1. Ua cov pa roj carbon dioxide anode taw qhia

Nrog cov kev txhim kho txuas ntxiv ntawm kev lag luam thiab kev tshawb fawb thiab thev naus laus zis, cov ntaub ntawv anode ib txwm muaj ntau dua qhia lawv cov kev txwv. Piv txwv li, tus nqi ntawm platinum yog siab dhau; kev txhim kho qhov tsis zoo ntawm graphite hauv chlor-alkali kev lag luam thiab cov pa oxygen system tsis zoo, thiab lub zog yogqis:txhuas cov hlau nplaum anode muaj qhov tsis zoo corrosion, tsis tshua muaj hluav taws xob electrocatalytic, thiab lub zog loj tau. Los ntawm cov yuav tsum tau ntawm thiaj li" ntsuab ntawv" xws li kev txuag hluav taws xob, kev noj kom tsawg, thiab kev ua qias tuaj, cov neeg cia siab kom pom cov khoom siv tshiab nrog lub neej ntev, kev ua haujlwm hluav taws xob siab, thiab tsis muaj cov pa phem. Nyob hauv ib puag ncig ntawm cov pa oxygen tshwm sim, tib neeg tau tsim cov hlau lead dioxide electrode (PbO₂): qhov tsis-stoichiometric sib xyaw ua ke uas ua tsis tau pa oxygen thiab muaj cov hmoov txhuas nyob ntev. Nws muaj ntau cov qauv siv lead ua, siv cov anode electrodeposition los ua tus-PbO₂, uas muajKev oxidation, corrosion tiv thaiv (siab ruaj khov nyob rau hauv muaj zog acid H₂S0₄lossis HN0₃), cov pa oxygen overpotential, zoo hluav taws xob conductivity, muaj zog khi lub zog, muaj zog oxidation thaum electrolyzed nyob rau hauv cov kua aqueous, tuaj yeemdaisloj tam sim no, thiab lwm yam. Tam sim no, nws tau siv dav hauv cov tshuab hauv electroplating, smelting, kev kho dej tsis huv, thiab lwm yam, thiab tsis tuaj yeem hloov los ntawm ntau lwm cov khoom siv electrode (xws li DSA, txhuas, titaniumtxheej nrog platinum).

1.1 Lead dioxide dioxidetus yam ntxwv

Nws yog dav siv hauv kev siv electrolytic ntawm ntau yam organic tshuaj thiab nyob rau hauv tus txheej txheem ntawm cov dej phwj tuaj kho thiab siab-purity dej npaj,daim ntawv thov ntau yam yog dav.Pb02 muaj qhov zoo ntawm kev ua hluav taws xob zoo heev, kev coj ua zoo thiab kev tawm paug rov qab, thiab tus nqi qis. Nws yog dav siv raws li qhov zoo electrode rau cov roj teeb txhuas kua qaub. Tam sim no, kev siv tus nqi ntawm cov hlau lead dioxide, cov khoom ua haujlwm zoo ntawm cov roj teeb ua kua qaub, tsis siab, thiab feem ntau tsis tshaj 50%. Cov pa oxygen muaj peev xwm loj, feem ntau 1.75V (piv rau calomel electrode), thiab muaj lub zog txo kev quab yuamntawmqhov kev ua tsis tau zoorau organickhoom siv(COD).

1.2 Hauv qab txheej ntawm Lead dioxide anode

Cov ntaub ntawv tam sim no siv raws li hauv qab txheej yog: platinum pab pawg hlau thiab lawv cov oxides, tin antimony oxide, iridium tantalum composite oxide hauv qab txheej, thiab lwm yam, lawv cov khoom yog raws li hauv qab no: (1) cov pab pawg platinum thiab lawv cov oxides: txheej hauv qabhraws li cov hluav taws xob zoo hluav taws xob, uas tuaj yeem txhim kho qhov sib cuam tshuam ntawm kev ua tiav ntawm cov xim txheej thiab cov substrate. (2) Tin antimony oxide: Lub tin antimony oxide txheej tau los ntawm thermal decomposition txoj kev yog ntom thiab zoo ib yam. Nrog rau cov kab hauv qab no, nws yog qhov nyuaj rau lub xaim hluav taws xob nkag mus rau titanium qhov chaw, cov pa oxygen atoms lossis 02-. Qhov sib txawv ntawm ions mus rau hauv titanium matrix kuj tseem thaiv, yog li zam qhov tsim ntawm Ti02. Tsis tas li, Ti02 yog qhov ua kom dav-bandgap N-hom semiconductor. Tom qab doping nrog Sb, cov xaim hluav taws xob ntxiv hauv Sn02 ntxaij ntoo hloov pentavalent Sn atom hauv Sn02 ntxaij nrog cov hluav taws xob ntxiv nkag mus rau hauv kev sib txuas ntawm pawg, uas zoo heev nce lub zog hluav taws xob hauv cov pawg sib xyaw. Txawm li cas los xij, thaum Sb muaj ntau dhau, qhov teeb meem tsis sib haum ntawm sn02 ntxaij yuav ntau zog, thiab hluav taws xob kev coj ntawm sn02 yuav raug txo kom tsawg. Yog li ntawd, cov ntsiab lus ntawm Sb cuam tshuam rau kev ua kom zoo tshaj thiab ua tsis tau zoo ntawm qhov kev ua tau zoo. Cov txheej hauv qab no tseem muaj qhov ua haujlwm ntawm kev txo kev ntxhov siab sab hauv ntawm txheej. (3) Titanium-tantalum composite oxide hauv qab txheej: Qhov hauv qab txheej no muaj cov yam ntxwv ntawm kev coj ua zoo, zoo corrosion tsis kam, thiab ua haujlwm tsis tshua muaj hluav taws xob. Txawm hais tias qhov hauv qab txheej txheej tshwm sim thaum cov txheej txheem electrolysis, tsis muaj cov tshuaj tiv thaiv electrolytic tshwm sim, yog li tsis muaj teeb meem tias txheej plating txheej tawm vim qhov no.

1.3 Nto txheej txheejntawm txhuasdioxide anode

PbO2 nto txheej txheej feem ntau npaj los ntawm ib hom qauv electrodeposition. Nws muaj ob lub qauv siv lead ua, α thiab β, thiab β-PbO2 muaj cov tshuaj tiv thaiv zoo thiab hluav taws xob hluav taws xob, thiab feem ntau yog siv los ua cov saum npoo txheej ntawm cov khoom siv hluav taws xob. Txawm li cas los xij, α-PbO2 muaj lub zog khi ruaj khov, thiab nws O-O atomic nrug yog nyob nruab nrab ntawm "txheej txheej hauv qab" thiab β-PbO2, uas tuaj yeem ua raws li kev tsis sib haum, txo cov electrodeposition distortion thiab ua kom muaj kev sib txuam ntawm cov nplaim thiab hauv qab txheej. Yog li ntawd, hauv cov txheej txheem electroplating, α-hom PbO2 tuaj yeem muab tso rau hauv qab muaj cov alkaline muaj zog ua ntej, thiab β-hom PbO2 tuaj yeem tso rau hauv qab cov kua qaub los txhim kho cov kev pab cuam lub neej ntawm cov electrode.

2. Ua teb daim ntawv thov ntawm cov hlau lead dioxide titanium-raws li electrode

Nyob hauv ib puag ncig ntawm cov pa oxygen tshwm sim, cov hlau lead dioxide electrodesyogtsim. PbO2 yog cov neeg tsis-ua kom muaj cov kab mob uas tsis txaus oxygen thiab muaj cov hmoov txhuas nyob ntev. Nws muaj ntau hom siv lead ua. Kev xeb (ntau dua qhov kev ruaj ntseg nyob rau hauv muaj zog acid H2S04 lossis HN03), cov pa oxygen siab dhau, qhov hluav taws xob zoo, kev sib xyaw hluav taws xob, lub zog ruaj khov thaum muaj hluav taws xob hauv cov tshuaj aqueous, tuaj yeemdaisloj tam sim no, thiab lwm yam,nws yog muaj peev xwm heev. Tam sim no, nws tau dav siv nyob rau hauv cov teb ntawm electroplating, smelting, pov tsegkev kho dej, cathode anti-corrosion, thiab lwm yam, uas tsis tuaj yeem hloov los ntawm ntau lwm cov khoom siv hluav taws xob (xws li DSA, txhuas, titanium platinum plating).

Hmoov txhuas electrodes muaj qhov tsawg tsis kam, muaj cov tshuaj lom neeg ruaj khov, qhov zoo ntawm kev txhim kho corrosion, hluav taws xob zoo hluav taws xob, thiab tuaj yeem siv rau cov dej loj. Lawv tau dav siv hauv kev kho hluav taws xob ntawm ntau yam organic thiab inorganic, kev kho dej phwj thiab cov siab-purity dej npaj cov txheej txheem. Daim ntawv thov daim teb yog dav heev.

2.1 Kev Lag Luam Tshuaj lom neeg

2.1.1 Chlo siab,PbO2 electrode tau siv nyob rau hauv chlorate kev lag luam tau ntev. Kev tsim khoom ntawm bromate thiab iodate siv PbO2 electrodes yog qhov paub tab, tshwj xeeb tshaj yog iodate. Vim yog cov qauv saum npoo ntawm PbO2 electrodes, ntxiv rau electrochemical cov tshuaj tiv thaiv, nws kuj tseem ua lub luag haujlwm catalytic.

2.1.2 Cov Ntsuas Hluav Taws Xob H2O2

H2O2 tsim los ntawm electrolysis feem ntau siv Pt li hluav taws xob. Qee tus neeg tau kawm txog kev siv MnO2, Fe3O4, graphite, thiab lwm yam li cov khoom siv anode, tab sis lawv tsis muaj kev vam meej, thiab PbO2 ua qhov anode tau txais txiaj ntsig nyiaj txiag zoo. Vim tias overpotential ntawm PbO2 electrode rau oxygen yog qis dua li ntawm Pt, tib neeg tau tshawb fawb txog kev hloov pauv hloov Pt electrode nrog PbO2 electrode. Lub sijhawm Tsov Rog Thoob Ntiaj Teb Zaum 2, Nyij Pooj tsis muaj kub dawb thiab H2O2 yog qhov tsim nyog los ntawm kev ua tub rog, yog li xyoo 1944-1945, nws pom tau qhov industrialization ntawm cov tsis muaj PbO2 electrodes hloov pauv Pt-based H2O2.

2.2 Kev Lag Luam Organic Tshuaj Lag Luam

Daim ntawv thov ntawm PbO2 electrodes hauv cov organic synthesis tsis yog paub tab zoo li hauv kev thov rau kev tsim hluavtaws, thiab ntau yam tseem tau tshawb.

2.2.1 Cov Chloroform.

Hauv kev npaj ntawm chloroform, PbO2 electrode yog siv es tsis tshua siv hluav taws xob Pt electrode. Cov nyhuv yog zoo tagnrho. Cov kev mob uas tsim nyog tshaj plaws rau electrosynthesis ntawm chloroform: NaCl 300g / L, EtOH 25ml / L, PH 8 ~ 10, ntsuas kub 60 ~ 70 ℃; Qhov anode ceev tam sim no yog 0.3 txog 0.5A / m2, qhov kev siv hluav taws xob tam sim no yog 80% rau 90%, lub xov tooj ntawm tes voltage yog 5V, tus nqi hloov pauv yog 98% mus rau 99%, thiab qhov ntshiab huv yog 99.5% rau 99.9%. Hauv kev npaj ntawm bromoform, qhov kev ua haujlwm tam sim no yog 92.5%, platinum yog 87%, thiab graphite yog 86%. PbO2 yog qhov ua tau zoo tshaj anode cov khoom hauv iodoform electrosynthesis. Cov hauj lwm tam sim no yog 90%, thiab qhov poob ntawm qhov tsis yog qhov tseem ceeb.

2.2.2 Isobutyric acid

Kev lag luam, isobutyric acid yog tsim los ntawm KMnO₄ntawm isobutanol hauv nruab nrab alkaline thiab oxidized thiab rectified los tsim 1t ntawm isobutyric acid. Ntxiv rau qhov tseem ceeb hauv cov khoom siv isobutanol, nws tseem xav tau txog 3.2tKMnO4, 1.6tH2SO4, Cov khoom siv ntu xws li 0.3tNa2CO3 muaj cov nqi siab thiab tsim ze li 2tMnO2 qhov chaw pov tseg, uas paug cov ib puag ncig. Kev siv cov tshuaj txhuas ua rau cov hmoov lead ua hluav taws xob ua kom siv los ntawm oxidize isobutanol rau isobutyric acid txo cov pa phem ib puag ncig.

2.2.3 Kev kho dej phwj tuaj

Titanium-based PbO2 electrodes yog siv los kho cov kab mob uas tsis yooj yim rau cov pa phem, cov pa lom thiab muaj kuab lom, thiab cov dej khib nyiab hauv cov organic. Kev txo qis ntawm 10 mg / L methyl txiv kab ntxwv tov nrog titanium-based PbO2 electrode qhia tau hais tias tshem tawm tus nqi ntawm cov txiv kab ntxwv methyl muaj ze li 100% thaum kho ntawm qhov ceev ntawm 36 mA / cm rau 12 min, thiab hlisiab dua electrocatalytic kev ua si. Cov. Siv PbO2 electrode tshiab los kho cov pa roj nitrobenzene, nws pom tias PbO2 electrode muaj COD kev tshem tawm ntau dua li cov graphite electrode zoo tib yam. Tom qab 5 teev ntawm electrolysis, COD tshem tawm tus nqi tau nce mus txog 65%. Lub siab electrolysis ua tau zoo yog vim lub siab cov pa oxygen loj muaj peev xwm ntawm PbO2 electrode. Hauv qab qhov anodic polarization, saum npoo ntawm PbO2 electrode yog nquag ua kom muaj · OH, uas yuav hnov ​​mob nrog nitrobenzene uas migrates rau electrode nto. Cov yam ntxwv ntawm Ti / PbO2 anode electrocatalytic oxidation ntawm cov organic paug. Cov kev sim pom tau hais tias cov electrode qhia tau qhov kev ua haujlwm zoo electrocatalytic rau kev ua paug ntawm phenol, thiab muaj cov ntaub ntawv zoo ib puag ncig tiv thaiv kev cia siab. PbO2 electrode pom tau zoo catalytic kev ua tau zoo rau kev degradation ntawm aniline. Tsis pub dhau 3 teev, tus aniline tuaj yeem txais tus nqi tshem tawm ntau dua. Tib lub sijhawm, PbO2 electrode kuj qhia tau zoo kev ruaj khov thiab kev pab lub neej. Cov txiaj ntsig ntawm kev tshawb fawb txog kev kho dej ntawm hydroxystyrene pov tseg nrog PbO2 electrode ua pov thawj tias nws feem ntau tsuas yog siv 3 ~ 6h los ua kom tag nrho nws mus rau hauv kev tsis haum lossis CO2.

Hlauhaslub zog tsis sib xws khoompiv rau lwm cov ntaub ntawv, uas ua rau nws zoo nkauj tshaj plaws xaiv rau lub substratentawmlead dioxide electrode. Txawm li cas los xij, tsis yog txhua cov hlau yog qhov tsim nyog rau lub cev ntawm cov hlau lead dioxide electrode. Nws yuav tsumvalve lub cev hlau nrog cov khoom siv tam sim no tsis muaj cov yam ntxwv tam sim no, xws li Ti, Ta, Nb, Zr thiab lwm yam. Ntawm cov hlau saum toj no, Ta muaj qhov zoo tshaj plaws corrosion tsis kam thiab tsis kam, thiab yog cov khoom siv zoo tshaj plaws rau kev siv ua substrate nyob rau hauv cov nqe lus ntawm kev ua haujlwm. Txawm li cas los xij, vim tias Ta muaj qhov sib koom ua ke rau oxygen, nws feem ntau yuav tsum nyob hauv qhov chaw anoxic, thiab Ta hlau nws kim heev, yog li nws tsis nquag siv nyob rau hauv ntau lawm. Ti yog qhov pheej yig, muaj qhov tsis sib xws, siab zog, thiab muaj cua sov nthuav dav ze ntawm cov hlau lead dioxide. Yog li no, Ti feem ntau xaiv los ua cov khoom txuas ntawm cov hlau lead txhuas electrode. Cov titanium substrate feem ntau adopts mesh qauv. Qhov no vim tias Ti cov ntxaij ua kom tawv thiab khov kho sib txuas rau txheej electrodeposited. Cov hmoov lead dioxide electrode raws li Ti daim phiaj tuaj yeem txo qhov kev tsis kam rau electrolyte ntws thiab txhim kho kev ua haujlwm tam sim no, tshwj xeeb tshaj yog nyob rau ntawm qhov siab tam sim no muaj txiaj ntsig tiv thaiv cov electrode los ntawm kev kub dhau.