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Nibii ni akɛtsuɔ nii yɛ CA mu (ni ji cyclohexanone kɛ cyclohexanol ni akɛfutu mli) lɛ mli lɛ ji gbɛ ni yaa nɔ ni baanyɛ aye blema gbɛi ni biɔ shihilɛi ni mli wa lɛ najiaŋ. Shi kɛlɛ, ŋmɛnɛŋmɛnɛ beaŋ density ni baa shi kɛ kɔɔyɔŋ nibii ni haa wala yibii lɛ yaa hiɛ lɛ haa enitsumɔi lɛ naa wa waa. Yɛ nitsumɔ nɛɛ mli lɛ, wɔtsakeɔ nikel hydroxide ni ji enyɔ kɛ vanadium koni ekɛha ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ aya hiɛ ni ekwɛ faradaic nitsumɔ ni nɔ kwɔ nɔ (>80%) yɛ hewalɛ babaoo ni baanyɛ aba lɛ nɔ (1.5–1.9 V kɛ hydrogen electrode ni anyɛɔ akuɔ sɛɛ aba). Shikpamɔ kɛ nilee mli nikasemɔi jie nitsumɔi titrii enyɔ ni V tsakemɔ tsuɔ lɛ kpo, ni nɔ ni fata he ji oyaiyeli ni haa nɔ ko yaa hiɛ ekoŋŋ kɛ cyclohexanone adsorption ni yaa hiɛ. 1536 μmol cm-2 h-1) yɛ nitsumɔhe nine ni sa ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni haa mɔ tsui nyɔɔ emli (300 mA cm-2) lɛ mli, yɛ be mli ni enine shɛɔ shifimɔ nɔ >50 h. Nitsumɔ nɛɛ tsɔɔ nɔ ko ni tsuɔ nii jogbaŋŋ ni haa adipic acid ni ji electrosynthesis lɛ feɔ nɔ ni yɔɔ sɛɛnamɔ babaoo kɛ nitsumɔhei ahewalɛ.
Adipic acid (AA) ji alifatik dicarboxylic acid ni he hiaa fe fɛɛ lɛ ateŋ ekome ni akɛtsuɔ nii titri yɛ nylon 66 kɛ polyamides loo polymers krokomɛi afeemɔ mli1. Yɛ nitsumɔhei lɛ, afeɔ AA kɛtsɔ cyclohexanol kɛ cyclohexanone (ni ji, AA mu) ni akɛfutu mli lɛ nɔ, ni akɛ 50–60 vol% nitric acid tsuɔ nii akɛ nɔ ni haa hulutsoo baa. Nɛkɛ gbɛ nɛɛ yɛ shihilɛ mli naagbai ni kɔɔ nitric acid kɛ nitrogen oxides (N2O kɛ NOx) ni ajieɔ kɛjɛɔ mli lɛ he akɛ kɔɔyɔɔ ni haa jeŋ dɔɔ lɛ2,3. Eyɛ mli akɛ abaanyɛ akɛ H2O2 atsu nii akɛ nɔ kroko ni haa hulutsoo baa shi moŋ, shi ejara ni wa kɛ shihilɛ ni mli wa ni eyɔɔ lɛ haa ewaa akɛ akɛbaatsu nii, ni gbɛ ni jara waaa ni sɛɛ tsɛɔ he miihia4,5,6.
Yɛ afii nyɔŋma ni eho lɛ mli lɛ, electrocatalytic tsofai kɛ fuel synthesis gbɛi lɛ egbala jeŋ nilelɔi ajwɛŋmɔ babaoo yɛ amɛ sɛɛnamɔi ni yɔɔ hewalɛ ni anyɛɔ atsakeɔ lɛ ni akɛtsuɔ nii kɛ nitsumɔ yɛ shihilɛi ni mli ejɔ mli (tamɔ, tsu mli dɔlɛ kɛ he ni eyɔɔ lɛ mli hewalɛ)7,8,9,10. Yɛ enɛ gbɛfaŋ lɛ, electrocatalytic tsakemɔ ni akɛ KA mu lɛ feɔ AA lɛ he nitsumɔ he miihia waa koni anyɛ ana sɛɛnamɔi ni yɔɔ ŋwɛi nɛɛ, kɛ agbɛnɛ hu koni ajie nitric acid kɛ nitrous oxide ni ajieɔ kɛjɛɔ mli ni akɛkpeɔ yɛ nifeemɔi ni afɔɔ feemɔ lɛ amli lɛ ni akɛtsuɔ nii lɛ kɛjɛ mli (Mfoniri 1a). Petrosyan kɛ ekrokomɛi tsu gbɛgbamɔ nitsumɔ lɛ he nii, ni amɛbɔ bɔ ni tsɔne ni haa wala yibii tsuɔ nii lɛ tsuɔ nii ehaa lɛ he amaniɛ (COR; akase tsɔne ni haa wala yibii loo tsɔne ni haa mɔ tsui nyɔɔ emli lɛ he nii akɛ eji KA mu) yɛ nickel oxyhydroxide (NiOOH) nɔ, shi ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni haa wala yibii lɛ feɔ mlɛo (NiOOH) lɛ nɔ. ni ana 11,12. Kɛjɛ nakai beaŋ kɛbaa nɛɛ, aná hiɛyaa ni sa kadimɔ yɛ nibii ni akɛ nikel tsuɔ nii koni akɛha COR nitsumɔ lɛ aya hiɛ lɛ afeemɔ mli. Nɔkwɛmɔnɔ, akɔɔble ni akɛ nikel haidroksaid (Cu-Ni(OH)2) wo mli lɛ fee nɔ ko ni haa Cα–Cβ mligbalamɔ yaa hiɛ yɛ cyclohexanol13 mli. Etsɛko tsɔ ni wɔbɔ Ni(OH)2 ni haa mɔ tsui nyɔɔ emli ni akɛ sodium dodecyl sulfonate (SDS) tsake lɛ he amaniɛ koni ekɛfee shihilɛ bibioo ko ni haa nu nyɛɛɛ atsɔ mli ni haa cyclohexanone14 feɔ nii.
a Naagbai ni yɔɔ AA feemɔ mli kɛtsɔ KA mu lɛ electrooxidation nɔ. b Elektrɔkatalitik COR ni abɔ he amaniɛ tsutsu ni ji Ni-ni damɔ shi kɛha nibii ni haa mɔ tsui nyɔɔ emli kɛ wɔ nibii ni haa mɔ tsui nyɔɔ emli yɛ electrode etɛ gbɛjianɔtoo kɛ batiri gbɛjianɔtoo ni hoɔ lɛ mli lɛ hetoo11,13,14,16,26. Akɛ saji fitsofitso ni kɔɔ nɔ ni yaa nɔ lɛ he kɛ nɔ ni yaa nɔ lɛ he lɛ ewo Supplementary Tables 1 kɛ 2. c Catalytic nitsumɔ ni wɔ NiV-LDH-NS catalysts kɛha COR yɛ H-cell reactor kɛ MEA, ni tsuɔ nii yɛ hewalɛi babaoo nɔ lɛ.
Eyɛ mli akɛ gbɛi ni yɔɔ ŋwɛi nɛɛ ha COR nitsumɔ lɛ tee hiɛ moŋ, shi Ni-based catalysts ni atsɔɔ mli lɛ jie AA Faraday nitsumɔ ni nɔ kwɔ (FE) (>80%) kpo yɛ hewalɛi ni baa shi fioo pɛ mli, ni bei pii lɛ, eshɛɛɛ 1.6 V kɛ akɛto hydrogen electrode ni anyɛɔ akuɔ sɛɛ (RHE, VRHE kuku) lɛ he. No hewɔ lɛ, ŋmɛnɛŋmɛnɛ beaŋ fã ko ni abɔ he amaniɛ (ni ji, ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ fɛɛ ni akɛ FE to he) ni ji AA lɛ baa shi be fɛɛ be yɛ 60 mA cm−2 (Mfoniri 1b kɛ Supplementary Table 1). 200 mA cm−2)15, ni tsiɔ electrocatalytic ŋaalee kɛha AA nitsumɔ ni yaa hiɛ waa lɛ naa kwraa (Mfoniri 1a; ŋwɛi). Bɔni afee ni ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ mli tsɔne lɛ aya hiɛ lɛ, abaanyɛ akɛ hewalɛ ni hi jogbaŋŋ (kɛha tsɔne ni yɔɔ tsɔnei etɛ mli lɛ) loo tsɔne ni yɔɔ tsɔnei enyɔ mli lɛ atsu nii, ni eji gbɛ ni yɔɔ mlɛo ni atsɔɔ nɔ atsakeɔ tsɔnei babaoo, titri lɛ oxygen evolution reaction (OER). Shi, kɛha COR ni yɔɔ anodic hewalɛi ni nɔ kwɔ lɛ, OER baanyɛ afee akaŋshilɔ wulu yɛ AA FE lɛ shibaa mli, ni no baaha hewalɛ ni akɛtsuɔ nii lɛ aba shi (Mfoniri 1a; shishigbɛ). Akɛ nɔkwɛmɔnɔ lɛ, kɛ́ wɔkwɛ hiɛyaa ni eho lɛ mli (Mfoniri 1b kɛ Supplementary Table 1), wɔnijiaŋjewui akɛ wɔna akɛ FE ni yɔɔ AA nɔ yɛ SDS-tsakemɔ Ni(OH)2 nɔ lɛ ba shi kɛjɛ 93% kɛtee 76% kɛ hewalɛ ni akɛtsuɔ nii lɛ ni yaa hiɛ kɛjɛɔ 1.5 VRHE kɛtee 1.7 theVRAAHE ni yɔɔ 1.7 the. CuxNi1-x(OH)2/CF ba shi kɛjɛ 93% kɛtee 69% kɛ hewalɛ ni yaa hiɛ kɛjɛ 1.52 VRHE kɛtee 1.62 VRHE16. No hewɔ lɛ, AA lɛ fã ko ni abɔ he amaniɛ lɛ eyaaa hiɛ yɛ gbɛ ni sa nɔ yɛ hewalɛi ni nɔ kwɔlɔ amli, ni no haaa AA nitsumɔ lɛ aya hiɛ babaoo, ni wɔkawie hewalɛ ni fa babaoo ni akɛtsuɔ nii yɛ AA FE ni baa shi lɛ hewɔ lɛ he. Kɛfata nikel-ni damɔ shi shiŋŋ lɛ nɔ lɛ, cobalt-ni damɔ shi shiŋŋ lɛ hu ejie sɛɛkuu nitsumɔ yɛ COR17,18,19 mli. Shi kɛlɛ, amɛ nitsumɔ lɛ baa shi yɛ hewalɛi ni nɔ kwɔlɔ amli, ni kɛ akɛto Ni-based catalysts he lɛ, amɛ yɛ hewalɛi babaoo yɛ nitsumɔhei nitsumɔi amli, tamɔ jara tsakemɔi wuji kɛ nibii bibii ni yɔɔ mli. No hewɔ lɛ, eji nɔ ni sa akɛ afee Ni-based catalysts ni yɔɔ ŋmɛnɛŋmɛnɛ beaŋ density ni nɔ kwɔ kɛ FE yɛ COR mli koni efee nɔ ni anyɛɔ atsuɔ he nii koni anyɛ ana AA yibiiwoo ni nɔ kwɔ.
Yɛ nitsumɔ nɛɛ mli lɛ, wɔbɔɔ amaniɛ akɛ vanadium (V)-tsakemɔ nikel ni akɛwo hydroxide nanosheets enyɔ mli (NiV-LDH-NS) ji electrocatalysts ni tsuɔ nii jogbaŋŋ kɛha AA nifeemɔ kɛtsɔ COR nɔ, ni tsuɔ nii yɛ hewalɛ babaoo nɔ kɛ OER ni tsiɔ naa waa, ni enine shɛɔ FE ni nɔ kwɔ kɛ ŋmɛnɛŋmɛnɛ beaŋ electroblice membranes ni yɔɔ H Mfoniri- ME1 mli lɛ fɛɛ nɔ; b). Wɔtsɔɔ klɛŋklɛŋ akɛ, acetylene oksideshin nitsumɔ ni fe Ni (OH)2 nanosheet catalyst (Ni (OH) 2-NS) lɛ baa shi, taakɛ akpaa gbɛ lɛ, yɛ hewalɛi ni nɔ kwɔlɔ amli, kɛjɛ 80% yɛ 1.5 VRHE kɛyashi 42% yɛ 1.9 VRHE. Nɔ ni tamɔɔɔ enɛ lɛ, beni atsake Ni(OH)2 kɛ V sɛɛ lɛ, NiV-LDH-NS jie ŋmɛnɛŋmɛnɛ beaŋ hewalɛ ni nɔ kwɔ kpo yɛ hewalɛ ko mli, ni nɔ ni he hiaa fe fɛɛ lɛ, ehiɛ FE ni nɔ kwɔ mli yɛ hewalɛ babaoo nɔ. Akɛ nɔkwɛmɔnɔ lɛ, yɛ 1.9 VRHE lɛ, etsɔɔ ŋmɛnɛŋmɛnɛ beaŋ 170 mA cm−2 kɛ FE ni ji 83%, ni ji nɔ ni hi fe fɛɛ ni haa COR yaa hiɛ yɛ three-electrode gbɛjianɔtoo lɛ mli (Fig. 1c kɛ Supplementary Table 1). Shikpamɔ kɛ tsɔɔmɔi ahe saji tsɔɔ akɛ V tsakemɔ lɛ haa shishijee nibii ni baa shi lɛ yaa hiɛ kɛjɛɔ Ni (OH)2 kɛyaa Ni oxyhydroxides (Ni3+xOOH1-x) ni yɔɔ sɛɛnamɔ waa lɛ nɔ, ni tsuɔ nii akɛ fã ni tsuɔ nii kɛhaa COR. Kɛfata he lɛ, V tsakemɔ lɛ ha cyclohexanone ni yɔɔ nɔ ni haa nɔ ko yaa hiɛ lɛ nɔ lɛ tee hiɛ, ni etsu gbɛfaŋnɔ titri ko he nii yɛ OER ni tsiɔ naa yɛ anodic hewalɛi ni nɔ kwɔlɔ lɛ amli. Kɛha NiV-LDH-NS nyɛmɔ lɛ kpojiemɔ yɛ shihilɛ ni yɔɔ diɛŋtsɛ mli lɛ, wɔfee MEA shwiemɔ tsɔne ni wɔtsɔɔ FE ni ji AA (82%) yɛ nitsumɔhe ko ni kɔɔ ŋmɛnɛŋmɛnɛ beaŋ tsɔne (300 mA cm−2), ni ji nɔ ni nɔ kwɔ kwraa fe wɔ tsutsu hetooi lɛ yɛ membrane shwiemɔ tsɔne kɛ Supplement Table (Fig 2). AA yibiiwoo ni kɛ lɛ kpãa gbee (1536 μmol cm−2 h−1) lɛ fa fe nɔ ni anáa kɛtsɔ hulutsoo nibii ni haa hulutsoo baa lɛ nɔ (<30 mmol gcatalyst−1 h−1)4. Agbɛnɛ hu, nɔ ni haa nɔ ko yaa hiɛ lɛ tsɔɔ shifimɔ kpakpa kɛji akɛ akɛ MEA tsu nii, ni ehiɛ FE >80% AA kɛha ŋmɛlɛtswai 60 yɛ 200 mA cm−2 kɛ FE >70% AA kɛha ŋmɛlɛtswai 58 yɛ 300 mA cm−2. Yɛ naagbee lɛ, shishijee nikasemɔ ko ni kɔɔ bɔ ni ebaanyɛ eba lɛ he (FEA) tsɔɔ bɔ ni electrocatalytic gbɛjianɔtoo ni akɛtsuɔ nii kɛfeɔ AA lɛ he ehiaaa tsɔ.
Taakɛ woji ni eho lɛ tsɔɔ lɛ, Ni(OH)2 ji nɔ ko ni haa mɔ tsui nyɔɔ emli ni tsɔɔ nitsumɔ kpakpa kɛha COR, no hewɔ lɛ, afee Ni(OH)2-NS13,14 klɛŋklɛŋ kwraa kɛtsɔ coprecipitation gbɛ nɔ. Nɔkwɛmɔnii lɛ tsɔɔ β-Ni (OH)2 gbɛjianɔtoo, ni X-ray diffraction (XRD; Fig. 2a) lɛ ma nɔ mi, ni nanosheets ni yɔɔ mlɛo waa (elɛɛmɔ: 2–3 nm, sɛɛgbɛ dalɛ: 20–50 nm) lɛ ji nɔ ni akwɛ kɛtsɔ ŋwɛi ŋta ni nɔ kwɔ ni akɛtsuɔ nii kɛtsɔɔ ŋwɛi ŋta ni ji atomic supplement microscopy (HRM Fig. (AFM) susumɔi (Mfoniri ni fata he 2). Ana nanosheets lɛ anaabuamɔ hu yɛ amɛ su ni yɔɔ mlɛo waa lɛ hewɔ.
Ni (OH)2-NS kɛ NiV-LDH-NS lɛ mli nibii ni haa mɔ he jɔɔ lɛ. FE, nɔ ni tsɔɔ mli, kɛ AA ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni yɔɔ b Ni (OH) 2-NS kɛ c NiV-LDH-NS nɔ yɛ nyɛmɔi srɔtoi amli. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔ ni yɔɔ susumɔi etɛ ni yɔɔ amɛ diɛŋtsɛ amɛhe ni akɛ catalyst kome tsuɔ nii lɛ mli. d HRTEM mfoniri ni ji NV-LDH-NS. Skel bar: 20 nm. HAADF-STEM mfoniri ni kɔɔ NiV-LDH-NS he kɛ shishijee shikpɔŋ he mfoniri ni kɛ lɛ kpãa gbee ni tsɔɔ bɔ ni Ni (eŋɔli), V (ŋmɔŋ), kɛ O (bluu) mlijaa lɛ yɔɔ ha. Skel bar: 100 nm. XPS adafitswaa ni kɔɔ Ni (OH) 2-NS (ŋwɛi) kɛ NiV-LDH-NS (shishi) he lɛ. i FE kɛ j ji AA nifeemɔi ni yɔɔ tsɔnei enyɔ ni haa mɔ tsui nyɔɔ emli lɛ anɔ fe 7 sɛɛkuu. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔ ni yɔɔ susumɔi etɛ ni yɔɔ amɛ diɛŋtsɛ amɛhe ni akɛ catalyst kome tsuɔ nii ni amɛyɔɔ 10% mli. Akɛ saji ni kɔɔ a–c kɛ f–j he lɛ haa yɛ saji ni aŋmala ashwie shi lɛ amli.
No sɛɛ lɛ, wɔkwɛ bɔ ni Ni(OH)2-NS lɛ tsuɔ nii ehaa yɛ COR nɔ lɛ mli. Kɛtsɔ electrolysis ni yɔɔ hewalɛ ni yaa nɔ daa lɛ nɔ lɛ, wɔnine shɛ 80% FE ni ji AA nɔ yɛ hewalɛ ni baa shi (1.5 VRHE) ni OER bɛ mli (Mfoniri 2b), ni tsɔɔ akɛ COR lɛ ji hewalɛ ni hi fe OER yɛ anodic hewalɛ ni baa shi mli. Ana akɛ nɔ titri ni jɛɔ mli baa ji glutaric acid (GA) ni FE ji 3%. Akɛ HPLC hu tsɔɔ bɔ ni succinic acid (SA), malonic acid (MA), kɛ oxalic acid (OA) ni yɔɔ mli lɛ fa ha (kwɛmɔ Mfoniri ni Akɛfata He 3 kɛha nibii lɛ amlijaa). Anaaa formic acid ko yɛ nibii ni afee lɛ mli, ni tsɔɔ akɛ abaanyɛ afee carbonate akɛ C1 nibii ni jɛɔ mli baa lɛ. Kɛha susumɔ nɛɛ kaa lɛ, akɛ tsɔne ni jɛɔ tsɔne ni ji 0.4 M cyclohexanone lɛ mli lɛ mli lɛ wo acid mli ni akɛ nibii ni tamɔ kɔɔyɔɔ lɛ tsɔ Ca(OH)2 tsɔne mli. Nɔ ni jɛ mli ba ji akɛ, tsofa lɛ bafee ŋmɔtɔ, ni ema nɔ mi akɛ carbonate lɛ ba yɛ electrolysis sɛɛ. Shi, yɛ srawa hewalɛ fɛɛ ni ajieɔ lɛ kpo yɛ srawa hewalɛ nifeemɔ lɛ mli lɛ faaa hewɔ lɛ (Mfoniri 2b, c) lɛ, carbonate lɛ mli nibii ni yɔɔ mli lɛ faaa ni ewa akɛ aaatsɔɔ bɔ ni eyɔɔ ha. Kɛfata he lɛ, abaanyɛ afee C2-C5 nibii krokomɛi hu, shi anyɛɛɛ atsɔɔ amɛyibɔ. Eyɛ mli akɛ ewa akɛ aaatsɔɔ nibii ni afee lɛ fɛɛ ayibɔ moŋ, shi 90% ni ji electrochemical equivalent lɛ fɛɛ tsɔɔ akɛ ana electrochemical nifeemɔi lɛ ateŋ babaoo, ni no haa wɔnáa shishitoo kɛha wɔ tsɔne he shishinumɔ. Yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ mli tsɔne ni baa shi lɛ hewɔ lɛ (20 mA cm−2), AA yibiiwoo lɛ ji 97 μmol cm−2 h−1 (Mfoniri 2b), ni kɛ 19 mmol h−1 g−1 yeɔ egbɔ ni damɔ tsɔne ni haa tsɔne lɛ tsuɔ nii lɛ nɔ (5 mg cm−2), ni baa shi fe tsɔne ni haa tsɔne lɛ mli la ni haa tsɔne lɛ tsuɔ nii lɛ (5 mg cm−1) lɛ. Beni hewalɛ ni akɛtsuɔ nii lɛ tee hiɛ kɛjɛ 1.5 kɛyashi 1.9 VRHE lɛ, eyɛ mli akɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ fɛɛ tee hiɛ (kɛjɛ 20 kɛyashi 114 mA cm−2), shi yɛ be kome too mli lɛ, AA FE lɛ ba shi waa, kɛjɛ 80% kɛyashi 42%. FE ni baa shi yɛ nyɛmɔi ni hi babaoo mli lɛ jɛ akaŋshii ni akɛhaa OER lɛ mli titri. 1.7 VRHE lɛ, OER akaŋshii lɛ kɛ AA FE lɛ baa shi waa, ni no haa AA nitsumɔ lɛ baa shi fioo kɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ fɛɛ ni yaa hiɛ lɛ. No hewɔ lɛ, eyɛ mli akɛ AA lɛ fã ko ni yɔɔ amrɔ nɛɛ mli lɛ tee hiɛ kɛjɛ 16 kɛtee 48 mA cm−2 ni AA nitsumɔ lɛ tee hiɛ (kɛjɛ 97 kɛtee 298 μmol cm−2 h−1), shi hewalɛ babaoo ni fata he lɛ tsu nii (2.5 W h gAA−1 babaoo kɛjɛ 1.5 of g2 mli), ni jɛ mli ba ji 1.9 eVR yɛ g2 mli. gAA−1 (akɛ akɔntaabuu lɛ he saji eha yɛ Nɔ ni Akɛfata He 1 lɛ mli). OER ni akadi tsutsu akɛ akaŋshilɔ kɛha COR hetoo yɛ anodic hewalɛi ni nɔ kwɔlɔ lɛ kɛ amaniɛbɔi ni eho lɛ kpãa gbee ni edamɔ shi kɛha kaa ni yaa hiɛ kɛha AA nitsumɔ mliyaa14,17.
Kɛha Ni (OH) 2-NS-based COR catalyst ni tsuɔ nii jogbaŋŋ lɛ feemɔ lɛ, wɔpɛi fã ni tsuɔ nii lɛ mli klɛŋklɛŋ. 473 cm-1 kɛ 553 cm-1 lɛ mli yitsei ni yɔɔ wɔ in situ Raman spectroscopy hetooi lɛ amli (Mfoniri ni fata he 4), ni kɛ Ni3 + -O bɔɔnd ni yɔɔ NiOOH lɛ mli lɛ shwiemɔ kɛ egbɛɛmɔ kpãa gbee, yɛ gbɛ kome nɔ. Aŋma akɛ NiOOH ji nɔ ni jɛɔ Ni(OH)2 shibaa kɛ Ni(OH)O ni abua naa yɛ anodic hewalɛ mli, ni eji nɔ ni tsuɔ nii yɛ electrocatalytic oxidation20,21 mli. No hewɔ lɛ, wɔkpaa gbɛ akɛ, kɛ́ wɔfee Ni (OH)2 kɛtee NiOOH lɛ, ebaanyɛ eha COR lɛ nitsumɔ ni haa mɔ tsui nyɔɔ emli lɛ aya hiɛ.
Wɔbɔ mɔdɛŋ ni wɔtsake Ni (OH) 2 kɛ dade srɔtoi kɛjɛ be mli ni ana akɛ heteroatom tsakemɔ haa sɛɛkuu lɛ yaa hiɛ yɛ tsakemɔ dade oxides/hydroxides22,23,24. Akɛ Ni kɛ dade ni ji enyɔ ni tsɔɔ hiɛ lɛ fee nɔkwɛmɔnii lɛ. Yɛ dade-tsakemɔ nɔkwɛmɔnii srɔtoi lɛ ateŋ lɛ, V-tsakemɔ nɔkwɛmɔnɔ (V:Ni atomic ratio 1:8) (ni atsɛɔ lɛ NiV-LDH-NS) tsɔɔ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni fa babaoo yɛ COR (Supplementary Fig. 5) mli, ni nɔ ni he hiaa fe fɛɛ lɛ, AA FE ni nɔ kwɔ yɛ samflɛ ni baanyɛ aba mli babaoo nɔ. Yɛ gbɛ titri ko nɔ lɛ, yɛ hewalɛ ni baa shi (1.5 VRHE) mli lɛ, NiV-LDH-NS ni yɔɔ amrɔ nɛɛ mli lɛ fa fe Ni(OH)2-NS (39 kɛ 20 mA cm−2) lɛ shii 1.9, ni AA FE lɛ ji nɔ ni akɛtoɔ nibii ni haa mɔ tsui nyɔɔ emli lɛ fɛɛ ahe (83% kɛ 80%). Yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni fa babaoo kɛ FE AA ni tamɔ nakai lɛ hewɔ lɛ, NiV-LDH-NS nitsumɔ lɛ fa fe Ni(OH)2-NS (204 vs. 97 μmol cm−2 h−1) lɛ shii 2.1, ni tsɔɔ bɔ ni V tsakemɔ lɛ woɔ ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ hiɛ nyam yɛ hewalɛi ni baa shi lɛ amli (Mfoniri 2).
Kɛji akɛ hewalɛ ni akɛtsuɔ nii lɛ yaa hiɛ (tamɔ, 1.9 VRHE), ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni yɔɔ NiV-LDH-NS lɛ nɔ lɛ fa fe nɔ ni yɔɔ Ni(OH)2-NS lɛ nɔ lɛ toi 1.5 (170 vs. 114 mA cm−2), ni nɔ ni yaa hiɛ lɛ tamɔ nɔ ni yɔɔ hewalɛ ni baa shi lɛ nɔ lɛ (1.9 shii abɔ). Nɔ ni sa kadimɔ ji akɛ, NiV-LDH-NS hiɛ AA FE ni nɔ kwɔ lɛ mli (83%) ni OER lɛ tsi enaa waa (O2 FE 4%; Mfoniri 2c), ni etsuɔ ​​nii fe Ni (OH) 2-NS kɛ tsutsu amaniɛbɔɔ ni kɔɔ nibii ni haa mɔ tsui nyɔɔ emli ni yɔɔ AA FE ni baa shi kwraa lɛ he yɛ anodic hewalɛi ni nɔ kwɔlɔ (Supplementary Table 1). Yɛ FE ni nɔ kwɔ ni yɔɔ AA mli yɛ samflɛ ni mli kwɔ mli (1.5–1.9 VRHE) lɛ hewɔ lɛ, AA yinɔ ni falɛ ji 867 μmol cm−2 h−1 (ni kɛ 174.3 mmol g−1 h−1 yeɔ egbɔ) lɛ ji nɔ ni anyɛ ana yɛ 1.9 VRHE, ni tsɔɔ bɔ ni etsuɔ ​​nii jogbaŋŋ ehaa yɛ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ mli. ni akɛ NiV-LDH-NS nɔkwɛmɔnii lɛ fɛɛ ni akɛwoɔ mli lɛ feɔ nɔ ni sa (Supplementary Fig. 6).
Kɛha shishinumɔ ni yɔɔ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni fa babaoo kɛ FE ni nɔ kwɔ yɛ hewalɛ babaoo nɔ yɛ Ni (OH)2 kɛ V tsakemɔ sɛɛ lɛ, wɔtsɔɔ bɔ ni NiV-LDH-NS lɛ yɔɔ ha lɛ mli. XRD hetooi lɛ tsɔɔ akɛ tsakemɔ ni akɛ V fee lɛ ha fã tsakemɔ ko ba kɛjɛ β-Ni(OH)2 kɛtee α-Ni(OH)2, ni anaaa kristalo henɔ ko ni kɔɔ V he (Mfoniri 2a). HRTEM hetooi lɛ tsɔɔ akɛ NiV-LDH-NS lɛ gboshinii ji bɔ ni Ni(OH)2-NS nanosheets ni yɔɔ mlɛo lɛ yɔɔ ha lɛ, ni eyɛ sɛɛgbɛ fãi ni tamɔ nakai nɔŋŋ (Mfoniri 2d). AFM susumɔi jie nanosheets lɛ mli nibii ni abua naa lɛ ahe su ni mli wa kpo, ni no ha anyɛɔ asusuɔ ŋmɔlɔ ni miihe ashɛ 7 nm (Supplementary Fig. 7), ni da fe Ni(OH)2-NS (ŋmɔlɔ: 2–3 nm) lɛ. Hewalɛ-gbɛfaŋnɔ X-ray spectroscopy (EDS) shikpɔŋ he mfoniri mlipɛimɔ (Mfoniri 2e) tsɔɔ akɛ V kɛ Ni nibii lɛ mlijaa jogbaŋŋ yɛ nanosheets lɛ mli. Kɛha tsɔne ni yɔɔ V mli lɛ mlitsɔɔmɔ kɛ bɔ ni etsuɔ ​​nii ehaa yɛ Ni nɔ lɛ, wɔkɛ X-ray fotoelektrɔn tsɔne ni akɛkwɛɔ nibii amli (XPS) (Mfoniri 2f–h) tsu nii. Ni(OH)2-NS jieɔ Ni2+ yitso ni yɔɔ ŋwɛigbɛ lɛ kpo (yoo yitso yɛ 855.6 eV, satelait yitso yɛ 861.1 eV, mfoniri 2f)25. s XPS spectrum ni ji Ni(OH)2-NS lɛ baanyɛ aja mli awo yitsei etɛ mli, ni amɛteŋ yitsei ni yɔɔ 529.9, 530.9 kɛ 532.8 eV lɛ ji lattice oxygen (OL), hydroxyl kuu (Ni-OH) kɛ oxygen ni ajieɔ kɛjɛɔ ŋwɛi ŋtayaai amli lɛ (O 2g) 26,27,28,29. Yɛ tsakemɔ ni akɛ V fee lɛ sɛɛ lɛ, V 2p3/2 yitso lɛ je kpo, ni abaanyɛ akumɔ mli awo yitsei etɛ ni yɔɔ 517.1 eV (V5+), 516.6 eV (V4+) kɛ 515.8 eV (V3+) lɛ amli, ni tsɔɔ akɛ V henɔi ni yɔɔ shishitoo mla ni nɔ kwɔ lɛ mli lɛ titri ji nɔ ni yɔɔ (Mfoniri 100). 2h) 25,30,31. Kɛfata he lɛ, Ni 2p yitso ni yɔɔ 855.4 eV yɛ NiV-LDH-NS mli lɛ tsake yɛ gbɛ ni ehiii nɔ (aaafee 0.2 eV) kɛ akɛto nɔ ni yɔɔ Ni(OH)2-NS lɛ he, ni tsɔɔ akɛ ajie electrons kɛjɛ V kɛtee Ni. Ni shihilɛ ni baa shi ni ana yɛ V tsakemɔ sɛɛ lɛ kɛ Ni K-edge X-ray absorption ni bɛŋkɛ-edge spectroscopy (XANES) lɛ hetooi lɛ kpãa gbee (kwɛmɔ “V Tsakemɔ Woɔ Catalyst Reduction Hewalɛ” fã ni yɔɔ shishi lɛ mli kɛha saji krokomɛi). NiV-LDH-NS lɛ yɛ COR tsamɔ sɛɛ kɛha ŋmɛlɛtswaa kome lɛ ji nɔ ni ahala lɛ akɛ NiV-LDH-POST ni ajie lɛ kpo jogbaŋŋ kɛtsɔ tsɔne ni akɛkwɛɔ nibii bibii ni akɛtsuɔ nii yɛ tsɔne mli lɛ nɔ, EDS shikpɔŋ he mfonirifeemɔ, X-ray tsɔne ni akɛkwɛɔ nibii amli, Raman tsɔne ni akɛkwɛɔ nibii amli, kɛ XPS susumɔi (Supplementary Figs. 8 kɛ 9). Nibii ni haa nɔ ko yaa hiɛ lɛ tee nɔ ehi shi akɛ nibii ni abua naa kɛ nanosheet ni yɔɔ mlɛo (Kpojiemɔ Fig. 8a–c). Nibii ni akwɛɔ lɛ amli kristalo lɛ ba shi ni V mli nibii lɛ ba shi yɛ V ni hoɔ kɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ sɛɛkuu hewɔ (Supplementary Fig. 8d–f). XPS spectra lɛ tsɔɔ akɛ V peak hewalɛ lɛ eba shi (Supplementary Fig. 9), ni akɛto V leaching lɛ he. Kɛfata he lɛ, O 1s spectrum mlipɛimɔ (Kpojiemɔ Mfoniri 9d) kɛ electron paramagnetic resonance (EPR) susumɔi (Kpojiemɔ Mfoniri 10) tsɔɔ akɛ, oxygen ni yɔɔ NiV-LDH-NS lɛ nɔ lɛ falɛ tee hiɛ yɛ 1 h ni akɛ electrolysis tsuɔ nii yɛ mli lɛ sɛɛ, ni baanyɛ aha Nipp shift ni ehiii lɛ aba. 9 kɛ 10 kɛha saji krokomɛi)26,27,32,33. No hewɔ lɛ, NiV-LDH-NS tsɔɔ tsakemɔ fioo ko yɛ gbɛjianɔtoo mli yɛ 1 h COR sɛɛ.
Kɛha gbɛfaŋnɔ ni he hiaa ni V tsuɔ yɛ COR hiɛyaa mli lɛ nɔmimaa lɛ, wɔkɛ NiV-LDH nibii ni haa mɔ tsui nyɔɔ emli lɛ fee ekome kɛ V:Ni atomik ratios sɔrɔtoi (1:32, 1:16, kɛ 1:4, ni atsɔɔ akɛ NiV-32, NiV-16, kɛ NiV-4, yɛ gbɛ kome nɔ) ja 1:8 kɛtsɔ coprecipitation me lɛ nɔŋŋ nɔ. EDS shikpɔŋ he mfonirifeemɔ hetooi lɛ tsɔɔ akɛ V:Ni atomic ratio ni yɔɔ tsɔne ni haa tsɔne lɛ tsuɔ nii lɛ mli lɛ bɛŋkɛɔ nɔ ni tsɔɔ hiɛ lɛ nɔ (Supplementary Fig. 11a–e). Kɛ V tsakemɔ lɛ tee hiɛ lɛ, V 2p spectrum lɛ mli hewalɛ yaa hiɛ, ni Ni 2p kpokpaa lɛ nɔ hewalɛ ni fiɔ mɔ lɛ yaa nɔ eshiɔ kɛyaa fã ni ehiii lɛ nɔ (Supplementary Fig. 12). Yɛ nakai beaŋ nɔŋŋ lɛ, OL lɛ mlijaa lɛ tee hiɛ fiofio. Nɔ ni jɛ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ mli ba lɛ tsɔɔ akɛ, abaanyɛ ajie OER lɛ jogbaŋŋ yɛ V tsakemɔ bibioo ko po sɛɛ (V:Ni atomic ratio ni ji 1:32), ni O2 FE lɛ baa shi kɛjɛɔ 27% kɛyaa 11% yɛ 1.8 VRHE yɛ V tsakemɔ sɛɛ (Supplementary Fig. 11f). Kɛ V:Ni ratio lɛ tee hiɛ kɛjɛ 1:32 kɛtee 1:8 lɛ, nɔ ni haa tsɔne lɛ tsuɔ nii lɛ tee hiɛ. Shi, kɛ V tsakemɔ lɛ tee hiɛ babaoo (V:Ni ratio ni ji 1:4) lɛ, ŋmɛnɛŋmɛnɛ beaŋ ŋmei lɛ baa shi, ni wɔsusuɔ akɛ eji ŋmei ni yɔɔ Ni nitsumɔ hei lɛ amli lɛ baa shi (titri lɛ NiOOH nitsumɔ fã lɛ; Supplementary Fig. 11f). Yɛ V tsakemɔ lɛ he hewalɛ ni tsiɔ mɔ naa kɛ Ni hei ni tsuɔ nii lɛ akwɛmɔ hewɔ lɛ, nɔ ni haa mɔ tsui nyɔɔ emli ni yɔɔ V:Ni ratio ni ji 1:8 lɛ jie FE kɛ AA nitsumɔ ni nɔ kwɔ fe fɛɛ kpo yɛ V:Ni ratio lɛ mlikwɛmɔ kaa lɛ mli. Bɔni afee ni atsɔɔ mli faŋŋ akɛ V:Ni ratio lɛ hiɔ shi daa yɛ electrolysis sɛɛ lɛ, atsɔɔ bɔ ni nibii ni akɛtsuɔ nii lɛ feɔ amɛnii amɛhaa lɛ mli. Nɔ ni jɛ mli ba lɛ tsɔɔ akɛ, kɛha tsɔnei ni haa tsɔne lɛ tsuɔ nii ni shishijee V:Ni ratios lɛ jeɔ shishi kɛjɛɔ 1:16 kɛyashiɔ 1:4 lɛ, V:Ni ratio lɛ ba shi kɛyashɛ aaafee 1:22 yɛ tsɔne lɛ sɛɛ, ni ekolɛ eji V ni hoɔ yɛ tsɔne lɛ sɛɛkuu lɛ hewɔ (Supplementary Fig. 13). Kaadi akɛ, ana AA FEs ni akɛtoɔ he lɛ beni shishijee V:Ni ratio lɛ yeɔ egbɔ loo nɔ ni fe 1:16 (Supplementary Fig. 11f), ni abaanyɛ atsɔɔ mli kɛtsɔ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ sɛɛkuu ni kɛ V:Ni ratios ni tamɔ nakai nɔŋŋ baa yɛ tsɔnei ni haa mɔ tsui nyɔɔ emli lɛ amli ni tsɔɔ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ nitsumɔ ni akɛtoɔ he lɛ mli lɛ nɔ.
Kɛha bɔ ni V-modified Ni(OH)2 he hiaa ha yɛ COR nitsumɔ lɛ mliyaa mli lɛ nɔmimaa babaoo lɛ, wɔfee gbɛi krokomɛi enyɔ ni akɛfeɔ nibii ni akɛ V woɔ Ni(OH)2-NS nibii amli. Ekome ji gbɛ ni atsɔɔ nɔ akɛfutuɔ nii, ni atsɛɔ nɔkwɛmɔnɔ lɛ akɛ NiV-MIX; ekroko lɛ ji gbɛ ni atsɔɔ nɔ ashɛreɔ nii ni nyiɛɔ sɛɛ, ni atsɛɔ nɔkwɛmɔnɔ lɛ akɛ NiV-SP. Akɛ sɛɛkuu lɛ mli saji fitsofitso eha yɛ Gbɛi ni Atsɔɔ nɔ Atsuɔ Nii lɛ fã lɛ mli. SEM-EDS shikpɔŋ he mfonirifeemɔ tsɔɔ akɛ V lɛ ye omanye yɛ Ni (OH) 2-NS nɔkwɛmɔnii enyɔ lɛ fɛɛ nɔ (Supplementary Fig. 14). 1.8 VRHE lɛ, AA nitsumɔ ni yɔɔ NiV-MIX kɛ NiV-SP tsɔne lɛ nɔ lɛ ji 78% kɛ 79%, ni amɛ fɛɛ amɛtsɔɔ nitsumɔ ni nɔ kwɔ fe Ni(OH)2-NS (51%). Kɛfata he lɛ, ajie OER ni yɔɔ NiV-MIX kɛ NiV-SP tsɔnei lɛ anɔ lɛ (FE O2: 7% kɛ 2%, yɛ gbɛ kome nɔ) kɛ akɛto Ni(OH)2-NS (FE O2: 27%) he. Nɛkɛ yibii nɛɛ maa nɔ ni hi ni V tsakemɔ ni yɔɔ Ni (OH) 2 mli lɛ tsuɔ yɛ OER nɔyeli nɔ lɛ nɔ mi (Supplementary Fig. 14). Shi kɛlɛ, tsɔnei ni haa mɔ tsui nyɔɔ emli lɛ ahilɛ-kɛhamɔ lɛ fite, ni ejie ehe kpo yɛ FE AA ni baa shi yɛ NiV-MIX nɔ kɛtee 45% kɛ NiV-SP nɔ kɛtee 35% yɛ COR sɛɛkuu kpawo sɛɛ, ni tsɔɔ akɛ ehe miihia ni atsɔ gbɛi ni sa nɔ atsu nii koni akɛha V henɔi lɛ ahi shi shiŋŋ, tamɔ Ni( la- Ni-)V tsakemɔ yɛ . nɔ titri ni haa mɔ tsui nyɔɔ emli yɛ nitsumɔ nɛɛ mli.
Wɔkwɛ bɔ ni Ni (OH) 2-NS kɛ NiV-LDH-NS lɛ damɔ shi shiŋŋ amɛha lɛ hu mli kɛtsɔ COR ni akɛwoɔ sɛɛkuu babaoo mli lɛ nɔ. Akɛ 1 h tsu nii yɛ sɛɛkuu fɛɛ sɛɛkuu mli ni atsake electrolyte lɛ yɛ sɛɛkuu fɛɛ sɛɛkuu sɛɛ. Yɛ 7th cycle lɛ sɛɛ lɛ, FE kɛ AA nitsumɔ yɛ Ni(OH)2-NS nɔ lɛ ba shi kɛ 50% kɛ 60%, yɛ be mli ni ana OER mliyaa (Fig. 2i, j). Yɛ sɛɛkuu fɛɛ sɛɛkuu sɛɛ lɛ, wɔpɛi sɛɛkuu voltammetry (CV) curves ni yɔɔ tsɔnei ni haa tsɔne lɛ tsuɔ nii lɛ amli lɛ mli ni wɔna akɛ Ni2+ lɛ oksideshin yitso lɛ baa shi fiofio, ni tsɔɔ akɛ Ni redox nyɛmɔ lɛ baa shi (Supplementary Fig. 15a–c). 15d) lɛ, wɔkɛ nitsumɔ mli fitemɔ (FE kɛ AA nitsumɔ ni baa shi) lɛ toɔ Ni ni jɛɔ tsɔne ni haa tsɔne lɛ tsuɔ nii lɛ mli lɛ he, ni no haa Ni foamed substrate ni jieɔ OER nitsumɔ lɛ kpo lɛ kpojiemɔ babaoo baa. Nɔ ni tamɔɔɔ enɛ lɛ, NiV-LDH-NS ha FE kɛ AA nitsumɔ lɛ shibaa lɛ ba shi kɛyashɛ 10% (Mfoniri 2i, j), ni tsɔɔ akɛ V tsakemɔ lɛ tsi Ni shwiemɔ naa jogbaŋŋ (Supplementary Fig. 15d). Bɔni afee ni wɔnu V tsakemɔ lɛ shifimɔ ni yaa hiɛ lɛ shishi lɛ, wɔfee tsɔɔmɔi ahe akɔntaabuu. Taakɛ woji ni eho lɛ tsɔɔ lɛ34,35, enthalpy tsakemɔ ni baa dade atoms ni yɔɔ demetallization gbɛjianɔtoo lɛ nɔ yɛ tsɔne ni haa tsɔne lɛ tsuɔ nii lɛ nɔ lɛ baanyɛ atsu nii akɛ nɔ ni tsɔɔ bɔ ni tsɔne lɛ tsuɔ nii ehaa lɛ mli jogbaŋŋ. No hewɔ lɛ, asusu enthalpy tsakemɔi ni baa Ni atoms lɛ demetallization gbɛjianɔtoo lɛ nɔ yɛ (100) ni asaa ama ekoŋŋ lɛ nɔ lɛ he Ni(OH)2-NS kɛ NiV-LDH-NS (NiOOH kɛ NiVOOH, yɛ gbɛ kome nɔ) lɛ he (atsɔɔ nɔkwɛmɔnɔ lɛ tsumaa lɛ mli fitsofitso yɛ Supplementary Fig.2 kɛ Supplement No1te). Atsɔɔ bɔ ni Ni kɛjɛɔ NiOOH kɛ NiVOOH mli lɛ jeɔ dade mli lɛ mli (Supplementary Fig. 17). Ni ni ajieɔ kɛjɛɔ dade mli lɛ he hewalɛ ni akɛtsuɔ nii yɛ NiVOOH (0.0325 eV) nɔ lɛ fa fe nɔ ni yɔɔ NiOOH (0.0005 eV) nɔ lɛ, ni tsɔɔ akɛ V tsakemɔ lɛ haa NiOOH lɛ shidaamɔ yaa hiɛ.
Kɛha OER ni tsiɔ nii anaa lɛ he hewalɛ ni yɔɔ NiV-LDH-NS nɔ lɛ nɔmimaa, titri lɛ yɛ anodic hewalɛi ni nɔ kwɔlɔ lɛ, afee srɔtofeemɔ electrochemical mass spectrometry (DEMS) koni akɛtao O2 ni damɔ hewalɛ nɔ lɛ mli yɛ nɔkwɛmɔnii srɔtoi anɔ. Nɔ ni jɛ mli ba lɛ tsɔɔ akɛ, kɛ́ cyclohexanone bɛ lɛ, O2 ni yɔɔ NiV-LDH-NS lɛ jeɔ kpo yɛ shishijee hewalɛ ni ji 1.53 VRHE, ni ji nɔ ni baa shi fioo fe O2 ni yɔɔ Ni(OH)2-NS (1.62 VRHE) lɛ (Supplementary Fig. 18). Nɔ ni jɛ mli ba nɛɛ tsɔɔ akɛ, ekolɛ OER ni tsiɔ NiV-LDH-NS naa yɛ COR beaŋ lɛ jeee nɔ ni jɛ emli OER nitsumɔ ni baa shi lɛ mli, ni kɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni fa fioo ni yɔɔ linear sweep voltammetry (LSV) curves ni yɔɔ NiV-LDH-NS lɛ nɔ lɛ kpãa gbee fe nɔ ni yɔɔ Ni (OHcy) 2-pplo1Sne ni bɛ nɔ lɛ. Yɛ cyclohexanone lɛ shishijee sɛɛ lɛ, O2 sutsakemɔ ni sɛɛ tsɛɔ (ekolɛ COR thermodynamic sɛɛnamɔ lɛ hewɔ) tsɔɔ FE ni nɔ kwɔ ni yɔɔ AA mli yɛ kpokpaa ni nyɛɔ etsuɔ ​​nii waa lɛ nɔ. Nɔ ni he hiaa fe fɛɛ lɛ, OER shishijee nyɛmɔ ni yɔɔ NiV-LDH-NS (1.73 VRHE) lɛ nɔ lɛ sɛɛ tsɛɔ fe nɔ ni yɔɔ Ni(OH)2-NS (1.65 VRHE) lɛ nɔ lɛ, ni kɛ FE ni nɔ kwɔ ni ji AA kɛ FE ni baa shi ni ji O2 ni yɔɔ NiV-LDH-NS nɔ lɛ kpãa gbee yɛ nyɛmɔi ni hi jogbaŋŋ babaoo mli (Mfoniri 2).
Kɛha shishinumɔ ni yaa hiɛ yɛ V tsakemɔ lɛ he lɛ, wɔpɛi OER kɛ COR nifeemɔi ni kɔɔ Ni (OH) 2-NS kɛ NiV-LDH-NS he lɛ mli kɛtsɔ amɛ Tafel slopes lɛ susumɔ nɔ. E sa nɛ wa kai kaa amlɔ nɛ ɔ, hɛ mi nyami nɛ ngɛ Tafel kpokpa a nɔ ɔ jeɔ Ni2+ kɛ yaa Ni3+ ɔ mi nɛ a peeɔ ngɛ LSV kaa ɔ mi kɛ jeɔ he wami nɛ ba si kɛ yaa he wami nɛ ya nɔ ɔ he je. 1.8 VRHE kɛha minitii 10 ni no sɛɛ lɛ wɔfee LSV kaai lɛ yɛ sɛɛkuu skan gbɛ nɔ, ni ji, kɛjɛ hewalɛ ni nɔ kwɔ kɛtee hewalɛ ni baa shi (Supplementary Fig. 20). Akɛ 100% iR nyɔmɔwoo tsake LSV shishijee ŋwɛi ŋta lɛ koni anyɛ ana Tafel ŋta lɛ. Yɛ be mli ni cyclohexanone bɛ lɛ, Tafel slope ni ji NiV-LDH-NS (41.6 mV dec−1) lɛ ba shi fe Ni (OH) 2-NS (65.5 mV dec−1) lɛ, ni tsɔɔ akɛ OER kinetics lɛ baanyɛ aya hiɛ kɛtsɔ V tsakemɔ lɛ nɔ (Kpojiemɔ Mfoniri 20c). Yɛ be mli ni ajie cyclohexanone lɛ kpo lɛ sɛɛ lɛ, Tafel slope ni ji NiV-LDH-NS (37.3 mV dec−1) lɛ ba shi fe Ni (OH)2-NS (127.4 mV dec−1) lɛ nɔ lɛ, ni tsɔɔ akɛ V tsakemɔ lɛ yɛ hewalɛ ni yɔɔ faŋŋ yɛ COR nɔ kɛ akɛto OER (Supplementary Fig.20d) he. Nibii nɛɛ tsɔɔ akɛ, eyɛ mli akɛ V tsakemɔ lɛ woɔ OER he hewalɛ kɛyashɛɔ he ko moŋ, shi ehaa COR kinetics lɛ yaa oya waa, ni no haa FE ni ji AA lɛ yaa hiɛ.
Bɔni afee ni wɔnu bɔ ni V tsakemɔ ni yɔɔ ŋwɛi nɛɛ tsuɔ nii ehaa yɛ FE kɛ AA nitsumɔ nɔ lɛ shishi lɛ, wɔkɛ wɔjwɛŋmɔ ma gbɛjianɔtoo lɛ he nikasemɔ lɛ nɔ. Amaniɛbɔi komɛi ni eho lɛ etsɔɔ akɛ heteroatom tsakemɔ baanyɛ aha kristalin ni yɔɔ tsɔne lɛ mli lɛ aba shi ni eha electrochemically active surface area (EAS) lɛ aya hiɛ, ni no baaha hei ni tsuɔ nii lɛ ayibɔ aya hiɛ ni no aha tsɔne lɛ nitsumɔ lɛ aya hiɛ36,37. Kɛha nɛkɛ gbɛ ni atsɔɔ nɔ atsuɔ nii nɛɛ mlipɛimɔ lɛ, wɔfee ECSA susumɔi dani electrochemical nitsumɔ kɛ sɛɛ mli, ni nɔ ni jɛ mli ba lɛ tsɔɔ akɛ ECSA ni ji Ni (OH) 2-NS kɛ NiV-LDH-NS lɛ ji nɔ ni akɛtoɔ he (Supplementary Fig. 21), ni nɔ ni fataaa he ji hewalɛ ni yɔɔ he ni nitsumɔ lɛ yɔɔ lɛ nɔ yɛ V tsakemɔ lɛ nɔ yɛ catalytic enhance lɛ nɔ.
Taakɛ nilee ni akpɛlɛɔ nɔ lɛ tsɔɔ lɛ, yɛ Ni(OH)2-ni haa dãa loo nibii krokomɛi ni haa mɔ tsui nyɔɔ emli lɛ mli lɛ, Ni(OH)2 klɛŋklɛŋ lɛ laajeɔ electrons kɛ protons ni no sɛɛ lɛ ebaa shi kɛyaa NiOOH nɔ kɛtsɔɔ electrochemical gbɛi anɔ yɛ anodic hewalɛ ko nɔ38,39,40,4. NiOOH ni afee lɛ tsuɔ nii akɛ COR henɔ ni tsuɔ nii diɛŋtsɛ ni ejieɔ hydrogen kɛ electrons kɛjɛɔ nucleophilic shishigbɛ kɛtsɔ tsofafeemɔ gbɛi anɔ koni ekɛfee nɔ ni yɔɔ oxidized lɛ20,41. Shi, abɔ amaniɛ nyɛsɛɛ nɛɛ akɛ, eyɛ mli akɛ NiOOH nɔ ni ajieɔ lɛ baanyɛ atsu nii akɛ gbɛ ni atsɔɔ nɔ atsɔɔ bɔ ni dãa lɛ yaa nɔ ehaa lɛ (RDS) kɛha dãa ni yɔɔ Ni (OH)2 nɔ lɛ, taakɛ atsɔɔ yɛ woji ni aŋmala nyɛsɛɛ nɛɛ amli lɛ, Ni3+ dãa lɛ baanyɛ afee nɔ ko ni baa trukaa kɛtsɔ non-redox electron transfer, of Ni42+3 nɔ. Nibii ni awie yɛ wolo lɛ nɔŋŋ mli lɛ ji nɔ ni tsirɛ wɔ ni wɔkɛ dimethylglyoxime disodium ŋmei octahydrate (C4H6N2Na2O2 8H2O) tsu nii akɛ nɔ ko ni akɛtaoɔ nii amli koni akɛwo Ni2 + nifeemɔ fɛɛ ni jɛɔ Ni3 + shibaa mli baa lɛ mli yɛ COR (Supplementary No2te kɛ Fig3 ) lɛ mli. Nɔ ni jɛ mli ba lɛ tsɔɔ bɔ ni Ni2+ lɛ feɔ, ni ema nɔ mi akɛ tsofa ni akɛbaa NiOOH lɛ shi kɛ Ni(OH)2 ni akɛbaatsu nii yɛ tsɔne mli lɛ ba yɛ be kome mli yɛ COR nifeemɔ lɛ mli. No hewɔ lɛ, nɔ ni haa mɔ tsui nyɔɔ emli lɛ baanyɛ adamɔ Ni (OH)2 ni baa shi kɛyaa NiOOH lɛ nɔ waa. No sɛɛ lɛ, wɔdamɔ shishitoo mla nɛɛ nɔ wɔtao mli kɛji akɛ V tsakemɔ lɛ baaha Ni(OH)2 lɛ nɔ aba shi oya ni no baaha COR lɛ aya hiɛ.
Wɔkɛ Raman ŋaai ni yɔɔ jɛmɛ lɛ tsu nii klɛŋklɛŋ koni wɔkɛtsɔɔ akɛ NiOOH ji nɔ ni tsuɔ nii kɛhaa COR yɛ Ni(OH)2-NS kɛ NiV-LDH-NS nɔ kɛtsɔ NiOOH lɛ feemɔ yɛ hewalɛi kpakpai amli kɛ esɛɛnyiɛmɔ ni nyiɛ sɛɛ lɛ nɔ yɛ cyclohexanone ni akɛba lɛ sɛɛ” (ni nyiɛɔ gbɛjianɔtoo ni awie he kɛtsɔ hiɛ lɛ sɛɛ. 3a). Kɛfata he lɛ, NiV-LDH-NS ni asaa ama ekoŋŋ lɛ nitsumɔ lɛ fe Ni(OH)2-NS lɛ nɔ lɛ, taakɛ Ni3+–O Raman okadi lɛ ni laajeɔ oya lɛ yeɔ he odase lɛ. No sɛɛ lɛ, wɔtsɔɔ akɛ NiV-LDH-NS jieɔ nyɛmɔ ni hi fioo ko kpo kɛha NiOOH feemɔ kɛ akɛto Ni (OH) 2-NS he yɛ cyclohexanone ni yɔɔ loo bɛ mli lɛ mli (Mfoniri 3b, c kɛ Mfoniri ni fata he 4c, d). Nɔ ni sa kadimɔ ji akɛ, OER nitsumɔ ni nɔ kwɔ ni NiV-LDH-NS lɛ tsuɔ lɛ haa ŋmeii babaoo ŋmɛɔ Raman susumɔ oti lɛ hiɛ ŋmɛlɛtswaa lɛ nɔ, ni no haa Raman yitso ni yɔɔ 1.55 VRHE lɛ laajeɔ (Supplementary Fig. 4d). 1.58 kɛha Ni(OH)2-NS kɛ VRHE < 1.53 kɛha NiV-LDH-NS) lɛ ji nɔ titri ni jɛɔ Ni2+ ions lɛ sɛɛkuu mli moŋ fe OER ni yɔɔ abs lɛ mli lɛ. No hewɔ lɛ, Ni2+ ni yɔɔ LSV curve lɛ mli lɛ mli oksideshin lɛ mli wa fe NiV-LDH-NS lɛ, ni tsɔɔ akɛ V tsakemɔ lɛ haa NiV-LDH-NS lɛ nyɛɔ etsakeɔ ehe (kwɛmɔ Supplementary Fig. 19 kɛha mlipɛimɔ fitsofitso lɛ).
1.5 VRHE yɛ 0.5 M KOH kɛ 0.4 M cyclohexanone mli kɛha 60 s sɛɛ. b Ni (OH)2-NS kɛ c NiV-LDH-NS ni yɔɔ 0.5 M KOH + 0.4 M cyclohexanone mli lɛ yɛ hewalɛi srɔtoi amli. d Ni (OH)2-NS kɛ NiV-LDH-NS ni yɔɔ Ni K-naa lɛ yɛ 0.5 M KOH kɛ e 0.5 M KOH kɛ 0.4 M cyclohexanone mli. Nɔ ni akɛwo mli lɛ tsɔɔ ŋwɛi ŋta ni yɔɔ 8342 kɛ 8446 eV teŋ. f Ni ni yɔɔ Ni(OH)2-NS kɛ NiV-LDH-NS mli lɛ shihilɛi ni yɔɔ hewalɛi srɔtoi amli. g Yɛ he ni Ni EXAFS lɛ tsɔɔ lɛ, dani akɛ cyclohexanone woɔ mli kɛ sɛɛ mli yɛ hewalɛi srɔtoi amli. h Ni (OH) 2-NS kɛ NiV-LDH-NS he tsɔɔmɔi ahe nɔkwɛmɔnii. Yɛ ŋwɛi: Yɛ Ni(OH)2-NS nɔ lɛ, tsakemɔ ni yaa nɔ blɛoo kɛjɛɔ Ni(OH)2-NS kɛyaa NiOOH mli lɛ tsuɔ nii akɛ RDS, yɛ be mli ni cyclohexanone baa Ni henɔi ni yɔɔ sɛɛnamɔ babaoo lɛ shi kɛtsɔɔ tsofafeemɔ gbɛi anɔ koni ekɛkwɛ Ni ni yɔɔ sɛɛnamɔ fioo lɛ nɔ koni ekɛfee AA. Yɛ shishigbɛ: Yɛ NiV-LDH-NS lɛ nɔ lɛ, V tsakemɔ lɛ haa tsɔne ni akɛtsakeɔ nii lɛ feɔ mlɛo, ni no haa ajieɔ RDS lɛ kɛjɛɔ tsɔne ni akɛtsakeɔ nii lɛ mli kɛyaa tsofafeemɔ gbɛ lɛ nɔ. i Gibbs hewalɛ ni aheee nɔ ko lɛ tsakeɔ yɛ Ni(OH)2-NS kɛ NiV-LDH-NS lɛ sɛɛkuu nɔ. Akɛ aj kɛ i he saji ni aŋmala ashwie shi lɛ haa yɛ saji ni aŋmala ashwie shi lɛ faili lɛ mli.
Kɛha atomik kɛ ilɛkrɔnik nibii lɛ asɛɛkuu lɛ mlipɛimɔ yɛ be mli ni nɔ ni haa nɔ ko yaa hiɛ lɛ baa shi lɛ, wɔfee shikpamɔi ni kɔɔ X-ray ni ajieɔ lɛ kpo lɛ he (XAS), ni ha wɔná dɛŋdade ni he wa ni akɛtaoɔ Ni henɔi lɛ amli hewalɛ mli yɛ gbɛi etɛ ni nyiɛɔ sɛɛ nɔ: OER, cyclohexanone injection, kɛ COR (potentialOCP kpokpaa ni agbele naa). Nɔkwɛmɔnɔ lɛ tsɔɔ K-edge XANES spectra ni ji Ni ni yɔɔ hewalɛ ni yaa hiɛ dani awoɔ cyclohexanone mli kɛ sɛɛ mli (Mfoniri 3d, e). Yɛ nakai nyɛmɔ lɛ nɔŋŋ mli lɛ, NiV-LDH-NS lɛ sɛɛ hewalɛ ni ajieɔ lɛ lɛ ji nɔ ni hi jogbaŋŋ fe Ni(OH)2-NS lɛ (Mfoniri 3d, e, inset). Akɛ Ni mlijaa mlijaa yɛ shihilɛ fɛɛ shihilɛ shishi lɛ to XANES spectra lɛ kɛ Ni K-edge absorption hewalɛ shift lɛ sɛɛkuu (Mfoniri 3f), kɛ spectrum ni akɛtsɔɔ mli lɛ ni ajie kɛjɛ woji ni akala lɛ amli (Supplementary Fig. 23)43.
Yɛ klɛŋklɛŋ gbɛ nɔ (dani abaajie cyclohexanone kpo, ni kɛ OER gbɛjianɔtoo lɛ kpãa gbee; Mfoniri 3f, abɛkugbɛ), yɛ nyɛmɔ ni yɔɔ tsɔne ni asaaa lɛ mli (<1.3 VRHE), Ni valence shihilɛ ni yɔɔ NiV-LDH-NS (+1.83) ni baanyɛ afee nɔ ni baa shi fioo fe Ni(7+)2 lɛ nɔ lɛ. electron ni ajieɔ kɛjɛɔ V kɛyaa Ni mli lɛ, ni kɛ XPS hetooi ni atsĩ tã yɛ yiteŋgbɛ lɛ kpãa gbee (Mfoniri 2f). Kɛji akɛ nyɛmɔ lɛ fe shishijee he lɛ (1.5 VRHE) lɛ, Ni ni yɔɔ NiV-LDH-NS (+3.28) lɛ mli lɛ valence shihilɛ lɛ tsɔɔ hiɛyaa ni yɔɔ faŋŋ fe tsutsu lɛ kɛ akɛto Ni(OH)2-NS (+2.49) lɛ he. Yɛ hewalɛ ni nɔ kwɔ mli (1.8 VRHE) lɛ, Ni nibii bibii ni anáa yɛ NiV-LDH-NS (+3.64) lɛ anɔ lɛ mli hewalɛ shihilɛ lɛ nɔ kwɔ fe Ni(OH)2-NS (+3.47) lɛ nɔ lɛ. Taakɛ amaniɛbɔi ni je kpo nyɛsɛɛ nɛɛ tsɔɔ lɛ, nɛkɛ gbɛ nɛɛ kɛ Ni4+ henɔi ni he hiaa waa lɛ afeemɔ kpãa gbee yɛ Ni3+xOOH1-x (Ni3+x ji Ni3+ kɛ Ni4+ henɔi ni efutu), ni tsutsu ko lɛ ejie nɔ ni haa mɔ tsui nyɔɔ emli lɛ kpo yɛ dãa mli nu ni ajieɔ kɛjɛɔ mli lɛ mli38,39,44. No hewɔ lɛ, NiV-LDH-NS nitsumɔ ni nɔ kwɔ ni yɔɔ COR lɛ baanyɛ ajɛ bɔ ni anyɛɔ ajieɔ nibii ni haa mɔ tsui nyɔɔ emli ni haa mɔ tsui nyɔɔ emli lɛ mli.
Yɛ gbɛ ni ji enyɔ nɔ lɛ (cyclohexanone ni akɛbaatsu nii yɛ ŋmɛlɛtswaa lɛ gbelemɔ sɛɛ, Mfoniri 3f), Ni ni yɔɔ nibii ni haa mɔ tsui nyɔɔ emli lɛ fɛɛ nɔ lɛ ba shi waa, ni kɛ Ni3+xOOH1-x ni cyclohexanone lɛ baa shi lɛ kpãa gbee, ni kɛ nɔ ni jɛɔ mli baa lɛ kpãa gbee yɛ Raman spectroscopy ni yɔɔ he ni eyɔɔ lɛ mli kɛyaa Nivalence al shihilɛ lɛ mli kɛyaa (Mfoniri 3f). shishijee shihilɛ (klɛŋklɛŋ gbɛ yɛ hewalɛ ni baa shi mli), ni tsɔɔ bɔ ni redox gbɛjianɔtoo ni ji Ni kɛyaa Ni3+xOOH1-x lɛ baanyɛ aku sɛɛ aba.
Yɛ gbɛ ni ji etɛ lɛ nɔ (COR gbɛjianɔtoo) yɛ COR nyɛmɔi (1.5 kɛ 1.8 VRHE; Mfoniri 3f, ninejurɔgbɛ), Ni ni yɔɔ Ni(OH)2-NS mli lɛ valence shihilɛ lɛ tee hiɛ fioo pɛ (+2.16 kɛ +2.40), ni ji nɔ ni baa shi kwraa fe nyɛmɔi kome too lɛ nɔŋŋ yɛ klɛŋklɛŋ gbɛ lɛ nɔ (+2.479 kɛ). Nibii nɛɛ tsɔɔ akɛ, yɛ cyclohexanone ni akɛwoɔ mɔ mli lɛ sɛɛ lɛ, COR lɛ ji nɔ ni tsiɔ ehe kɛjɛɔ Ni2+ kɛyaa Ni3+x (ni ji, Ni sɛɛkuu) lɛ mli moŋ fe tsofafeemɔ gbɛ ni yɔɔ NiOOH kɛ cyclohexanone ni yɔɔ Ni(OH)2-NS lɛ teŋ lɛ nɔ, ni no haa Ni hiɔ shi yɛ shihilɛ ni baa shi mli. No hewɔ lɛ, wɔmuɔ sane naa akɛ Ni sɛɛkuu baanyɛ atsu nii akɛ RDS yɛ COR gbɛjianɔtoo lɛ mli yɛ Ni (OH) 2-NS nɔ. Nɔ ni tamɔɔɔ enɛ lɛ, NiV-LDH-NS hiɛ Ni henɔi lɛ amli sɛɛnamɔ ni nɔ kwɔ mli (>3) yɛ COR nifeemɔ lɛ mli, ni sɛɛnamɔ lɛ ba shi kwraa (eshɛɛɛ 0.2) kɛ akɛto klɛŋklɛŋ gbɛ ni yɔɔ nyɛmɔ kome lɛ nɔŋŋ mli lɛ he (1.65 kɛ 1.8 VRHE), ni tsɔɔ akɛ V tsakemɔ kinetically ni ji Ni+ maoxidation lɛ tsiɔ Ni3 lɛ shi. fe tsofafeemɔ gbɛ ni atsɔɔ nɔ ajieɔ cyclohexanone lɛ shi lɛ. X-ray ni ajieɔ lɛ kpo lɛ hetooi lɛ hu jie Ni–O (kɛjɛ 1.6 kɛyashi 1.4 Å) kɛ Ni–Ni(V) (kɛjɛ 2.8 kɛyashi 2.4 Å) tsakpaai ni yɔɔ cyclohexanone lɛ hiɛ lɛ tsakemɔ ni yeɔ emuu kpo. Enɛ kɛ Ni(OH)2 fã lɛ ni asaa ama shi kɛyaa NiOOH fã lɛ mli lɛ kɛ tsofa ni akɛbaa NiOOH fã lɛ nɔ kɛtsɔ cyclohexanone nɔ lɛ kpãa gbee (Mfoniri 3g). Shi, cyclohexanone lɛ tsi Ni (OH) 2-NS lɛ shibaa lɛ naa waa (kwɛmɔ Nɔ ni Akɛfata He 4 kɛ Nɔ ni Akɛfata He Fig. 24 kɛha saji krokomɛi).
Yɛ fɛɛ mli lɛ, yɛ Ni (OH) 2-NS (Fig. 3h, ŋwɛi) lɛ nɔ lɛ, shishijee shishijee gbɛ ni jɛɔ Ni (OH)2 fã lɛ mli kɛyaa NiOOH fã lɛ mli lɛ baanyɛ atsu nii akɛ RDS ni ji COR gbɛjianɔtoo lɛ fɛɛ moŋ fe tsofafeemɔ gbɛ ni ji AA feemɔ kɛjɛɔ cyclohexanone mli yɛ tsofafeemɔ ni baa shi yɛ NiOOH lɛ mli lɛ. Yɛ NiV-LDH-NS (Fig. 3h, shishigbɛ) lɛ nɔ lɛ, V tsakemɔ lɛ haa Ni2+ kɛyaa Ni3+x lɛ mli oksideshin kinetics lɛ yaa hiɛ, ni no haa NiVOOH lɛ feemɔ yaa oya (shi jeee ni akɛ tsofa ni akɛbaatsu nii lɛ baatsu nii), ni no tsiɔ RDS lɛ kɛyaa tsofa lɛ gbɛ lɛ nɔ. Bɔni afee ni wɔnu Ni sɛɛkuu ni V tsakemɔ lɛ kɛba lɛ shishi lɛ, wɔfee akɔntaabuui krokomɛi ni kɔɔ tsɔɔmɔ he. 3h lɛ, wɔkase Ni (OH) 2-NS kɛ NiV-LDH-NS lɛ sɛɛkuu gbɛjianɔtoo lɛ. Akɛ hydroxyl kui ni yɔɔ Ni(OH)2-NS kɛ NiV-LDH-NS lɛ nɔ lɛ jieɔ proton kɛtsɔ OH- ni ajieɔ kɛjɛɔ tsɔne mli lɛ nɔ koni ekɛfee tsɔne ni haa wala yibii ni bɛ tsɔne mli lɛ. Tsofai ni kɛ amɛhe kpãa gbee lɛ ji nɔ ni nyiɛ sɛɛ nɛɛ:
Akɛ Gibbs hewalɛ tsakemɔ ni aheee nɔ ko yɛ sɛɛkuu lɛ mli lɛ to he akɔntaa (Mfoniri 3i), ni NiV-LDH-NS (0.81 eV) tsɔɔ Gibbs hewalɛ tsakemɔ ni bɛ nyɔmɔwoo lɛ bibioo kwraa fe Ni(OH)2-NS (1.66 eV), ni tsɔɔ akɛ V tsakemɔ lɛ ha voltage ni he hiaa kɛha Ni sɛɛkuu lɛ ba shi. Wɔheɔ wɔyeɔ akɛ, kɛ́ wɔtswa sɛɛkuu lɛ he adafi lɛ, ebaanyɛ eba hewalɛ ni tsiɔ COR muu lɛ fɛɛ naa lɛ shi (kwɛmɔ bɔ ni etsuɔ ​​nii ehaa lɛ he nikasemɔ ni yɔɔ shishigbɛ lɛ mli fitsofitso), ni no baaha nɔ ni yaa nɔ lɛ aya hiɛ oya yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei ni fa babaoo lɛ amli.
Nibii amlipɛimɔ ni yɔɔ ŋwɛi nɛɛ tsɔɔ akɛ V tsakemɔ lɛ kɛ Ni(OH)2 lɛ he gbɛjianɔtoo hee baa oya, ni no haa nɔ ni afeɔ lɛ yaa hiɛ, ni no hu haa COR lɛ mli ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ yaa hiɛ. Shi kɛlɛ, Ni3+x hei lɛ hu baanyɛ aha OER nitsumɔ lɛ aya hiɛ. Kɛjɛ LSV curve ni cyclohexanone bɛ mli lɛ mli lɛ, eka shi faŋŋ akɛ NiV-LDH-NS ni yɔɔ amrɔ nɛɛ mli lɛ fa fe Ni(OH)2-NS (Supplementary Fig. 19), ni haa COR kɛ OER nifeemɔi lɛ feɔ akaŋshii nifeemɔi. No hewɔ lɛ, FE ni AA lɛ nɔ kwɔ waa fe NiV-LDH-NS lɛ nyɛŋ atsɔɔ mli jogbaŋŋ kɛtsɔ V tsakemɔ ni woɔ fã ni atoɔ ekoŋŋ lɛ hiɛ nyam lɛ nɔ.
Akpɛlɛɔ nɔ akɛ yɛ alkaline adafitswaa mli lɛ, tsɔne ni haa nu mli nibii ni yɔɔ ŋwɛi lɛ feɔ lɛ nyiɛɔ Langmuir–Hinshelwood (LH) nɔkwɛmɔnɔ lɛ sɛɛ. Yɛ gbɛ pɔtɛɛ ko nɔ lɛ, shishigbɛ kɛ OH− anions lɛ ji akaŋshii coadsorbed yɛ catalyst lɛ hiɛ, ni adsorbed OH− lɛ ji oxidized kɛyaa hydroxyl kui ni tsuɔ nii (OH *), ni tsuɔ nii akɛ electrophiles kɛha oxidation ni nucleophiles, gbɛ ni atsɔɔ nɔ atsuɔ nii tsutsu kɛtsɔ akɔntaabuu, data47ore nɔ. No hewɔ lɛ, nibii ni haa mɔ tsui nyɔɔ emli lɛ ayibɔ kɛ amɛmlijaa (organic substrate kɛ OH−) baanyɛ akudɔ nibii ni haa mɔ tsui nyɔɔ emli lɛ ahe nɔ, ni no baaha FE kɛ nɔ ni ataoɔ lɛ yibiiwoo lɛ aya hiɛ14,48,49,50. Yɛ wɔgbɛfaŋ lɛ, wɔsusuɔ akɛ cyclohexanone ni nɔ kwɔ ni yɔɔ NiV-LDH-NS mli lɛ yeɔ COR gbɛjianɔtoo lɛ nɔ, ni nɔ ni tamɔɔɔ enɛ lɛ, cyclohexanone ni yɔɔ Ni (OH) 2-NS mli lɛ yeɔ OER gbɛjianɔtoo lɛ nɔ.
Kɛha susumɔ ni yɔɔ ŋwɛi nɛɛ kaa lɛ, wɔfee shikpamɔi enyɔ ni kɔɔ nibii ni haa mɔ tsui nyɔɔ emli lɛ ahe (C, cyclohexanone, kɛ COH−) klɛŋklɛŋ. 1.8 VRHE) yɛ Ni (OH) 2-NS kɛ NiV-LDH-NS tsɔnei ni yɔɔ cyclohexanone C srɔtoi (0.05 ~ 0.45 M) kɛ COH− nibii ni yɔɔ shiŋŋ (0.5 M) lɛ anɔ. No sɛɛ lɛ, abu FE kɛ AA nitsumɔ lɛ he akɔntaa. Kɛha NiV-LDH-NS tsɔne ni haa mɔ tsui nyɔɔ emli lɛ, wekukpaa ni kã AA yibiiwoo kɛ cyclohexanone C teŋ lɛ tsɔɔ “volcanic henɔ” ni yɔɔ LH gbɛ nɔ lɛ mli (Mfoniri 4a), ni tsɔɔ akɛ cyclohexanone ni nɔ kwɔ ni akɛwoɔ mli lɛ kɛ OH− ni akɛwoɔ mli lɛ yeɔ akaŋ. Yɛ be mli ni Ni(OH)2-NS lɛ, AA yibiiwoo lɛ tee hiɛ yɛ gbɛ kome nɔ kɛ C ni ji cyclohexanone lɛ nɔyaa kɛjɛ 0.05 kɛyashi 0.45 M, ni tsɔɔ akɛ eyɛ mli akɛ cyclohexanone lɛ falɛ babaoo lɛ fa moŋ (0.45 M), shi ehiɛ ni ekɛhaa lɛ faaa lolo. Kɛfata he lɛ, kɛ COH− tee hiɛ kɛyashi 1.5 M lɛ, ana “lasu gɔŋ henɔ” ko ni tsɔɔ Ni (OH) 2-NS lɛ nɔ ni damɔ C ni ji cyclohexanone lɛ nɔ, ni nitsumɔ lɛ mli sɛɛkuu lɛ sɛɛ tsɛɔ kɛ akɛto NiV-LDH-NS he, ni etsɔɔ bɔ ni cyclohexano-NSu2Hno-NSu-pplementary ni yɔɔ Niclohexano2-NS lɛ nɔ lɛ bɛ hewalɛ ha lɛ mli. 25a kɛ Kaadi 5). Kɛfata he lɛ, FE ni AA yɔɔ NiV-LDH-NS lɛ nɔ lɛ nuɔ C-cyclohexanone he waa ni eyaa hiɛ oya kɛyashɛɔ nɔ ni fe 80% beni C-cyclohexanone lɛ tee hiɛ kɛjɛ 0.05 M kɛtee 0.3 M lɛ, ni tsɔɔ akɛ cyclohexanone lɛ ji nɔ ni yɔɔ mlɛo yɛ NiV-LDH-LDH nɔ. Nɔ ni tamɔɔɔ enɛ lɛ, C-cyclohexanone lɛ mli nibii ni yaa hiɛ lɛ tsiii OER ni yɔɔ Ni(OH)2-NS lɛ nɔ lɛ naa jogbaŋŋ, ni ekolɛ eji nɔ ni jɛ cyclohexanone lɛ mli nibii ni fa bɔ ni sa lɛ amli. Nɔ ni tamɔɔɔ enɛ lɛ, niiamlitaomɔ kroko ni kɔɔ COH− ni damɔ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ nɔ lɛ hu ma nɔ mi akɛ, cyclohexanone lɛ mli nibii ni akɛwoɔ mli lɛ tee hiɛ kɛ akɛto NiV-LDH-NS he, ni baanyɛ akpɛlɛ COH− ni nɔ kwɔ nɔ yɛ COR nifeemɔ lɛ mli ni ekɛ FE ni ji AA lɛ baa shi (Supplementary, c5b kɛ 5).
AA kɛ EF ni ji b Ni(OH)2-NS kɛ NiV-LDH-NS lɛ nitsumɔ yɛ cyclohexanone ni C sɔrɔtoi yɔɔ mli yɛ 0.5 M KOH mli lɛ nɔ. c Nibii ni haa mɔ tsui nyɔɔ emli lɛ ahewalɛ ni yɔɔ NiOOH kɛ NiVOOH nɔ lɛ. 0.5 M KOH kɛ 0.4 M cyclohexanone yɛ 1.80 VRHE ni akɛ gbɛi ni nyɛɔ etsuɔ ​​nii ni bɛ naagbee kɛ nɔ ni yaa nɔ daa lɛ tsuɔ nii. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔ ni yɔɔ susumɔi etɛ ni yɔɔ amɛ diɛŋtsɛ amɛhe ni akɛ nɔkwɛmɔnɔ kome tsuɔ nii ni amɛyɔɔ 10% mli. e Yiteŋ: Yɛ Ni(OH)2-NS lɛ nɔ lɛ, cyclohexanone ni yɔɔ shishigbɛ C lɛ shwieɔ shi yɛ gbɛ ni waaa nɔ, ni no haa akaŋshii ni naa wa baa kɛha OER. Yɛ shishigbɛ: Yɛ NiV-LDH-NS lɛ nɔ lɛ, anaa cyclohexanone C ni fa babaoo yɛ ŋwɛi kɛ cyclohexanone ni shwieɔ shi lɛ ni yaa hiɛ, ni no haa OER lɛ tsiɔ naa. Akɛ saji ni kɔɔ a–d he lɛ haa yɛ saji ni aŋmala ashwie shi lɛ mli.
Kɛha cyclohexanone ni ajieɔ lɛ kpo yɛ NiV-LDH-NS nɔ lɛ kaa lɛ, wɔkɛ electrochemical ni akɛ quartz kristalo microbalance (E-QCM) fata he lɛ tsu nii koni wɔkɛkwɛ bɔ ni nibii ni ajieɔ lɛ kpo lɛ ayibɔ tsakeɔ yɛ be ni sa mli. Nɔ ni jɛ mli ba lɛ tsɔɔ akɛ shishijee tsɔne ni akɛwoɔ NiV-LDH-NS nɔ lɛ fa fe nɔ ni yɔɔ Ni(OH)2-NS yɛ OCP maŋ lɛ mli lɛ shii 1.6, ni nɛkɛ srɔtofeemɔ ni yɔɔ tsɔne ni akɛwoɔ tsɔne mli lɛ mli lɛ tee hiɛ babaoo be mli ni nyɛmɔ lɛ tee hiɛ kɛyashɛ 1.5 VRHE (Supplementary Fig. 26). Akɛ spin-polarized DFT akɔntaabuu lɛ tsu nii koni akɛtao bɔ ni cyclohexanone lɛ shwieɔ NiOOH kɛ NiVOOH nɔ lɛ mli (Mfoniri 4c). Cyclohexanone shwieɔ Ni-teŋgbɛ yɛ NiOOH nɔ kɛ hewalɛ ni shwieɔ shi (Eads) ni ji -0.57 eV, yɛ be mli ni cyclohexanone baanyɛ shwieɔ Ni-teŋgbɛ loo V-teŋgbɛ yɛ NiVOOH nɔ, he ni V-teŋgbɛ lɛ haa Eads ni baa shi kwraa (eV6) ni kwɛɔ nɔ. tsɔne ni akɛwoɔ NiVOOH nɔ lɛ.
Kɛha nɔmimaa kroko akɛ cyclohexanone ni ajieɔ lɛ kpo lɛ baanyɛ aha AA feemɔ aya hiɛ ni etsi OER naa lɛ, wɔkɛ gbɛ ni nyɛɔ etsuɔ ​​nii ni bɛ naagbee lɛ tsu nii koni wɔkɛha cyclohexanone lɛ aya hiɛ yɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ nɔ (kɛha Ni (OH) 2-NS kɛ NiV-LDH-NS), ni previous lɛ ji nɔ ni tsirɛ lɛ. 51, 52 Pɔtɛɛ lɛ, wɔkɛ nyɛmɔ ni ji 1.8 VRHE tsu nii kɛha COR, no sɛɛ lɛ wɔtsake kɛtee OCP shihilɛ lɛ mli, ni no sɛɛ lɛ wɔtsake kɛtee 1.8 VRHE mli ekoŋŋ. Yɛ shihilɛ nɛɛ mli lɛ, cyclohexanone baanyɛ abua ehe naa yɛ nɔ ni haa tsɔne lɛ tsuɔ nii lɛ nɔ yɛ OCP shihilɛ lɛ mli yɛ electrolyses lɛ ateŋ (kwɛmɔ Gbɛi lɛ fã lɛ kɛha gbɛjianɔtoi ni yɔɔ fitsofitso lɛ). Nɔ ni jɛ mli ba lɛ tsɔɔ akɛ, kɛha Ni(OH)2-NS kɛ NiV-LDH-NS lɛ, kɛ akɛ tsɔne ni haa mɔ tsui nyɔɔ emli ni bɛ naagbee lɛ tsu nii lɛ, ehaa tsɔne ni haa mɔ tsui nyɔɔ emli lɛ tsuɔ nii jogbaŋŋ kɛ akɛto tsɔne ni haa mɔ tsui nyɔɔ emli ni yaa nɔ daa lɛ he (Mfoniri 4d). Nɔ ni sa kadimɔ ji akɛ, Ni(OH)2-NS tsɔɔ hiɛyaa ni sa kadimɔ waa yɛ COR (AA FE: kɛjɛ 51% kɛyashi 82%) kɛ OER (O2 FE: kɛjɛ 27% kɛyashi 4%) nɔyeli mli fe NiV-LDH-NS, ni akɛto anɔkwale ni eji akɛ cyclohexanone ni abua naa lɛ baanyɛ afee nɔ ni fe . tsɔne ni haa mɔ he jɔɔ lɛ (ni ji, Ni(OH)2-NS) kɛtsɔ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ nɔ.
Yɛ fɛɛ mli lɛ, abaanyɛ akɛ OER ni tsiɔ NiV-LDH-NS naa lɛ aha cyclohexanone ni ajieɔ lɛ kpo lɛ ni yaa hiɛ lɛ (Mfoniri 4e). Yɛ Ni(OH)2-NS (Mfoniri 4e, ŋwɛi) lɛ nɔ lɛ, cyclohexanone ni bɛ hewalɛ ni shwieɔ shi lɛ ha cyclohexanone ni shwieɔ shi lɛ ba shi fioo, ni OH * ni shwieɔ shi lɛ hu fa babaoo yɛ nɔ ni haa hulutsoo lɛ yaa hiɛ lɛ nɔ. No hewɔ lɛ, OH* henɔi ni fa fe nine lɛ baaha akaŋshii ni naa wa aba kɛha OER ni ebaaha AA FE lɛ aba shi. Nɔ ni tamɔɔɔ enɛ lɛ, yɛ NiV-LDH-NS (Mfoniri 4e, shishigbɛ) lɛ nɔ lɛ, V tsakemɔ lɛ ha cyclohexanone lɛ he nyɛmɔ lɛ tee hiɛ, ni no ha cyclohexanone lɛ hiɛ C lɛ tee hiɛ ni ekɛ OH * ni ajie lɛ lɛ tsu nii jogbaŋŋ kɛha COR, ni ewo AA feemɔ he hewalɛ ni ekɛtsiɔ naa.
Kɛfata nɔ ni V tsakemɔ lɛ tsuɔ yɛ Ni henɔi lɛ kɛ cyclohexanone adsorption lɛ he lɛ mlitaomɔ he lɛ, wɔtao mli hu kɛji V tsakeɔ AA feemɔ gbɛ kɛjɛɔ COR mli. Akɛ COR gbɛi srɔtoi babaoo etsɔɔ yɛ woji lɛ amli, ni wɔpɛi bɔ ni amɛbaanyɛ amɛfee amɛnii amɛha yɛ wɔ hetoohamɔ gbɛjianɔtoo lɛ mli (kwɛmɔ Supplementary Fig. 27 kɛ Supplementary Note 6 kɛha saji krokomɛi)13,14,26. Klɛŋklɛŋ lɛ, abɔ amaniɛ akɛ COR gbɛ lɛ klɛŋklɛŋ gbɛ lɛ baanyɛ akɔ shishijee oksideshin ni ji cyclohexanone lɛ he koni efee 2-hydroxycyclohexanone (2)13,14 ni yɔɔ teŋgbɛ lɛ. Kɛha gbɛ ni atsɔɔ nɔ atsuɔ he nii lɛ he odaseyeli lɛ, wɔkɛ 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO) tsu nii koni wɔkɛmɔ nibii ni tsuɔ nii ni yɔɔ teŋgbɛ ni akɛwoɔ tsɔne ni haa tsɔne lɛ tsuɔ nii lɛ nɔ lɛ mli ni wɔkase EPR lɛ he nii. EPR hetooi lɛ jie C-centered radicals (R ) kɛ hydroxyl radicals (OH ) ni yɔɔ tsɔnei enyɔ lɛ fɛɛ nɔ lɛ kpo yɛ COR nifeemɔ lɛ mli, ni tsɔɔ akɛ Cα − H dehydrogenation ni jɛɔ cyclohexanone mli lɛ feɔ enolate radical (1) ni yɔɔ teŋgbɛ lɛ, ni no sɛɛ lɛ, OH (Fig25) lɛ feɔ nɔ ni haa mɔ tsui nyɔɔ emli. 28). Eyɛ mli akɛ ana nibii ni yɔɔ teŋgbɛ lɛ nɔŋŋ yɛ tsɔnei enyɔ lɛ fɛɛ nɔ moŋ, shi R okadi lɛ fã ni yɔɔ NiV-LDH-NS lɛ nɔ lɛ fa fe Ni(OH)2-NS lɛ, ni ekolɛ eji nɔ ni jɛ cyclohexanone lɛ hewalɛ ni ekɛwoɔ nii amli lɛ mliyaa lɛ hewɔ (Supplementary Table 3 kɛ Note 7). Wɔkɛ 2 kɛ 1,2-cyclohexanedione (3) tsu nii hu akɛ shishijee nibii ni akɛtsuɔ nii kɛhaa electrolysis koni wɔkɛka kɛji V baatsake sɛɛ mli nibii ni haa hulu tsoɔ lɛ. Nibii ni jɛɔ electrolysis mli baa ni baanyɛ afee teŋgbɛ nibii (2 kɛ 3) ni yɔɔ Ni (OH) 2-NS kɛ NiV-LDH-NS nɔ lɛ tsɔɔ nibii ni akɛtoɔ he lɛ ahe halamɔi, ni tsɔɔ akɛ COR nifeemɔ ni yɔɔ Ni (OH) 2-NS loo NiV-LDH-NS nɔ lɛ tee nɔ kɛtsɔ gbɛi ni tamɔ nakai nɔŋŋ nɔ (Mfoniri 5b). Kɛfata he lɛ, AA ji nɔ titri ni anáa pɛ beni akɛ 2 tsu nii akɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ, ni tsɔɔ akɛ AA lɛ ji nɔ ni anáa kɛtsɔ oksideshin gbɛjianɔtoo ko nɔ tɛ̃ɛ kɛtsɔ Cα − Cβ bond ni ji 2 lɛ mligbalamɔ nɔ moŋ fe oksideshin ni nyiɛ sɛɛ kɛyaa 3 nɔ yɛ nibii ni haa mɔ tsui nyɔɔ emli lɛ fɛɛ nɔ, ejaakɛ atsake lɛ titri kɛtee GA mli beni repplementing the 3 was9 30).
EPR okadi ni ji NiV-LDH-NS yɛ 0.5 M KOH + 0.4 M saiklohɛksanɔn mli. b Nɔ ni jɛ 2-hydroxycyclohexanone (2) kɛ 1,2-cyclohexanedione (3) lɛ mlipɛimɔ mli ba. Akɛ 0.5 M KOH kɛ 0.1 M 2 loo 3 tsu nii yɛ 1.8 VRE mli ŋmɛlɛtswaa kome. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔ ni yɔɔ susumɔi enyɔ ni yɔɔ amɛ diɛŋtsɛ amɛhe ni akɛ catalyst kome tsuɔ nii. c COR gbɛi ni atsɔɔ nɔ atsuɔ nii yɛ nibii enyɔ ni haa mɔ tsui nyɔɔ emli lɛ anɔ. d COR gbɛ lɛ he mfoniri ni yɔɔ Ni(OH)2-NS (abɛkugbɛ) kɛ d NiV-LDH-NS (ninejurɔgbɛ) lɛ nɔ. Akpɔlɔi tsuji tsɔɔ gbɛi ni V tsakemɔ lɛ woɔ he hewalɛ yɛ COR gbɛjianɔtoo lɛ mli. Akɛ saji ni aŋmala ashwie shi kɛha a kɛ b lɛ ewo saji ni aŋmala ashwie shi lɛ faili lɛ mli.
Yɛ fɛɛ mli lɛ, wɔtsɔɔ akɛ Ni (OH) 2-NS kɛ NiV-LDH-NS haa COR lɛ yaa hiɛ kɛtsɔɔ gbɛ ni tamɔ nakai nɔŋŋ nɔ: cyclohexanone lɛ shwieɔ tsɔne lɛ nɔ, ni ejieɔ nu kɛjɛɔ mli ni efiteɔ electrons lɛ ni efeɔ 1, ni no sɛɛ lɛ OH * lɛ haa efeɔ oxide kɛfeɔ multiFig to5AA tsakemɔi). Shi, beni akɛ cyclohexanone tsu nii akɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ, ana OER akaŋshii yɛ Ni(OH)2-NS pɛ nɔ, yɛ be mli ni abua oxygen ni baa shi fe fɛɛ lɛ naa beni akɛ 2 kɛ 3 tsu nii akɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ. No hewɔ lɛ, srɔtofeemɔi ni ana yɛ tsɔne ni haa mɔ tsui nyɔɔ emli lɛ mli lɛ baanyɛ ajɛ tsakemɔi ni baa RDS hewalɛ gbɛtsii nii lɛ kɛ cyclohexanone adsorption nyɛmɔ ni V tsakemɔ lɛ kɛbaa lɛ mli moŋ fe tsakemɔi ni baa gbɛ ni atsɔɔ nɔ atsuɔ nii lɛ mli. No hewɔ lɛ, wɔpɛi RDS ni ji gbɛi ni atsɔɔ nɔ atsuɔ nii yɛ tsɔnei enyɔ lɛ fɛɛ nɔ lɛ mli. Nibii ni atsĩ tã yɛ yiteŋgbɛ lɛ tsɔɔ akɛ, V tsakemɔ lɛ tsiɔ RDS ni yɔɔ COR lɛ mli lɛ kɛjɛɔ sɛɛkuu lɛ mli kɛyaa tsofafeemɔ mli, ni ehaa NiOOH fã lɛ kɛ Ni henɔi ni yɔɔ sɛɛnamɔ waa lɛ hiɔ shi yɛ NiV-LDH-NS (Mfoniri 3f, Supplementary No4 kɛ Supplementary Fig.4). Wɔtee nɔ wɔpɛi bɔ ni ŋmɛnɛŋmɛnɛ beaŋ shweremɔ ni damɔ shi kɛha ŋmɛnɛŋmɛnɛ beaŋ shweremɔ ni yɔɔ kpokpai srɔtoi ni baanyɛ aba lɛ amli lɛ eko fɛɛ eko mli lɛ mli yɛ CV susumɔ lɛ mli (kwɛmɔ Supplementary Fig. 31 kɛ Note 8 kɛha saji fitsofitso) ni wɔfee H/D kinetic isotope tsakemɔ kaai, ni kɛ ekomefeemɔ tsɔɔ akɛ yɛ RDSVOR-cle of the C . Cα − H bond yɛ tsofafeemɔ mli moŋ fe shishijee mli (kwɛmɔ Supplementary Fig. 32 kɛ Note 8 kɛha saji krokomɛi).
Kɛtsɔ ŋwɛi mlipɛimɔ lɛ nɔ lɛ, atsɔɔ nɔ fɛɛ nɔ ni V tsakemɔ lɛ kɛbaa lɛ mli yɛ mfoniri 5d lɛ mli. Ni(OH)2-NS kɛ NiV-LDH-NS nibii ni haa mɔ tsui nyɔɔ emli lɛ tsɔɔ ŋwɛi tsakemɔ mli yɛ anodic hewalɛ ni nɔ kwɔ mli ni amɛhaa COR tsuɔ nii kɛtsɔɔ gbɛ ni tamɔ nakai nɔŋŋ nɔ. Yɛ Ni(OH)2-NS (Mfoniri 5d, abɛkugbɛ) lɛ nɔ lɛ, sɛɛkuu gbɛ lɛ ji RDS yɛ COR nifeemɔ lɛ mli; Yɛ be mli ni NiV-LDH-NS (Mfoniri 5d, ninejurɔgbɛ) lɛ nɔ lɛ, V tsakemɔ lɛ ha sɛɛkuu gbɛjianɔtoo lɛ tee hiɛ oya ni etsake RDS lɛ ewo Cα−H dehydrogenation ni ji cyclohexanone lɛ mli koni efee 1. Kɛfata he lɛ, cyclohexanone adsorption lɛ ba yɛ V he lɛ ni eye ebua ni ekɛ su-LDH lɛ tee hiɛ yɛ NiNSV- lɛ nɔ.
Kɛji akɛ wɔsusu electrocatalytic nitsumɔ ni hi jogbaŋŋ ni NiV-LDH-NS ni yɔɔ FE ni nɔ kwɔ fe nɔ ni baanyɛ aba lɛ he lɛ, wɔfee MEA ko koni wɔnine ashɛ AA nitsumɔ ni yaa nɔ lɛ nɔ. Akɛ NiV-LDH-NS tsu nii akɛ anode, jarayeli PtRu/C akɛ cathode53 kɛ anion tsakemɔ membrane (henɔ: FAA-3-50) (Mfoniri 6a kɛ Mfoniri Krokomɛi 33)54. Akɛni tsɔne ni haa mɔ tsui nyɔɔ emli lɛ ba shi ni FE ni ji AA lɛ kɛ 0.5 M KOH yeɔ egbɔ yɛ nikasemɔ ni yɔɔ ŋwɛi nɛɛ mli hewɔ lɛ, anolyte lɛ mli nibii ni yɔɔ mli lɛ ji nɔ ni hi jogbaŋŋ kɛyashɛ 1 M KOH (Supplementary Fig. 25c). Atsɔɔ LSV ŋwɛi ŋta ni aŋmala ashwie shi lɛ mli yɛ Supplementary Fig. 34 lɛ mli, ni tsɔɔ akɛ COR nitsumɔ ni NiV-LDH-NS lɛ tsuɔ lɛ nɔ kwɔ kwraa fe Ni(OH)2-NS lɛ. Kɛha NiV-LDH-NS lɛ nɔyeli lɛ kpojiemɔ lɛ, afee ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛlɛtswaa ni jeɔ shishi kɛjɛɔ 50 kɛyashi 500 mA cm−2 ni aŋmala ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni kɛ lɛ kpãa gbee lɛ he saji awo wolo nɔ. Nɔ ni jɛ mli ba lɛ tsɔɔ akɛ NiV-LDH-NS jieɔ tsɛŋemɔ hela ni ji 1.76 V lɛ kpo yɛ ŋmɛnɛŋmɛnɛ beaŋ 300 mA cm−2, ni ji aaafee 16% ni baa shi fe Ni(OH)2-NS (2.09 V) lɛ nɔ lɛ, ni tsɔɔ bɔ ni etsuɔ ​​nii jogbaŋŋ ehaa yɛ AA feemɔ mli (Mfoniri 6b).
Batri ni hoɔ lɛ he mfoniri. b 1 M KOH kɛ 0.4 M cyclohexanone mli yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei srɔtoi amli. c AA kɛ FE yibiiwoo yɛ Ni(OH)2-NS kɛ NiV-LDH-NS nɔ yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei srɔtoi amli. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔ ni yɔɔ susumɔi enyɔ ni yɔɔ amɛ diɛŋtsɛ amɛhe ni akɛ catalyst kome tsuɔ nii. d Wɔ nitsumɔ lɛ mli nibii ni haa mɔ tsui nyɔɔ emli lɛ kɛ batiri gbɛjianɔtoi krokomɛi ni abɔ he amaniɛ lɛ atoɔ he14,17,19. 200 kɛ 300 mA cm−2 yɛ be kakadaŋŋ mli kaa lɛ mli lɛ, 200 kɛ 300 mA cm−2 yɛ Supplementary Table 2. e Cell voltage kɛ FE ni yɔɔ AA nɔ yɛ NiV-LDH-NS nɔ. Akɛ saji ni ahala lɛ haa akɛ saji ni ahala lɛ faili.
6c lɛ, NiV-LDH-NS lɛ titri ji nɔ ni kwɛɔ FE kpakpa nɔ (83% kɛyashi 61%) yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni nɔ kwɔ mli (200 kɛyashi 500 mA cm-2), ni no haa AA nitsumɔ lɛ yaa hiɛ (1031 kɛyashi 1900 μmol cm-2 h-1). Yɛ nakai beaŋ lɛ, adipic acid anions 0.8 pɛ ji nɔ ni ana yɛ katod fã lɛ mli yɛ electrolysis sɛɛ, ni tsɔɔ akɛ cyclohexanone tsakemɔ lɛ he ehiaaa yɛ wɔgbɛfaŋ (Supplementary Fig. 35). Nɔ ni tamɔɔɔ enɛ lɛ, kɛ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛlɛtswaa ni yaa hiɛ lɛ nɔŋŋ lɛ, FE ni yɔɔ AA nɔ yɛ Ni(OH)2-NS lɛ nɔ lɛ ba shi kɛjɛ 61% kɛtee 34%, ni no ha ewa akɛ aaaha AA nitsumɔ lɛ aya hiɛ (762 kɛyashi 1050 μmol cm-2 h-1). Yɛ gbɛ titri ko nɔ lɛ, AA nitsumɔ lɛ po ba shi fioo yɛ akaŋshii ni naa wa ni jɛ OER lɛ mli lɛ hewɔ, ni no hewɔ lɛ FE ni AA lɛ ba shi waa kɛ ŋmɛnɛŋmɛnɛ beaŋ ŋmɔlɔ ni yaa hiɛ lɛ (kɛjɛ 200 kɛyashi 250 mA cm−2, Supplementary Fig. 5). Kɛha wɔ nilee lɛ, nɔ ni jɛɔ tsɔne ni haa mɔ tsui nyɔɔ emli mli baa kɛtsɔ MEA ni akɛ NiV-LDH-NS tsɔnei tsuɔ nii yɛ mli lɛ nɔ lɛ feɔ nɔ ni tsutsu lɛ abɔ he amaniɛ akɛ tsɔnei ni haa mɔ tsui nyɔɔ emli ni akɛ Ni-based tsɔnei tsuɔ nii yɛ mli lɛ tsuɔ nii (Supplementary Table 2). 6d lɛ, NiV-LDH-NS tsɔɔ sɛɛnamɔi ni sa kadimɔ waa yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni haa mɔ tsui nyɔɔ emli, tsɔne ni haa mɔ tsui nyɔɔ emli, kɛ FE ni ji AA lɛ he kɛ akɛto Co-based catalyst ni tsuɔ nii jogbaŋŋ lɛ he, ni ji, graphene-supported Co3O4 (Co3O4/GDY)17. Kɛfata he lɛ, wɔpɛi hewalɛ ni akɛtsuɔ nii yɛ AA feemɔ mli lɛ mli ni wɔtsɔɔ akɛ AA ni akɛtsuɔ nii lɛ faaa kwraa, 2.4 W h gAA-1 pɛ yɛ ŋmɛnɛŋmɛnɛ beaŋ 300 mA cm-2 kɛ 1.76 V ni ji tsɛŋemɔ hela mli hewalɛ (akɛ akɔntaabuu fitsofitso eha yɛ Supplementary Note 1 lɛ mli). Kɛ akɛto nɔ ni hi fe fɛɛ ni jɛ 4.1 W h gAA-1 kɛha Co3O4/GDY ni abɔ he amaniɛ tsutsu lɛ he lɛ, hewalɛ ni akɛtsuɔ nii kɛhaa AA nitsumɔ yɛ wɔ nitsumɔ lɛ mli lɛ ba shi 42% ni nitsumɔ lɛ tee hiɛ shii 4 (1536 vs. 319 μmol cm-2 h-1)17.
Akwɛ NiV-LDH-NS catalyst lɛ shifimɔ kɛha be kakadaŋŋ AA nifeemɔ yɛ MEA mli yɛ ŋmɛnɛŋmɛnɛ beaŋ densities ni ji 200 kɛ 300 mA cm-2, yɛ gbɛ kome nɔ (Mfoniri 6e). Akɛni OH− lɛ yeɔ oya yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei ni fa babaoo mli hewɔ lɛ, tsɔne ni haa hulutsoo lɛ feɔ ehee lɛ falɛ ni yɔɔ 300 mA cm-2 lɛ fa fe nɔ ni yɔɔ 200 mA cm-2 lɛ (kwɛmɔ kuku ni ji “Electrochemical susumɔi” kɛha mlitsɔɔmɔ). Yɛ ŋmɛnɛŋmɛnɛ beaŋ 200 mA cm-2 lɛ mli lɛ, COR nitsumɔ lɛ mlijaa ji 93% yɛ klɛŋklɛŋ ŋmɛlɛtswai 6 lɛ mli, no sɛɛ lɛ eba shi fioo kɛyashɛ 81% yɛ ŋmɛlɛtswai 60 sɛɛ, yɛ be mli ni tsɛŋemɔ hela lɛ mli hewalɛ tee hiɛ fioo kɛ 7% (kɛjɛ 1.62 V kɛyashi 1.73 V), ni tsɔɔ akɛ ehi shi jogbaŋŋ. Yɛ be mli ni ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ mli tsɔne lɛ yaa hiɛ kɛyashɛɔ 300 mA cm−2 lɛ, AA nitsumɔ lɛ tee nɔ ehi shi tamɔ nɔ ni etsakeee (eba shi kɛjɛ 85% kɛtee 72%), shi tsɔne ni haa wala yibii lɛ mli hewalɛ yaa hiɛ waa (kɛjɛ 1.71 kɛtee 2.09 V, ni kɛ 22% kpãa gbee) yɛ kaa lɛ mli (Figuree). Wɔsusuɔ akɛ yiŋtoo titri ni haa nitsumɔ lɛ fiteɔ lɛ ji anion tsakemɔ membrane (AEM) lɛ fitemɔ kɛtsɔ cyclohexanone nɔ, ni no haa tsɛŋemɔ hela lɛ mli tsɛŋemɔ hela lɛ mli hewalɛ kɛ tsɛŋemɔ hela lɛ mli hewalɛ ni yaa hiɛ lɛ yaa hiɛ (Supplementary Fig. 36), ni nɔ ni fata he ji tsɛŋemɔ hela ni haa mɔ he jɔɔ lɛ fioo kɛjɛɔ anode lɛ mli kɛyaa anode lɛ mli, ni nɔ ni jɛɔ mli baa lɛ mli . kpa tsɔne ni akɛwoɔ tsɔne mli lɛ. Kɛfata he lɛ, FE ni baa shi yɛ AA mli lɛ hu baanyɛ ajɛ nibii ni haa mɔ tsui nyɔɔ emli lɛ amli nu lɛ mli, ni no haa Ni foam lɛ gbeleɔ kɛhaa OER lɛ. Kɛha bɔ ni AEM ni efite lɛ tsuɔ nii ehaa yɛ shifimɔ ni yɔɔ 300 mA cm−2 lɛ nɔ lɛ he tsɔɔmɔ lɛ, wɔkɛ AEM hee tsake lɛ yɛ 46 h ni akɛ electrolysis tsuɔ nii yɛ mli lɛ sɛɛ. Taakɛ akpaa gbɛ lɛ, atsake tsɔne ni haa tsɔne lɛ tsuɔ nii jogbaŋŋ lɛ mli jogbaŋŋ, ni tsɔne lɛ mli hewalɛ lɛ ba shi waa kɛyashɛ shishijee sɛɛnamɔ lɛ nɔ (kɛjɛ 2.09 kɛyashi 1.71 V) ni no sɛɛ lɛ etee hiɛ fioo yɛ ŋmɛlɛtswai 12 ni nyiɛ sɛɛ lɛ mli ni akɛ electrolysis tsuɔ nii (kɛjɛ 1.71 kɛyashi 1.79 V; mfoniri ni ji 65% lɛ nɔyaa).
Yɛ fɛɛ mli lɛ, wɔnyɛ wɔnine shɛ 60 h ni yaa nɔ AA nifeemɔ shifimɔ nɔ yɛ ŋmɛnɛŋmɛnɛ beaŋ 200 mA cm−2, ni tsɔɔ akɛ FE kɛ AA lɛ mli tsɔne lɛ mli tsɔne lɛ mli hewalɛ lɛ hi jogbaŋŋ. 300 mA cm−2 ni ji ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni fa fe fɛɛ lɛ hu wɔkwɛ ni wɔnine shɛ 58 h nɔ, ni wɔkɛ ehee tsake AEM lɛ yɛ 46 h sɛɛ. Nibii ni akaseɔ yɛ ŋwɛi nɛɛ tsɔɔ bɔ ni nɔ ni haa mɔ tsui nyɔɔ emli lɛ damɔ shi shiŋŋ ehaa lɛ mli, ni etsɔɔ faŋŋ akɛ ehe miihia ni afee AEMs ni he wa fe fɛɛ lɛ wɔsɛɛ koni akɛha MEA lɛ ahilɛ-kɛhamɔ ni yaa hiɛ be kakadaŋŋ lɛ aya hiɛ kɛha AA nitsumɔ ni yaa nɔ yɛ nitsumɔhei ni hi jogbaŋŋ amrɔ nɛɛ amli.
Kɛtsɔ wɔ MEA lɛ nitsumɔ nɔ lɛ, wɔkɛ AA nifeemɔ gbɛjianɔtoo ni yeɔ emuu ni nɔ ni fata he ji niyenii ni akɛhaa, electrolysis, neutralization, kɛ mligbalamɔ nibii (Supplementary Fig. 37) lɛ he ŋaa. Afee shishijee nitsumɔ mlipɛimɔ koni akɛpɛi shika helɛtemɔ mli gbɛjianɔtoo lɛ mli kɛtsɔ alkaline electrolyte electrocatalytic carboxylate nifeemɔ nɔkwɛmɔnɔ55 nɔ. Yɛ shihilɛ nɛɛ mli lɛ, shika ni akɛwoɔ nitsumɔ mli, nitsumɔi, kɛ nibii ni akɛtsuɔ nii lɛ fata he (Mfoniri 7a kɛ Supplementary Fig. 38), ni shika ni anáa lɛ jɛɔ AA kɛ H2 nifeemɔ mli. TEA hetooi lɛ tsɔɔ akɛ yɛ wɔ nitsumɔ shihilɛi lɛ amli (ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ mli tsɔne lɛ 300 mA cm-2, tsɔne lɛ mli hewalɛ 1.76 V, FE 82%), shika ni akɛwoɔ mli kɛ shika ni anáa lɛ fɛɛ ji US$2429 kɛ US$2564, yɛ gbɛ kome nɔ, ni etsɔɔ shishi akɛ sɛɛnamɔ ni ji US$135 kɛha Susete9 ni afee lɛ tɔn kome).
a AA electrochemical gbɛjianɔtoo lɛ he nyɔmɔwoo fɛɛ ni yɔɔ shishijee sane lɛ shishi lɛ kɛ FE ni ji 82%, ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni ji 300 mA cm−2, kɛ 1.76 V. Yɛ sensitivity mlipɛimɔ lɛ mli lɛ, parameters ni akase lɛ pɛ ji nɔ ni atsake ni parameters krokomɛi lɛ ahi shi daa yɛ TEA model lɛ nɔ. d Nɔ ni FE sɔrɔtoi kɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni haa mɔ he jɔɔ lɛ tsuɔ yɛ AA electrosynthesis sɛɛnamɔ lɛ kɛ sɛɛnamɔ ni jɛɔ Ni(OH)2-NS kɛ NiV-LDH-NS mli baa lɛ nɔ, ni asusuɔ akɛ tsɔne lɛ mli hewalɛ lɛ hiɔ shi daa yɛ 1.76 V. Akɛ saji ni akɛwoɔ mli kɛha a–d lɛ haa yɛ saji ni aŋmalaa lɛ mli.
Yɛ nɛkɛ susumɔ nɛɛ nɔ lɛ, wɔtee nɔ wɔtao bɔ ni FE kɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ tsuɔ nii ehaa yɛ AA electrosynthesis lɛ sɛɛnamɔ he lɛ mli. Wɔna akɛ sɛɛnamɔ ni anáa lɛ kɔɔ FE ni ji AA lɛ he waa, ejaakɛ FE ni baa shi lɛ kɛ nitsumɔ he nyɔmɔwoo lɛ yaa hiɛ waa, ni no haa shika fɛɛ ni akɛtsuɔ nii lɛ yaa hiɛ waa (Mfoniri 7b). Yɛ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛlɛtswaa lɛ he lɛ, ŋmɛnɛŋmɛnɛ beaŋ ŋmɛnɛŋmɛnɛ beaŋ ŋmɛlɛtswaa ni nɔ kwɔ (>200 mA cm-2) yeɔ ebuaa ni ehaa shika ni akɛwoɔ shikatoohe lɛ kɛ tso maa he nyɔmɔwoo lɛ baa shi, titri lɛ kɛtsɔ electrolytic cell area lɛ ni ajieɔ lɛ shi lɛ nɔ, ni no haa sɛɛnamɔ lɛ yaa hiɛ (Mfoniri 7c). Kɛ akɛto ŋmɛnɛŋmɛnɛ beaŋ density lɛ he lɛ, FE yɛ hewalɛ ni sa kadimɔ waa yɛ sɛɛnamɔ nɔ. Kɛtsɔ bɔ ni FE kɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne lɛ tsuɔ nii ehaa yɛ sɛɛnamɔ nɔ lɛ he mfonirifeemɔ nɔ lɛ, wɔnaa bɔ ni ehe hiaa ni aná FE ni nɔ kwɔ (>60%) yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔnei ni kɔɔ nitsumɔhei ahe (>200 mA cm-2) lɛ mli faŋŋ koni sɛɛnamɔ aba. Yɛ FE sɛɛnamɔ ni nɔ kwɔ ni yɔɔ AA lɛ hewɔ lɛ, nɔ ni akɛtsuɔ nii kɛ NiV-LDH-NS akɛ nɔ ni haa mɔ tsui nyɔɔ emli lɛ yaa nɔ ehiɔ shi yɛ 100–500 mA cm−2 (pentagram dots; Mfoniri 7d) teŋ. Shi, kɛha Ni(OH)2-NS lɛ, FE ni baa shi yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni fa babaoo mli (>200 mA cm−2) lɛ kɛ yibii ni esaaa baa (kɔɔyɔɔ; Mfoniri 7d), ni maa bɔ ni tsɔnei ni haa FE ni fa babaoo yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni fa babaoo mli lɛ he hiaa ha lɛ nɔ mi.
Kɛfata bɔ ni nibii ni haa mɔ tsui nyɔɔ emli lɛ he hiaa ha yɛ shika kɛ nitsumɔ he nyɔmɔwoo ni baa shi lɛ he lɛ, wɔ TEA mlipɛimɔ lɛ tsɔɔ akɛ abaanyɛ aha sɛɛnamɔ ni anáa lɛ aya hiɛ yɛ gbɛi enyɔ nɔ. Klɛŋklɛŋ nɔ lɛ ji ni akɛ potassium sulfate (K2SO4) lɛ afee ekome kɛhɔ̃ɔ yɛ jara nɔ akɛ nɔ ni jɛɔ tsɔne ni haa mɔ he jɔɔ lɛ mli baa, shi shika ni baanyɛ ajɛ mli aba lɛ ji US$828/t AA-1 (Saji ni fata he 9). Nɔ ni ji enyɔ lɛ ji ni afee nibii ni akɛtsuɔ nii lɛ jogbaŋŋ, ni nɔ ni fata he ji nibii ni akɛtsuɔ nii ekoŋŋ loo AA mligbalamɔ he ŋaalee ni he ehiaaa tsɔ (gbɛi krokomɛi ni atsɔɔ nɔ ajieɔ neutralization kɛ separation units lɛ). Nibii ni akɛtsuɔ nii amrɔ nɛɛ baanyɛ aha nibii ahe nyɔmɔwoo aya hiɛ (ni ji nɔ ni fe fɛɛ ni ji 85.3%), ni 94% jɛ cyclohexanone kɛ KOH ($2069/t AA-1; Mfoniri 7a) hewɔ, shi taakɛ atsĩ tã yɛ yiteŋgbɛ lɛ, gbɛ ni atsɔɔ nɔ atsuɔ he nii lɛ fɛɛ he yɛ sɛɛnamɔ lolo. Wɔkɛɔ akɛ, abaanyɛ ajie nibii ahe nyɔmɔwoo shi babaoo kɛtsɔ gbɛi ni etee hiɛ babaoo ni akɛjieɔ KOH kɛ cyclohexanone ni afeee nɔ ko lɛ nɔ, tamɔ electrodialysis kɛha KOH14 ni ajieɔ lɛ kwraa (asusuɔ akɛ shika ni akɛwoɔ mli lɛ ji US$1073/t AA-1 kɛtsɔ electrodialysis nɔ; Nɔ ni fata he 9).
Yɛ kukufoo mli lɛ, wɔnine shɛ aluminum atom electrolysis ni tsuɔ nii jogbaŋŋ yɛ ŋmɛnɛŋmɛnɛ beaŋ tsɔne ni mli wa nɔ kɛtsɔ V ni akɛwo Ni (OH) 2 nanosheets lɛ mli lɛ nɔ. Yɛ 1.5–1.9 VRHE kɛ 170 mA cm−2 ni ji 170 mA cm−2 lɛ shishi lɛ, AA FE ni yɔɔ NiV-LDH-NS lɛ shɛ 83–88%, yɛ be mli ni OER lɛ tsi enaa jogbaŋŋ kɛyashɛ 3%. V tsakemɔ lɛ ha Ni2+ lɛ ba shi kɛtee Ni3+x lɛ nɔ ni eha cyclohexanone lɛ shweremɔ tee hiɛ. Shikpamɔ kɛ tsɔɔmɔi ahe saji tsɔɔ akɛ, sɛɛkuu ni tsirɛɔ lɛ haa ŋmɛnɛŋmɛnɛ beaŋ shweremɔ ni yaa hiɛ kɛha cyclohexanone oxidation lɛ yaa hiɛ ni eshiɔ RDS ni yɔɔ COR lɛ kɛjɛɔ sɛɛkuu mli kɛyaa dehydrogenation ni Cα − H scission fata he lɛ nɔ, yɛ be mli ni cyclohexanone ni yaa hiɛ lɛ tsiɔ OER naa. MEA lɛ hiɛyaa lɛ ha AA nitsumɔ yaa nɔ yɛ nitsumɔhe ŋmɛnɛŋmɛnɛ 300 mA cm−2, AA nitsumɔ ni aŋmala ashwie shi ni ji 82%, kɛ nitsumɔ ni ji 1536 μmol cm−2 h−1. ŋmɛlɛtswai 50 kaa ko tsɔɔ akɛ NiV-LDH-NS yɛ shifimɔ kpakpa ejaakɛ ebaanyɛ ekwɛ AA FE ni nɔ kwɔ nɔ yɛ MEA mli (> 80% kɛha ŋmɛlɛtswai 60 yɛ 200 mA cm−2; > 70% kɛha ŋmɛlɛtswai 58 yɛ 300 mA cm−2). Esa akɛ akadi akɛ ehe miihia ni afee AEMs ni he wa babaoo koni anyɛ ahi shi be kakadaŋŋ yɛ nitsumɔhei ni hi jogbaŋŋ ni yɔɔ amrɔ nɛɛ amli. Kɛfata he lɛ, TEA lɛ maa shika gbɛfaŋ sɛɛnamɔi ni yɔɔ gbɛi ni atsɔɔ nɔ atsuɔ nii kɛfeɔ AA lɛ he lɛ nɔ mi, kɛ bɔ ni ehe hiaa ni afee nibii ni haa mɔ tsui nyɔɔ emli kɛ tsɔnei ni etee hiɛ ni akɛgbalaa nibii amli lɛ koni akɛba shika helɛtemɔ shi babaoo lɛ nɔ mi.