whakakorea te hiahia mō ngā rūma anolyte me te catholyte, ngā wāhanga hanawiti, me ngā rauemi motuhake, ā, ka whakanui ake i te whai huatanga o te pūngao pūtau me te whakaiti i te uaua o te pūnaha, ka māmā ake te whakanui ake. Mā te whirihoranga kua whakaarohia ka whakaratohia he tūāpapa mō te whanaketanga ā-muri o ngā tipu hurihanga CO2 e whai hua ana ki te hangarau me te ōhanga.
Ki te kore e kīia tētahi atu mea, i whakamahia ngā rauemi matū me ngā whakarewa katoa i te wā i riro mai ai. I hokona mai te whakakorikori waikura bismuth (Bi2O3, 80 nm) mai i US Research Nanomaterials, Inc. I whakaratohia mai te paura polymer (AP1-CNN8-00-X) e IONOMR. I hokona mai te N-propanol (nPA) waitohu Omnisolv® me te wai tino parakore (18.2 Ω, pūnaha purenga wai Milli–Q® Advantage A10) mai i Millipore Sigma. I hokona mai te methanol me te acetone kua whakamanahia e te ACS mai i VWR Chemicals BDH® me Fisher Chemical. I konatunatua te paura polymer ki te ranunga acetone me te methanol i te ōwehenga o te 1:1 mā te taumaha hei whiwhi i te marara polymer me te kukū o te 6.5 wt.%. Whakaritea te waituhi whakakorikori mā te whakaranu i te 20 karamu Bi2O3, te wai tino parakore, te nPA me te marara ionomer ki roto i te ipu 30ml. I roto i te hanganga he 30 wt.% te whakakorikori, he ōwehenga papatipu o te ionomer ki te whakakorikori o te 0.02 me te ōwehenga papatipu o te waipiro ki te wai o te 2:3 (40 wt.% nPA). I ​​mua i te whakaranu, i tāpirihia te 70g o te rauemi huri zirconia 5mm a Glen Mills ki te ranunga. I whakatakotoria ngā tauira ki runga i te roera pounamu mamati Fisherbrand™ i te 80 rpm mō ngā hāora 26. Tukua te waituhi kia noho mō te 20 meneti i mua i te paninga. I pania te waituhi Bi2O3 ki te taputapu tono aunoa a Qualtech (QPI-AFA6800) mā te whakamahi i te whakakī waea taiwhanga 1/2″ x 16″ (RD Specialties – 60 mil diameter) i te 22°C. I pania te 5 mL o te waituhi whakakorikori ki te kawe horapa hau waro Sigraacet 39 BB 7.5 x 8 inihi (rokiroki pūtau wahie) mā te whakatakotoranga tokotoko i te tere toharite pumau o te 55 mm/hēkona. Whakawhitihia ēnei irahiko pania ki te oumu ka whakamaroke i te 80 °C. Kei roto i ngā Pikitia S4a me te b te tukanga paninga tokotoko me ngā whakaahua o te paninga GDE. I whakapumautia e te taputapu hihi-X fluorescence (XRF) (Fischerscope® XDV-SDD, Fischer-Technolgy Inc. USA) ko te utaina o te paninga GDE he 3.0 mg Bi2O3/cm2.
Mō ngā whirihoranga kiriuhi hiato kei roto ko te kiriuhi whakawhiti anion (AEM) me te CEM pokaia. I whakamahia te Nafion NC700 (Chemours, USA) me te matotoru ingoa o te 15 µm hei paparanga CEM. I rehuhia tika te whakakorikori anodic ki runga i te FEM me te ōwehenga ionomer ki te waro o te 0.83 me te horahanga hipoki o te 25 cm2. I whakamahia te konukawata tautoko me te horahanga mata nui (50 wt.% Pt/C, TEC 10E50E, TANAKA konganuku utu nui) me te uta o te 0.25 mg Pt/cm2 hei whakakorikori anode. I whakamahia te Nafion D2020 (Ion Power, USA) hei ionomer mō te paparanga anode o te whakakorikori. Ka mahia te pokaia CEM mā te tapahi i ngā rārangi whakarara i runga i te kiriata CEM i ngā wā 3mm. Kei te whakaatuhia ngā taipitopito o te tukanga pokaia i roto i ngā Pikitia S12b me c. Mā te whakamahi i te rorohiko rorohiko X-ray, i whakaūtia ko te āputa poka he 32.6 μm, e whakaaturia ana i te Pikitia S12d me te e. I te wā o te huihuinga pūtau, i whakatakotoria he kiriuhi CEM kua pania ki te whakakorikori ki runga i te pepa Toray 25 cm2 (5 wt% PTFE i maimoatia, Fuel Cell Store, USA). I ​​whakatakotoria he kiriuhi AEM (PiperION, Versogen, USA) he matotoru 25, 40, 80 μm rānei ki runga i te CEM, kātahi ki runga i te katote GDE. I tapahia te kiriuhi AEM kia 7.5 × 7.5 cm te rahi hei taupoki i te mara rere katoa, ā, i rumakina mō te pō ki roto i te otinga pāhare pākawa waro 1 M i mua i te huihuinga. E whakamahi ana te anode me te katote i ngā mokowā PTFE he matotoru hei whakatutuki i te kōpeketanga GDE tino pai o te 18%. Kei te whakaaturia ngā taipitopito o te tukanga huihuinga pākahiko i te Pikitia S12a.
I te wā whakamātautau, i puritia te pūtau kua huihui ki te 60 °C (30, 60, me te 80 °C mō ngā rangahau e pā ana ki te pāmahana) me te 0.8 L/min o te hau hauwai i tukuna ki te anode me te 2 L/min o te hauhā waro i tukuna ki te cathode. I whakamakukuhia ngā rerenga hau anodic me te cathodic i te 100% te haumākū whanaunga me te 259 kPa te pēhanga cathodic tino. I te wā e whakahaerehia ana, i konatunatua te rerenga hau cathode ki te 1 M KOH solution i te tere o te 2 mL/min hei whakatairanga i te whakamahinga o te moenga whakakorikori cathode me te kawe ionic. Whakaranua he rerenga hau anode ki te wai deionized i te tere o te 10 ml/min hei tango i te waikawa formic i te anode. Kei te whakaatuhia ngā taipitopito o ngā whakaurunga me ngā putanga o te taputapu i te Pikitia S5. Kei roto i te hau putanga cathode te CO2, ā, ka whakaputa i te CO me te H2. Ka tangohia te mamaoa wai mā te condenser (te whakawhiti wera pāmahana iti i te 2°C). Ka kohia te hau e toe ana mō te tātari wā hau. Ka haere hoki te rere o te anode mā roto i tētahi pūwhakamātautau hei wehe i te wai mai i te hau. Ka kohia te wai para ki roto i ngā ipu ma, ā, ka tātarihia mā te whakamahi i te ine auau wai hei ine i te waikawa formic i puta. I whakahaerehia ngā whakamātautau hikohiko mā te whakamahi i tētahi potentiostat Garmy (nama tohutoro 30K, Gamry, USA). I ​​mua i te ine i te pihi pōraritanga, i whakatikatikaina te pūtau e 4 ngā wā i roto i te awhe mai i te 0 ki te 250 mA/cm2 mā te whakamahi i te voltammetry raina me te tere matawai o te 2.5 mA/cm2. I whiwhihia ngā pihi pōraritanga i roto i te aratau galvanostatic me te pūtau e puritia ana i tētahi kiato iahiko mō te 4 meneti i mua i te tango tauira i te hau cathode me te wai anolyte.
Ka whakamahia e mātou he hiko tohutoro hauwai i roto i te MEA hei wehe i te kaha katote me te kaha anodic. Kei te Pikitia S6a te hanganga o te hiko tohutoro. I whakamahia he kiriuhi Nafion (Nafion 211, IonPower, USA) hei piriti ionic hei hono i te kiriuhi MEA me te hiko tohutoro. I honoa tetahi pito o te rīpene Nafion ki te hiko tohatoha hau 1 cm2 (GDE) kua utaina ki te 0.25 mg Pt/cm2 (50 wt% Pt/C, TEC10E50E, TANAKA Precious Metals) kua ruia ki runga i te pepa waro 29BC (Fuel Cell Store, USA). ). Ka whakamahia he taputapu polyetheretherketone motuhake (PEEK) hei hiri hau me te whakarite kia pai te hononga i waenga i ngā rīpene GDE me Nafion, me te hono i te hiko tohutoro ki te taputapu pūtau wahie. Ko tetahi atu pito o te rīpene Nafion kua honoa ki te taha e puta mai ana o te pākahiko CEM. E whakaatu ana te Pikitia S6b i te wāhanga whakawhiti o te hiko tohutoro kua whakauruhia ki te MEA.
I muri i te haerenga o te hau putanga mā te whakapūmau me te wehewehe hau-wai, ka tangohia ngā tauira hau mai i te katote. I tātarihia te hau i kohia kia toru ngā wā, neke atu rānei, mā te whakamahi i te 4900 Micro GC (tatari ngota 10 μm, Agilent). I kohia ngā tauira ki roto i ngā putea tauira hau pepa konumohe maha-paparanga kore mahi Supel™ (Sigma-Aldrich) mō tētahi wā kua tohua (30 hēkona) ā, i whakaurua ā-ringa ki roto i te chromatograph hau moroiti i roto i ngā haora e rua i muri i te kohikohinga. I whakatakotoria te pāmahana weronga ki te 110°C. I wehea te hau waro hauota (CO) me te hauwai (H2) ki runga i te pou MS5A 10 m kua whakamahanatia (105 °C) kua pēhia (28 psi) mā te whakamahi i te argon (Matheson Gas-Matheson Purity) hei hau kawe. Ka kitea ēnei hononga mā te whakamahi i te Pūoko Ārahi Wera (TCD) kua hangaia. Kei te whakaatuhia ngā chromatogram GC me ngā pihi whakatikatika CO me H2 i te Pikitia S7. I kohia ngā tauira waikawa formic wai mai i te anode mō tētahi wā kua tohua (120 hēkona) ā, i tātarihia mā te whakamahi i tētahi tātari pūwero PTFE 0.22 μm ki roto i ngā ipu 2 mL. I tātarihia ngā hua wai i roto i ngā ipu mā te whakamahi i tētahi pūnaha chromatography wai mahi-teitei (HPLC) bioinert Agilent 1260 Infinity II, i werohia ai te 20 μl o te tauira mā roto i tētahi autosampler (G5668A) me te wāhanga neke o te waikawa whanariki 4 mM (H2SO4). ) i te tere rere o te 0.6 ml/min (papu quaternary G5654A). I ​​wehea ngā hua ki runga i tētahi Aminex HPX-87H 300 × 7.8 mm (Bio-Rad) kua wera (35°C, oumu pou G7116A) i mua i tētahi pou tiaki Micro-Guard Cation H. I kitea te waikawa formic mā te whakamahi i tētahi taputapu kite rarangi diode (DAD). i te roanga ngaru o te 210 nm me te whānui o te 4 nm. Kei te whakaatuhia te kōromata HPL me te pihi whakatikatika paerewa waikawa formic i te Pikitia S7.
Ka tatauhia ngā hua hau (CO me te H2) FE mā te whakamahi i te whārite e whai ake nei, ā, ka tatauhia ngā mole katoa o te hau mā te whakamahi i te whārite hau tino pai:
I roto i ēnei: ​​\({n}_{i}\): te maha o ngā irahiko i roto i te tauhohenga hikohiko. \(F\): Te pūmau o Faraday. \({C}_{i}\): Te kukū o te hua wai HPLC. \(V\): te rōrahi o te tauira wai i kohia i roto i te wā kua whakaritea t. \(j\): te mātotoru o ia au. \(A\): Te horahanga āhuahanga o te irahiko (25 cm2). \(t\): te wā tauira. \(P\): te pēhanga tino. \({x}_{i}\): Te ōrau mole o te hau i whakatauhia e te GC. \(R\): te pūmau hau. \(T\): te pāmahana.
I inehia te kukū o ngā kationa anodic mā te whakamahi i te inductively coupled plasma atomic emission spectroscopy (ICP-OES). Ko ngā kationa ka mimiti, ka horapa rānei ki roto i te anode ko Ti, Pt, Bi me K. Haunga a K, ko ngā kationa katoa i raro iho i te rohe kitenga. Ka hangaia he iona i roto i te otinga ka waiho te anode kia honoa ki ngā proton, ki ētahi atu kationa rānei. Nō reira, ka taea te tatau i te parakore o te waikawa formic penei
Ko te whakaputanga formate/FA e tohu ana i te nui o te FA e whakaputaina ana mō ia kWh o te hiko e pau ana mā te whakamahi i tētahi whirihoranga MEA motuhake, i roto i te mol/kWh. Ka tatauhia i runga i te kiato o ia au, te ngaohiko pūtau me te whai huatanga o Faraday i raro i ngā tikanga whakahaere motuhake.
Tātaihia te nui o te waikawa formic i whakapūngaohia ki te anode i runga i te taurite papatipu whānui. E toru ngā tauhohenga whakataetae ka puta i te cathode: te whanaketanga hauwai, te whakahekenga o te CO2 ki te CO, me te whakahekenga o te CO2 ki te waikawa formic. Nā te mea he tukanga whakapūngao waikawa formic kei roto i a Anton, ka taea te wehewehe i te waikawa formic FE kia rua ngā wāhanga: te kohinga waikawa formic me te whakapūngao waikawa formic. Ka taea te tuhi i te taurite papatipu whānui penei:
I whakamahia e mātou te GC hei ine i te nui o te waikawa formic, te hauwai, me te CO i kohia e te HPLC. Me mōhio ko te nuinga o te waikawa formic i kohia mai i te anode mā te whakamahi i te whakatakotoranga e whakaaturia ana i te Pikitia Tāpiri S5. He iti noa te nui o te formate i kohia mai i te rūma cathode, tata ki te rua ngā whakarea o te rahi, ā, he iti iho i te 0.5% o te nui katoa o te SC.
Ko te tauira kawe tonu e whakamahia ana i konei e ahu mai ana i ngā mahi o mua i runga i ngā pūnaha rite34. Ka whakamahia he pūnaha honohono o ngā whārite Poisson-Nerst-Planck (PNP) hei whakatau i te kukū wai me te pūmanawa hikohiko i roto i ngā wāhanga kawe hiko me te ioni. Kei roto i te SI he tirohanga whānui o ngā whārite matua me te āhuahanga tauira.
Ka whakatauhia e tēnei pūnaha te kukū o ngā matū wai e waru (\({{{{{{\rm{C}}}}}}}}{{{{{{\rm{O}}}}}}}}}_{2 \left ({{{{{{\rm{aq}}}}}}}\right)}\), \({{{{{{\rm{H}}}}}}}}^{+ }\ ), \ ({{{{{\rm{O}}}}}}{{{{{{\rm{H}}}}}}^{-}\), \({{{ {{{ \rm{ HCO}}}}}}}}_{3}^{-}\), \({{{{{{\rm{CO}}}}}}}_{3}^{ 2-} \ ),\ ({{{{{\rm{HCOOH}}}}}}}\), \({{{{{{{\rm{HCOO}}}}}}}}^{- }\) me \({{{ {{{\rm{K}}}}}}}^{+}\)), te pūmanawa hiko pūmau i roto i te wāhanga kawe ionic (\({\phi }_{I}\ )) me te kawe irahiko anodic me te cathodic. Ngā pūmanawa hiko pūmau i roto i ngā wāhanga (\({\phi }_{A}\) me \({\phi }_{C}\) ia). Engari, kāore e tutukihia ngā mahi korekore hiko ā-rohe me ngā mahi tohatoha utu, ka whakatauhia tika te rohe utu ātea mā te whakamahi i te whārite a Poisson; Mā tēnei huarahi ka taea e tātou te whakatauira tika i ngā pānga pana a Donnan i ngā atanga CEM|AEM, CEM|Pore, me AEM|Pore. Hei tāpiri, ka whakamahia te ariā irahiko pūmau (PET) hei whakaahua i te kawe utu i roto i ngā paparanga anodic me te cathodic o te whakakorikori. Ki te mōhio pai o ngā kaituhi, ko tēnei mahi te tono tuatahi o te PET i roto i ngā pūnaha he maha ngā rohe utu ātea.
I whakamātauria ngā tauira katote GDE BOT me EOT mā te whakamahi i tētahi Zeiss Xradia 800 Ultra me tētahi pūtake hihi-X 8.0 keV, ngā momo mimiti me te whānui o te mara, me te hanumi whakaahua1. 901 ngā whakaahua i kohia mai i te -90° ki te 90° me te wā whakaatu o te 50 hēkona. I mahia te whakahounga mā te whakamahi i tētahi tātari whakaata whakamuri me te rahi voxel o te 64 nm. I mahia te tātaritanga o te wehewehenga me te tohatoha rahi matūriki mā te whakamahi i tētahi waehere motuhake kua tuhia.
Ko te whakaahuatanga o te irahiko mā te whakamahi i te maripi taimana hei whakauru i ngā MEA whakamātautau ki roto i te kapia epoxy hei whakarite mō te tapahi tino angiangi mā te whakamahi i te maripi taimana. I tapahia te wāhanga whakawhiti o ia MEA ki te matotoru o te 50 ki te 75 nm. I whakamahia he karu hiko tuku Talos F200X (Thermo Fisher Scientific) mō ngā inenga o te karu hiko tuku matawai (STEM) me te ine i te tirohanga hihi-X marara-pūngao (EDS). Kei te karu hiko he pūnaha EDS Super-X me ngā pūoko SDD kore matapihi e 4, ā, e mahi ana i te 200 kV.
I tangohia ngā tauira whakarara hihi-X paura (PXRD) i runga i te ine whakarara hihi-X paura Bruker Advance D8 me te irahiko Cu Kα kua tātarihia ki te Ni e whakahaerehia ana i te 40 kV me te 40 mA. Ko te awhe matawai kei waenga i te 10° ki te 60°, ko te rahi o te hikoinga he 0.005°, ā, ko te tere kohi raraunga he 1 hēkona mō ia hikoinga.
I inehia te whānuitanga RAS i te taha o te whakakōkī Bi2O3 Bi L3 hei pānga o te pūmanawa mā te whakamahi i tētahi pūtau i hangaia i te kāinga. I whakaritea te waituhi ionomer whakakōkī Bi2O3 mā te whakamahi i te 26.1 mg Bi2O3 i konatunatua ki te 156.3 μL otinga ionomer (6.68%), ā, i whakakorengia ki te 1 M KOH, te wai (157 μL) me te waipiro isopropyl (104 μL) hei whiwhi i te waituhi ionomer. Ko te tauwehenga whakakōkī he 0.4. I pania te waituhi ki ngā rau graphene i ngā wāhi tapawhā (10×4 mm) tae noa ki te ekenga o te uta whakakōkī Bi2O3 ki te 0.5 mg/cm2. Ko te toenga o te rau graphene kua pania ki te Kapton hei wehe i ēnei wāhi mai i te electrolyte. I whakaurua te rau graphene kua pania ki te whakakōkī ki waenganui i ngā PTFE e rua, ā, i whakauhia ki te tinana pūtau (PEEK) mā te whakamahi i ngā tīwiri, Pikitia S8. Ko Hg/HgO (1 M NaOH) te hiko tohutoro, ā, ko te pepa waro te hiko taupatupatu. I whakatikatikahia te hiko tohutoro Hg/HgO mā te whakamahi i tētahi waea konukawata i rumakina ki roto i te 0.1 M KOH kua whakakīia ki te hauwai hei huri i ngā pūmanawa katoa i inehia ki tētahi tauine hiko hauwai whakahurihuri (RHE). I whiwhihia ngā hihi XRD mā te aroturuki i te pūmanawa o tētahi hiko mahi pepa Bi2O3/graphene i rumakina ki roto i te 0.1 M KOH, i whakamahanatia ki te 30 °C. Ka huri te irahiko i roto i te pākahiko, me te tomokanga irahiko kei raro o te pūtau me te putanga kei runga hei whakarite kia pā te irahiko ki te paparanga whakakorikori ina puta he mirumiru. I whakamahia he potentiostat CH Instruments 760e hei whakahaere i te pūmanawa irahiko mahi. Ko te raupapa pūmanawa he pūmanawa ara iahiko tuwhera: -100, -200, -300, -400, -500, -800, -850, -900, -1000, -1100, -1500 me te +700 mV i runga i te RHE. Kua whakatikatikaina ngā pūmanawa iR katoa.
I whakahaerehia te tirotiro i te hanganga pai o te mimiti hihi-X (XAFS) o te taha Bi L3 (~13424 eV mō te konganuku Bi) i runga i te hongere 10-ID, te Pūtake Whakaahua Matatau (APS), te Taiwhanga Whakaata Ā-Motu o Argonne. Taiwhanga Ine Tauira Ā-Motu. I whakamahia he monochromator Si(111) karaihe-rua i whakamataohia ki te hauota wai hei whakatikatika i te kaha hihi-X, ā, i whakamahia he whakaata pania ki te rhodium hei whakaiti i te ihirangi harmonic. I rerekē ngā kaha matawai mai i te 13200 ki te 14400 eV, ā, i inehia te fluorescence mā te whakamahi i te huinga diode PIN silicon 5 × 5 kāore he tātari, he kohao Soller rānei. Ko te kaha whakawhiti kore o te tuarua o ngā derivative ka whakatikatikaina i te 13271.90 eV mā te taha L2 o te pepa Pt. Nā te matotoru o te pūtau hikohiko, kāore i taea te ine i te whānuitanga o te paerewa tohutoro i te wā kotahi. Nō reira, ko te huringa matawai-ki-matawai i tatauhia i roto i te kaha hihi-X taupatupatu he ±0.015 eV i runga i ngā inenga maha puta noa i te whakamātautau. Ko te matotoru o te paparanga Bi2O3 ka hua ake he taumata mimiti-ā-roto o te hihi-ā-rangi; ka mau tonu te aronga pumau o ngā irahiko e pā ana ki te hihi taunga me te pūoko, ā, ka tata rite tonu ngā matawai katoa. I whakamahia te whānuitanga tata-mara XAFS hei whakatau i te āhua waikura me te āhua matū o te bismuth mā te whakataurite ki te rohe XANES o ngā paerewa Bi me Bi2O3 mā te whakamahi i te raupapatanga whakauru huinga raina o te pūmanawa Athena (putanga 0.9.26). mā te waehere IFEFFIT 44.
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