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Hydrogen he ŋaalee nitsumɔ lɛ ji nɔ ni yɔɔ shika helɛtemɔ ni kɔɔ ŋmɔshi nibii ahe lɛ mli. Taakɛ nɔ ni he hiaa dani aná hydrogen nitoo lɛ, nibii ni tsuɔ nii ni yɔɔ shiŋŋ kɛha hydrogenation (de)hydrogenation nifeemɔ he miihia. Kɛbashi amrɔ nɛɛ, nɛkɛ he nɛɛ ji he ni akɛ dade ni jara wa tsuɔ nii waa. Yɛ biɛ lɛ, wɔkɛ nɔ ko hee ni jara waaa ni damɔ kobalt nɔ (Co-SAs/NPs@NC) ni dade kome ni aja mli waa lɛ kɛ nanoparticles kpakpai feɔ ekome kɛtsuɔ nii koni anyɛ ana formic acid dehydrogenation ni tsuɔ nii jogbaŋŋ lɛ he ŋaa. Kɛtsɔ nibii ni hi fe fɛɛ ni ji CoN2C2 ni gbɛ eshwa kɛ ato nanoparticles ni dalɛ ji 7-8 nm lɛ nɔ, ni akɛ propylene carbonate tsu nii akɛ nɔ ni haa nu mli tseɔ lɛ, ana gas ni hi jogbaŋŋ ni ji 1403.8 ml g-1 h-1, ni nɔ ko nɔ ko bɛ ni laajeɔ yɛ 5 sɛɛkuu sɛɛ. nitsumɔ, ni hi fe jarayeli Pd/C lɛ toi 15. Yɛ shihilɛ mli lɛ, shikpamɔi tsɔɔ akɛ, kɛ akɛto dade atom kome kɛ nanoparticle catalysts ni kɔɔ he lɛ he lɛ, Co-SAs/NPs@NC haa HCOO * ni ji monodentate teŋgbɛ lɛ mli nibii ni he hiaa waa lɛ shwieɔ shi ni etsuɔ ​​nii, ni no haa CH bond cleavage ni nyiɛɔ sɛɛ lɛ yaa hiɛ. Akɔntaabuu ni atsɔɔ mli lɛ tsɔɔ akɛ, cobalt nanoparticles ni akɛwoɔ mli lɛ haa d-band teŋgbɛ ni yɔɔ Co atom kome mli lɛ tsakeɔ kɛyaa he ko ni tsuɔ nii, ni no haa tsakpaa ni yɔɔ carbonyl O ni yɔɔ HCOO * teŋgbɛ lɛ kɛ Co teŋgbɛ lɛ teŋ lɛ yaa hiɛ, ni no haa hewalɛ gbɛtsii nii lɛ baa shi.
Abuɔ hydrogen akɛ eji hewalɛ ni he hiaa waa kɛha jeŋ muu fɛɛ hewalɛ tsakemɔ ni ebaanyɛ efee nɔ titri ni haa anyɛɔ ashɛɔ carbon neutrality1 he. Yɛ egbɔmɔtsoŋ nibii tamɔ la ni tsoɔ kɛ emli tsɔne ni baa shi lɛ hewɔ lɛ, hydrogen nitoo kɛ tsɔne ni akɛyaa lɛ ji saji titrii ni haa anáa hydrogen shika helɛtemɔ2,3,4. Akɛ nu ni ji hydrogen carriers (LOHCs), ni toɔ hydrogen ni ejieɔ kɛtsɔɔ tsofai ni akɛtsuɔ nii lɛ anɔ lɛ etsɔɔ akɛ eji tsabaa. Kɛ akɛto molecular hydrogen he lɛ, nibii ni tamɔ nɛkɛ (methanol, toluene, dibenzyltoluene, kɛ ekrokomɛi) lɛ ahe nitsumɔ waaa ni ehi jogbaŋŋ5,6,7. Yɛ blema LOHC srɔtoi lɛ ateŋ lɛ, formic acid (FA) lɛ yɛ tsofa ni gbeɔ mɔ ni baa shi (LD50: 1.8 g/kg) kɛ H2 hewalɛ ni ji 53 g/L loo 4.4 wt%. Nɔ ni sa kadimɔ ji akɛ, FA ji LOHC pɛ ni baanyɛ ato ni ejie hydrogen yɛ shihilɛi ni mli wa mli yɛ nibii ni sa ni haa etsuɔ ​​nii lɛ ahiɛ, no hewɔ lɛ ehe ehiaaa ni akɛ hewalɛ babaoo awo mli1,8,9. Yɛ anɔkwale mli lɛ, afee dade nibii ni hi jogbaŋŋ kɛha formic acid lɛ mli nu ni ajieɔ kɛjɛɔ mli lɛ, nɔkwɛmɔnɔ, palladium-based dade nibii tsuɔ nii shii 50-200 fe dade nibii ni jara waaa10,11,12. Shi, kɛji akɛ osusu dade ni tsuɔ nii lɛ jara he, ákɛ nɔkwɛmɔnɔ lɛ, palladium jara fe shii 1000.
Cobalt, dade ni tsuɔ nii waa ni yɔɔ shiŋŋ taomɔ yaa nɔ egbalaa niiamlitaolɔi babaoo ni yɔɔ nikasemɔ kɛ nitsumɔhei amli lɛ amiishɛɛ.
Eyɛ mli akɛ afee nibii ni jara waaa ni damɔ Mo kɛ Co nɔ, kɛ agbɛnɛ nanocatalysts ni akɛ noble/base metal alloys fee lɛ, 14,16 kɛha FA dehydrogenation moŋ, shi amɛ nitsumɔ ni baa shi fiofio yɛ be mli ni nifeemɔ lɛ yaa nɔ lɛ ji nɔ ni anyɛɛɛ ajo naa foi yɛ dade, CO2, kɛ H2 nitsumɔ hei ni tsuɔ nii lɛ ahewɔ. loo formate anions (HCOO-), FA mujiwoo, nibii bibii ni abua naa kɛ CO ni baanyɛ afee gbeyei17,18. Wɔ kɛ mɛi krokomɛi tsɔɔ nyɛsɛɛ nɛɛ akɛ atom kome ni haa mɔ tsui nyɔɔ emli (SACs) ni yɔɔ CoIINx hei ni egbɛ eshwa waa akɛ hei ni tsuɔ nii lɛ haa bɔ ni formic acid dehydrogenation lɛ tsuɔ nii ehaa lɛ yaa hiɛ kɛ akɛtoɔ nanoparticles17,19,20,21,22,23,24 he. Yɛ Co-NC nibii nɛɛ amli lɛ, N atoms tsuɔ nii akɛ hei wuji ni woɔ FA deprotonation he hewalɛ yɛ be mli ni ehaa shihilɛ ni yɔɔ shiŋŋ lɛ yaa hiɛ kɛtsɔ Co atom ni yɔɔ teŋgbɛ lɛ nɔ, yɛ be mli ni Co atoms haa H adsorption hei ni ewoɔ CH22 scission he hewalɛ, 25,26. Nɔ ni yɔɔ awerɛho ji akɛ, nɛkɛ nibii nɛɛ anitsumɔ kɛ amɛshifimɔ lɛ kɛ ŋmɛnɛŋmɛnɛ beaŋ dade nibii ni yɔɔ srɔtoi ni yɔɔ ekome kɛ nɔ ni yɔɔ srɔtoi lɛ teŋ jɛkɛ lolo (Mfoniri 1) 13 .
Hewalɛ ni fa fe nine ni jɛɔ nibii ni anyɛɔ atsakeɔ tamɔ hulu loo kɔɔyɔɔ mli lɛ baanyɛ aba kɛtsɔ nu ni akɛ electrolysis tsuɔ nii yɛ mli lɛ nɔ. Abaanyɛ akɛ hydrogen ni anáa lɛ ato kɛtsɔ LOHC, ni ji nu ko ni hydrogen kɛ dehydrogen ni anyɛɔ atsakeɔ lɛ nɔ. Yɛ dehydrogenation gbɛ nɔ lɛ, nɔ pɛ ni jɛɔ mli baa ji hydrogen, ni akuɔ sɛɛ akɛ nu ni hiɛɔ lɛ baa eshishijee shihilɛ mli ni akɛ hydrogen woɔ mli ekoŋŋ. Yɛ naagbee lɛ, abaanyɛ akɛ hydrogen atsu nii yɛ gas stɛshinii, batrei, nitsumɔhei, kɛ ekrokomɛi amli.
Nyɛsɛɛ nɛɛ, abɔ amaniɛ akɛ SACs pɔtɛɛ nitsumɔ lɛ baanyɛ aya hiɛ yɛ dade atom srɔtoi loo dade hei krokomɛi ni nanoparticles (NPs) loo nanoclusters (NCs)27,28 kɛhaa lɛ ahiɛ. Enɛ gbeleɔ gbɛi kɛha nibii krokomɛi ni akɛwoɔ mli kɛ nitsumɔ, kɛ agbɛnɛ hu kɛha geometry kɛ electronic structure ni yɔɔ monatomic hei lɛ tsakemɔ. Yɛ nɛkɛ gbɛ nɔ lɛ, substrate adsorption/nitsumɔ baanyɛ afee nɔ ni hi jogbaŋŋ, ni ekɛ catalytic nitsumɔ ni hi fe fɛɛ aha29,30. Enɛ haa wɔnáa susumɔ akɛ wɔbaafee nibii ni sa ni haa mɔ tsui nyɔɔ emli ni akɛ hybrid active sites tsuɔ nii. Eyɛ mli akɛ SACs ni atsake amɛ lɛ ejie nyɛmɔ kpele kpo yɛ nibii srɔtoi ni haa mɔ tsui nyɔɔ emli lɛ amli31,32,33,34,35,36 moŋ, shi bɔ ni wɔle lɛ, amɛgbɛfaŋnɔ yɛ hydrogen nitoo mli lɛ mli kãaa shi faŋŋ. Yɛ enɛ gbɛfaŋ lɛ, wɔbɔɔ gbɛ ni yɔɔ srɔtoi ni yɔɔ hewalɛ ni akɛfeɔ cobalt-ni damɔ hybrid catalysts (Co-SAs/NPs@NCs) ni nanoparticles ni atsɔɔ shishi kɛ dade ŋtayaai aŋkroaŋkroi yɔɔ mli lɛ he amaniɛ. Co-SAs/NPs@NC ni afee lɛ jogbaŋŋ lɛ jieɔ formic acid dehydrogenation nitsumɔ ni hi jogbaŋŋ kpo, ni hi fe nibii ni jeee nɔ ni hi jogbaŋŋ (tamɔ CoNx, cobalt atom kome, cobalt@NC kɛ γ-Mo2N) kɛ dade nibii ni hi jogbaŋŋ po. In-situ su kɛ DFT akɔntaabuu ni kɔɔ nibii ni tsuɔ nii ahe lɛ tsɔɔ akɛ dade hei aŋkroaŋkroi tsuɔ nii akɛ hei ni tsuɔ nii, ni nanoparticles ni yɔɔ ŋmɛnɛŋmɛnɛ nibii ni afee lɛ mli lɛ haa d-band teŋgbɛ Co atoms lɛ yaa hiɛ, ewoɔ adsorption kɛ HCOO * nitsumɔ he hewalɛ, ni no haa hewalɛ ni tsiɔ nii anaa lɛ baa shi. .
Zeolite imidazolate mfonirifeemɔi (ZIFs) ji nibii ni tsɔɔ hiɛ ni yɔɔ fãi etɛ ni haa nibii ni haa nitrogen ni akɛwo mli lɛ tsuɔ nii (dade-NC nibii ni haa mɔ tsui nyɔɔ emli) koni eye ebua dade srɔtoi37,38. No hewɔ lɛ, Co (NO3)2 kɛ Zn (NO3)2 kɛ 2-methylimidazole ni yɔɔ methanol mli lɛ feɔ ekome ni amɛfeɔ dade ni kɛ amɛhe kpãa gbee ni yɔɔ tsɔne mli lɛ. Yɛ be mli ni ajie CoZn-ZIF lɛ kɛjɛ mli ni egbi lɛ sɛɛ lɛ, ajie lɛ kpo yɛ hulutsoo be srɔtoi amli (750–950 °C) yɛ kɔɔyɔɔ ni ji 6% H2 kɛ 94% Ar mli. Taakɛ atsɔɔ yɛ mfoniri ni yɔɔ shishigbɛ nɛɛ mli lɛ, nibii ni jɛɔ mli baa lɛ yɛ he ni amɛtsuɔ nii yɛ lɛ sui srɔtoi ni atsɛɔ amɛ Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 (Mfoniri 2a). ) . Atsɔɔ shikpamɔ pɔtɛɛ komɛi ni kɔɔ nibii ni afee lɛ ahe lɛ mli fitsofitso yɛ mfoniri 1 kɛ 2. C1-C3. Afee X-ray diffraction (VTXRD) ni tsakeɔ hulutsoo lɛ koni akɛkwɛ bɔ ni nɔ ni haa hulutsoo lɛ yaa hiɛ ehaa lɛ nɔ. Kɛji pyrolysis latsaa lɛ shɛ 650 °C lɛ, XRD mfoniri lɛ tsakeɔ waa yɛ ZIF (Fig. S4) 39 kristalo gbɛjianɔtoo lɛ gbee shi hewɔ. Beni hulutsoo be lɛ yaa hiɛ lɛ, ŋwɛi ŋtayaai enyɔ ni mli kwɔlɔ jeɔ kpo yɛ XRD mfoniri ni ji Co-SAs/NPs@NC-750 kɛ Co-SAs/NPs@NC-750 lɛ mli yɛ 20–30° kɛ 40–50°, ni damɔ shi kɛha ŋwɛi ŋta ni ji amorphous carbon (Mfoniri C5). 40. E sa nɛ wa kai kaa, hɛ mi nyami etɛ pɛ nɛ a na ngɛ 44.2°, 51.5° kɛ 75.8°, nɛ ji dade kobalt (JCPDS #15-0806) ɔ nɔ, kɛ 26.2°, nɛ ji graphitic carbon (JCPDS # 41-1487) ɔ nɔ. X-ray ni yɔɔ Co-SAs/NPs@NC-950 lɛ tsɔɔ akɛ graphite-tamɔ kobalt nibii bibii ni yɔɔ nɔ ni haa nɔ ko yaa hiɛ lɛ nɔ. Raman spectrum lɛ tsɔɔ akɛ etamɔ nɔ ni Co-SAs/NPs@NC-950 lɛ yɛ D kɛ G yitsei ni mli wa ni amɛhe ejɔ fe nɔkwɛmɔnii krokomɛi lɛ, ni tsɔɔ akɛ graphitization lɛ fa babaoo ( Mfoniri S6 ). 1261 m2 g-1 kɛ 0.37 cm3 g-1) fe nɔkwɛmɔnii krokomɛi ni ZIFs lɛ ateŋ babaoo ji NC nibii ni jɛ mli ba. nibii (Mfoniri S7 kɛ Okadi S1). Atomik tsɔne ni akɛkwɛɔ nibii amli lɛ tsɔɔ akɛ, kobɔlt ni yɔɔ Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@ lɛ mli lɛ ji 2.69 wt.%, 2.74 wt.% kɛ 2.73 wt.%. NC-750 lɛ mli (Okadi S2). Zn ni yɔɔ Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 lɛ mli lɛ yaa hiɛ fiofio, ni no jɛɔ Zn fãi lɛ amli shweremɔ kɛ amɛhe ni shwieɔ shi lɛ mli baa. Nɔyaa yɛ latsaa mli latsaa mli (Zn, latsaa he = 907 °C) 45.46. Elemental analysis (EA) tsɔɔ akɛ N mlijaa oha mlijaa lɛ baa shi kɛ pyrolysis latsaa lɛ yaa hiɛ, ni O ni fa babaoo lɛ baanyɛ ajɛ molecular O2 ni jɛɔ kɔɔyɔɔ mli lɛ mli lɛ hewɔ. (Okpɔnɔ nɔ S3). Yɛ cobalt mli nibii komɛi amli lɛ, nanoparticles kɛ coatoms ni yɔɔ srɔto lɛ hiɔ shi, ni no haa nɔ ni haa nibii yaa hiɛ lɛ yaa hiɛ waa, taakɛ awie he yɛ shishigbɛ lɛ.
Co-SA/NPs@NC-T lɛ he mfoniri ni atsɔɔ mli, he ni T ji pyrolysis latsaa (°C) lɛ. b TEM mfoniri. c Mfoniri ni kɔɔ mɛi ni kɛ amɛhe woɔ nitsumɔ mli lɛ ahe. Akɛ kooyigbɛ tsuru ekadi Co atom komekomei lɛ. d EDS henɔ ni ji Co-SA/NPs@NC-950.
Nɔ ni sa kadimɔ ji akɛ, tsɔne ni akɛkwɛɔ nibii bibii amli (TEM) lɛ tsɔɔ akɛ kobalt nanoparticles (NPs) srɔtoi ni dalɛ ji 7.5 ± 1.7 nm pɛ yɛ Co-SAs/NPs@NC-950 ( Mfoniri 2 b kɛ S8 ) lɛ mli. Akɛ carbon ni tamɔ graphite ni akɛ nitrogen ewo mli lɛ ewo nɛkɛ nibii bibii nɛɛ amli. 0.361 kɛ 0.201 nm lɛ teŋ jɛkɛmɔ lɛ kɛ graphitic carbon (002) kɛ dade Co (111) mli nibii bibii lɛ kpãa gbee. Kɛfata he lɛ, ŋwɛi ŋta ni yɔɔ ŋwɛi ŋta lɛ mli lɛ jie lɛ kpo akɛ, Co NPs ni yɔɔ Co-SAs/NPs@NC-950 lɛ mli lɛ, atomik kobalt babaoo ebɔle amɛhe (Mfoniri 2c). Shi, atom mli kobalt atom pɛ ji nɔ ni ana yɛ nɔkwɛmɔnii enyɔ krokomɛi lɛ ayelikɛbuamɔ nɔ (Mfoniri S9). HAADF-STEM mfoniri tsɔɔ C, N, Co kɛ Co NPs ni mli egbala lɛ mlijaa kome yɛ Co-SAs/NPs@NC-950 (Mfoniri 2d). Nibii nɛɛ fɛɛ tsɔɔ akɛ, Co ŋtayaai ni gbɛ eshwa kɛ nanoparticles ni akɛwo N-doped graphite-tamɔ carbon mli lɛ yeɔ omanye yɛ NC ŋtayaai ni yɔɔ Co-SAs/NPs@NC-950 lɛ amli lɛ ahe, yɛ be mli ni dade ŋtayaai pɛ ji mɛi ni yɔɔ srɔto.
Akɛ X-ray fotoelektron spektroskopi (XPS) kase bɔ ni nibii ni ana lɛ yɔɔ ha kɛ tsofai ni yɔɔ mli lɛ. XPS spectra ni yɔɔ tsɔnei etɛ lɛ amli lɛ tsɔɔ akɛ nibii ni ji Co, N, C kɛ O yɛ, shi Zn yɛ Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 pɛ mli (Mfoniri 2). ). C10). Beni pyrolysis latsaa lɛ yaa hiɛ lɛ, nitrogen ni yɔɔ mli lɛ fɛɛ baa shi be mli ni nitrogen henɔi lɛ bafeɔ nɔ ni bɛ shiŋŋ ni efiteɔ kɛyaa NH3 kɛ NOx kɔɔyɔɔ mli yɛ latsaa ni yaa hiɛ lɛ mli (Table S4) 47 . No hewɔ lɛ, carbon ni yɔɔ mli lɛ fɛɛ tee hiɛ fiofio kɛjɛ Co-SAs/NPs@NC-750 kɛtee Co-SAs/NPs@NC-950 kɛ Co-SAs/NPs@NC-950 (Mfoniri S11 kɛ S12). Nɔkwɛmɔnɔ ni pyrolyzed yɛ hulutsoo be ni mli wa mli lɛ yɛ nitrogen atoms lɛ mlijaa bibioo, ni tsɔɔ akɛ esa akɛ NC tsɔnei ni yɔɔ Co-SAs/NPs@NC-950 lɛ amli lɛ ayibɔ afee bibioo fe nɔkwɛmɔnii krokomɛi amli lɛ. Enɛ haa kobalt mli nibii bibii lɛ feɔ sintering ni mli wa waa. O 1s ŋwɛi ŋta lɛ tsɔɔ yitsei enyɔ C=O (531.6 eV) kɛ C–O (533.5 eV), yɛ amɛteŋ (Mfoniri S13) 48 . Taakɛ atsɔɔ yɛ mfoniri 2a lɛ mli lɛ, abaanyɛ atsu N 1s ŋwɛi ŋta lɛ he nii awo sui ejwɛ ni ji pyridine nitrogen N (398.4 eV), pyrrole N (401.1 eV), graphite N (402.3 eV) kɛ Co-N (399.2 eV) lɛ mli. Co-N bonds yɛ nɔkwɛmɔnii etɛ lɛ fɛɛ mli, ni tsɔɔ akɛ N atom komɛi kɛ monometallic hei kpãa gbee, shi sui lɛ yɛ srɔto kwraa49. Nibii ni akɛwoɔ la mli lɛ baanyɛ aha Co-N nibii ni yɔɔ mli lɛ aba shi kɛjɛ 43.7% yɛ Co-SA/NPs@NC-750 mli kɛyashi 27.0% yɛ Co-SAs/NPs@NC-850 kɛ Co 17.6%@NC-950 mli. yɛ -CA/NPs mli, ni kɛ C mli nibii ni yaa hiɛ lɛ kpãa gbee (Mfoniri 3a), ni tsɔɔ akɛ amɛ Co-N coordination yibɔ lɛ baanyɛ atsake ni C50 atoms lɛ atsake amɛ fã ko. Zn 2p spectrum lɛ tsɔɔ akɛ nɛkɛ nɔ nɛɛ yɛ Zn2+ su mli titri. (Mfoniri S14) 51. Co 2p lɛ hulutsoo be lɛ jieɔ ŋwɛi ŋwɛi ŋwɛi enyɔ ni he gbɛi waa kpo yɛ 780.8 kɛ 796.1 eV, ni akɛtoɔ Co 2p3/2 kɛ Co 2p1/2 he (Mfoniri 3b). Kɛ akɛto Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 he lɛ, Co-N yitso ni yɔɔ Co-SAs/NPs@NC-950 lɛ mli lɛ tsakeɔ kɛyaa fã ni hi lɛ nɔ, ni tsɔɔ akɛ Co atom kome ni yɔɔ ŋwɛi -SAs/NPs@NC-950 lɛ mli lɛ yɛ electron depletion shihilɛ ni nɔ kwɔ fe fɛɛ yɛ nɔ ni jɛɔ mli baa lɛ mli. Ehe miihia ni wɔkadi akɛ Co-SAs/NPs@NC-950 pɛ jie zero-valent cobalt (Co0) lɛ yitso ni bɛ hewalɛ kpo yɛ 778.5 eV, ni tsɔɔ akɛ nanoparticles ni jɛɔ SA cobalt ni abua naa yɛ hulutsoo be mli lɛ mli baa lɛ yɛ.
a N 1s kɛ b Co 2p ŋwɛi ŋta ni ji Co-SA/NPs@NC-T. c XANES kɛ d FT-EXAFS ŋwɛibɔfoi ni yɔɔ Co-K-naa ni ji Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750. e WT-EXAFS ŋwɛi ŋta ni ji Co-SAs/NPs@NC-950, Ko-SAs/NPs@NC-850, kɛ Ko-SAs/NPs@NC-750. f FT-EXAFS ni sa kɛha Co-SA/NPs@NC-950.
No sɛɛ lɛ, akɛ X-ray absorption spectroscopy (XAS) ni akɛ be tsuɔ nii yɛ mli lɛ tsu nii koni akɛpɛi bɔ ni Co bɔɔ nii ni yɔɔ nɔkwɛmɔnɔ ni asaa he lɛ mli lɛ yɔɔ ha lɛ mli. Cobalt valence maji ni yɔɔ Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 Edge gbɛjianɔtoo ni ajieɔ lɛ kpo kɛtsɔ X-ray ni bɛŋkɛɔ ŋmɔ lɛ mli ni ajieɔ lɛ kpo yɛ Co-K edge (XANES) spectrum lɛ nɔ. Taakɛ atsɔɔ yɛ mfoniri 3c lɛ mli lɛ, ŋwɛi ŋta ni bɛŋkɛɔ nɔkwɛmɔnii etɛ lɛ anaa lɛ yɛ Co kɛ CoO foil lɛ teŋ, ni tsɔɔ akɛ Co henɔi lɛ a-valence shihilɛ lɛ jeɔ shishi kɛjɛɔ 0 ​​kɛyashiɔ +253. Kɛfata he lɛ, ana tsakemɔ ko kɛmiiya hewalɛ ni baa shi mli kɛjɛ Co-SAs/NPs@NC-950 kɛtee Co-SAs/NPs@NC-750 kɛ Co-SAs/NPs@NC-750, ni tsɔɔ akɛ Co-SAs/NPs@NC-750 yɛ oksideshin shihilɛ ni baa shi. Tsɔɔmɔ gbɛjianɔtoo. Taakɛ linear ni akɛtoɔ he lɛ tsɔɔ lɛ, abuɔ Co valence shihilɛ ni yɔɔ Co-SAs/NPs@NC-950 lɛ he akɔntaa akɛ eji +0.642, ni ji nɔ ni baa shi fe Co valence shihilɛ ni yɔɔ Co-SAs/NPs@NC-850 (+1.376) lɛ. 750 (+1.402). Nibii nɛɛ tsɔɔ akɛ, mɛi ni yɔɔ Co-SAs/NPs@NC-950 lɛ ateŋ mɛi ni yɔɔ Co-SAs/NPs@NC-950 lɛ ateŋ mɛi ni yɔɔ ŋwɛi lɛ ateŋ mɛi komɛi kɛ amɛhe woɔ nitsumɔ mli, ni enɛ kɛ XRD kɛ HADF-STEM nibii ni jɛ mli ba lɛ kpãa gbee, ni abaanyɛ atsɔɔ mli kɛtsɔ cobalt nanoparticles kɛ cobalt kome ni kɛ amɛhe feɔ ekome lɛ nɔ. . Fourier tsakemɔ X-ray ŋmɛlɛtswaa kpakpa (FT-EXAFS) ŋwɛi ŋta ni yɔɔ Co K-edge lɛ mli lɛ tsɔɔ akɛ ŋwɛi ŋta titri ni yɔɔ 1.32 Å lɛ ji Co-N/Co-C ŋta lɛ nɔ, yɛ be mli ni dade Co -Co gbɛ ni gbɛɔ eshwaa lɛ yɛ 2.18 pɛ ni anaa yɛ Co-SAs /Fig5d Å mli). Kɛfata he lɛ, wavelet tsakemɔ (WT) lɛ tsɔɔ hewalɛ ni fe fɛɛ yɛ 6.7 Å-1 ni akɛto Co-N/Co-C he, yɛ be mli ni Co-SAs/NPs@NC-950 pɛ tsɔɔ hewalɛ ni fe fɛɛ ni akɛto 8.8 he. Nɔ kroko ni mli wa fe fɛɛ ji Å−1 kɛyashi Co–Co tsakpaa lɛ nɔ (Mfoniri 3e). Kɛfata he lɛ, EXAFS mlipɛimɔ ni lessor lɛ fee lɛ tsɔɔ akɛ yɛ pyrolysis latsaa ni ji 750, 850 kɛ 950 °C lɛ, Co-N tsakpaa yibɔi lɛ ji 3.8, 3.2 kɛ 2.3, yɛ gbɛ kome nɔ, ni Co-C tsakpaa yibɔi lɛ ji 0. 0.1, S.3 kɛ S.5. Yɛ gbɛ pɔtɛɛ ko nɔ lɛ, abaanyɛ akɛ nɔ ni jɛ mli ba lɛ ato CoN2C2 kui ni gbɛ eshwa kɛ nanoparticles ni yɔɔ Co-SAs/NPs@NC-950 lɛ he. Nɔ ni tamɔɔɔ enɛ lɛ, yɛ Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 mli lɛ, CoN3C kɛ CoN4 pɛ ji nɔ ni yɔɔ mli. Eyɛ faŋŋ akɛ, kɛ́ pyrolysis latsaa lɛ tee hiɛ lɛ, N atom ni yɔɔ CoN4 kuu lɛ mli lɛ, C atom lɛ yeɔ amɛ najiaŋ fiofio, ni cobalt CA lɛ feɔ nanoparticles.
Akɛ shihilɛi ni akase tsutsu lɛ tsu nii koni akɛkase bɔ ni shihilɛi ni akɛsaa he lɛ tsuɔ nii ehaa yɛ nibii srɔtoi lɛ ahe (Fig. S16)17,49. Taakɛ atsɔɔ yɛ mfoniri 4 a lɛ mli lɛ, Co-SAs/NPs@NC-950 nitsumɔ lɛ nɔ kwɔ kwraa fe Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 lɛ. Nɔ ni sa kadimɔ ji akɛ, Co nɔkwɛmɔnii etɛ ni asaa lɛ fɛɛ jie nitsumɔ ni hi fe fɛɛ kpo kɛ akɛto jarayeli dade ni jara wa ni akɛtsuɔ nii (Pd/C kɛ Pt/C) lɛ he. Kɛfata he lɛ, Zn-ZIF-8 kɛ Zn-NC nɔkwɛmɔnii lɛ tsuuu nii kɛyaa formic acid dehydrogenation he, ni tsɔɔ akɛ Zn mli nibii lɛ jeee hei ni tsuɔ nii, shi amɛ hewalɛ ni amɛyɔɔ yɛ nitsumɔ lɛ nɔ lɛ faaa kwraa. Kɛfata he lɛ, Co-SAs/NPs@NC-850 kɛ Co-SAs/NPs@NC-750 nitsumɔ lɛ tsɔ pyrolysis ni ji enyɔ nɔ yɛ 950°C kɛha ŋmɛlɛtswaa kome, shi eba shi fe Co-SAs/NPs@NC-750 nɔ lɛ. 950 (Mfoniri S17). Nibii nɛɛ ahe mfonirifeemɔ tsɔɔ akɛ Co nanoparticles yɛ nɔkwɛmɔnii ni afee lɛ ekoŋŋ lɛ amli, shi ŋwɛi ŋta pɔtɛɛ ni yɔɔ shishi lɛ kɛ graphite-tamɔ carbon ni bɛ lɛ ha nitsumɔ ni baa shi kɛ akɛto Co-SAs/NPs@NC-950 he (Mfoniri S18–S20). Akɛ nitsumɔ ni kɔɔ nɔkwɛmɔnii ni yɔɔ Co precursor yibɔi srɔtoi lɛ ahe lɛ hu to he, ni nitsumɔ ni nɔ kwɔ fe fɛɛ lɛ ji nɔ ni atsɔɔ yɛ 3.5 mol ni akɛfataa he lɛ mli (Table S6 kɛ Figure S21). Eyɛ faŋŋ akɛ, dade ŋwɛi ŋtayaai srɔtoi lɛ afeemɔ ji nɔ ni hydrogen ni yɔɔ pyrolysis kɔɔyɔɔ lɛ mli lɛ kɛ pyrolysis be lɛ náa nɔ hewalɛ. No hewɔ lɛ, akwɛ Co-SAs/NPs@NC-950 nibii krokomɛi amli koni ana bɔ ni formic acid ni haa nu mli tsɔɔ lɛ tsuɔ nii eha. Nibii fɛɛ ni akɛtsuɔ nii lɛ tsɔɔ akɛ amɛtsuɔ nii jogbaŋŋ yɛ gbɛ ni sa nɔ kɛyashi nɔ ni hi jogbaŋŋ; shi kɛlɛ, amɛteŋ eko kwraa bɛ ni hi fe Co-SAs/NPs@NC-950 (Mfoniri S22 kɛ S23). Nibii lɛ ahe gbɛjianɔtoo lɛ tsɔɔ akɛ kɛ pyrolysis be lɛ tee hiɛ lɛ, nɔ ni yɔɔ monoatomic Co-N shihilɛi amli lɛ baa shi fiofio yɛ dade atoms ni abua naa kɛyaa nanoparticles mli lɛ hewɔ, ni tsɔɔ srɔtofeemɔ ni yɔɔ nitsumɔ mli yɛ nɔkwɛmɔnii ni yɔɔ pyrolysis be ni ji 100-2000 lɛ ateŋ. henɔi. 0.5 h, 1 h, kɛ 2 h (Mfoniri S24–S28 kɛ Okadi S7).
Graf ni kɔɔ gas falɛ kɛ be ni anáa yɛ dehydrogenation ni jɛɔ fuel kuu mli kɛtsɔ catalysts srɔtoi ni akɛtsuɔ nii lɛ nɔ. 110 °C, Tactical: 98 °C, fãi 4 b Co-SAs/NPs@NC-950 ( 30 mg), nibii srɔtoi ni haa mɔ tsui nyɔɔ emli. c Gas sutsakemɔ mlijaa ni akɛtoɔ heterogeneous catalysts ni yɔɔ bɔɔ nii ni wala yɔɔ mli lɛ amli yɛ 85–110 °C. d Co-SA/NPs@NC-950 nibii ni akɛtsuɔ nii ekoŋŋ lɛ akasemɔ. 110 °C, Tactual: 98 °C, nɔ fɛɛ nɔ ni baa lɛ heɔ ŋmɛlɛtswaa kome. Tɔmɔ bars damɔ shi kɛha srɔtofeemɔi ni abu he akɔntaa kɛjɛ kaai etɛ ni tsuɔ nii amli.
Yɛ fɛɛ mli lɛ, bɔ ni FA dehydrogenation catalysts lɛ tsuɔ nii jogbaŋŋ lɛ damɔ shihilɛi ni yɔɔ mli lɛ anɔ waa, titri lɛ nɔ ni akɛtsuɔ nii lɛ nɔ. Kɛ akɛ nu tsu nii akɛ nɔ ni haa hulu tsoɔ lɛ, Co-SAs/NPs@NC-950 jieɔ shishijee nifeemɔ ni yaa hiɛ fe fɛɛ lɛ kpo, shi sɛɛkuu ba, ekolɛ protons loo H2O18 ni yeɔ hei ni tsuɔ nii lɛ anɔ lɛ hewɔ. 1,4-dioxane (DXA), n-butyl acetate (BAC), toluene (PhMe), triglyme kɛ cyclohexanone (CYC) lɛ hu etsɔɔɔ hiɛyaa ko, ni yɛ propylene carbonate (PC) ) (Mfoniri 4b kɛ Table S8). Nakai nɔŋŋ hu, nibii ni akɛfataa he tamɔ triethylamine (NEt3) loo sodium formate (HCCONa) lɛ bɛ hewalɛ kpakpa kroko yɛ tsɔne ni haa tsɔne lɛ tsuɔ nii jogbaŋŋ lɛ nɔ (Mfoniri S29). 1403.8 mL g−1 h−1 (Fig. S30), ni ji nɔ ni nɔ kwɔ kwraa fe Co catalysts fɛɛ ni abɔ he amaniɛ tsutsu lɛ (ni SAC17, 23, 24 fata he). Yɛ shikpamɔi srɔtoi amli lɛ, kɛji akɛ nibii ni tee nɔ yɛ nu mli kɛ nibii ni akɛfataa he lɛ fataaa he lɛ, ana dehydrogenation kɛ nu ni bɛ mli lɛ halamɔi ni shɛɔ 99.96% (Table S9). Nibii ni asusuɔ he lɛ ji 88.4 kJ/mol, ni akɛtoɔ dade ni hi jogbaŋŋ ni haa mɔ tsui nyɔɔ emli lɛ ahewalɛ ni akɛtsuɔ nii lɛ he (Mfoniri S31 kɛ Table S10).
Kɛfata he lɛ, wɔkɛ nibii krokomɛi ni haa mɔ he jɔɔ lɛ ayibɔ toɔ formic acid dehydrogenation he yɛ shihilɛi ni tamɔ nakai nɔŋŋ shishi (Mfoniri 4c, okpɔlɔi S11 kɛ S12). Taakɛ atsɔɔ yɛ mfoniri 3c lɛ mli lɛ, gas ni ajieɔ kɛjɛɔ Co-SAs/NPs@NC-950 mli lɛ fa fe heterogeneous base metal catalysts ni ale babaoo lɛ, ni eyɛ shii 15 kɛ 15 fe jarayeli 5% Pd/C kɛ 5% Pd/C, yɛ gbɛ kome nɔ, kɛ 10 shikome. % Pt/C nɔ ni haa mɔ tsui nyɔɔ emli.
Nɔ ni he hiaa waa yɛ (de)hydrogenation nibii ni akɛtsuɔ nii lɛ mli ji amɛ shifimɔ. No hewɔ lɛ, afee nibii ni akɛtsuɔ nii ekoŋŋ lɛ ahe kaai ni nyiɛ sɛɛ kɛtsɔ Co-SAs/NPs@NC-950 nɔ. Taakɛ atsɔɔ yɛ mfoniri 4 d lɛ mli lɛ, shishijee nitsumɔ kɛ nibii ni ahalaa lɛ tee nɔ ehi shi yɛ foidamɔi enumɔ ni nyiɛ sɛɛ lɛ amli (kwɛmɔ Table S13 hu). Afee be kakadaŋŋ mli kaai ni gas ni ajieɔ lɛ tee hiɛ linearly yɛ ŋmɛlɛtswai 72 mli (Mfoniri S32). Cobalt ni yɔɔ Co-SA/NPs@NC-950 ni akɛtsu nii lɛ mli lɛ ji 2.5 wt%, ni ebɛŋkɛ nɔ ni yɔɔ tsɔne hee lɛ mli lɛ he waa, ni tsɔɔ akɛ kobalt ni hoɔ yɛ faŋŋ mli lɛ bɛ (Table S14). Akwɛɛɛ su tsakemɔ ko ni yɔɔ faŋŋ loo dade nibii bibii ni abua naa dani nifeemɔ lɛ ba kɛ sɛɛ mli ( Mfoniri S33 ). AC-HAADF-STEM kɛ EDS nibii ni akɛtsuɔ nii yɛ be kakadaŋŋ mli kaai amli lɛ tsɔɔ akɛ atomik gbɛfaŋnɔ hei lɛ ahiɔ shi ni amɛgbɛɔ amɛshwaa yɛ gbɛ kome nɔ, ni tsakemɔi ni sa kadimɔ ko bɛ gbɛjianɔtoo lɛ mli (Mfoniri S34 kɛ S35). Nibii ni yɔɔ Co0 kɛ Co-N lɛ mli lɛ yɛ XPS mli lolo, ni etsɔɔ akɛ Co NPs kɛ dade hei aŋkroaŋkroi lɛ hiɔ shi ekome, ni no hu maa Co-SAs/NPs@NC-950 catalyst lɛ shifimɔ nɔ mi (Mfoniri S36).
Kɛha hei ni tsuɔ nii waa ni haa formic acid dehydrogenation lɛ yaa nɔ lɛ, asaa nibii ni ahala ni yɔɔ dade teŋgbɛ kome pɛ (CoN2C2) loo Co NP ni damɔ nikasemɔi ni eho lɛ anɔ17. Nɔ ni kɔɔ formic acid ni ajieɔ nu kɛjɛɔ mli lɛ he lɛ ji Co-SAs/NPs@NC-950 > Co SA > Co NP (Table S15), ni tsɔɔ akɛ CoN2C2 hei ni egbɛ eshwa lɛ tsuɔ nii fe NPs . Nibii ni tee nɔ lɛ tsɔɔ akɛ, hydrogen sutsakemɔ lɛ nyiɛɔ klɛŋklɛŋ gbɛjianɔtoo ni haa mɔ tsui nyɔɔ emli lɛ sɛɛ, shi ŋwɛibɔfoi babaoo ni yɔɔ cobalt mli nibii srɔtoi lɛ amli lɛ ashishijee lɛ jeee ekome, ni tsɔɔ akɛ jeee formic acid pɛ nɔ nibii ni tee nɔ lɛ damɔɔɔ, shi moŋ edamɔɔ he ni etsuɔ ​​nii yɛ lɛ hu nɔ (Mfoniri 2). C37). Nikasemɔi krokomɛi ni kɔɔ kinetic he lɛ tsɔɔ akɛ, kɛ akɛto cobalt dade yitsei ni bɛ X-ray diffraction mlipɛimɔ lɛ he lɛ, ana akɛ kinetic gbɛjianɔtoo ni kɔɔ cobalt mli nibii ahe lɛ ji 1.02 yɛ shishigbɛ ŋwɛigbɛ (ni shɛɛɛ 2.5%), ni tsɔɔ akɛ monoatomic cobalt centers lɛ mlijaa lɛ miihe ashɛ ekome. klɛŋklɛŋ. he ni tsuɔ nii (mfoniri S38 kɛ S39). Kɛji akɛ Co mli nibii ni yɔɔ mli lɛ shɛ 2.7% lɛ, r yaa hiɛ trukaa, ni tsɔɔ akɛ nanoparticles lɛ kɛ atom aŋkroaŋkroi lɛ yeɔ jogbaŋŋ koni amɛná nitsumɔ ni nɔ kwɔ. Beni Co mli nibii lɛ amli nibii lɛ yaa hiɛ lɛ, ŋwɛi ŋta lɛ bafeɔ nɔ ni bɛ linear, ni kɛ nanoparticles lɛ ayibɔ ni yaa hiɛ kɛ monatomic shihilɛi ni baa shi lɛ baa. No hewɔ lɛ, LC dehydrogenation nitsumɔ ni hi jogbaŋŋ ni Co-SA/NPs@NC-950 lɛ jɛɔ dade hei aŋkroaŋkroi kɛ nanoparticles lɛ nifeemɔ ni kɛ amɛhe feɔ ekome lɛ mli baa.
Akɛ Fourier tsakemɔ (in situ DRIFT) ni haa mɔ tsui nyɔɔ emli lɛ tsu nii kɛyoo nɔ ni haa mɔ tsui nyɔɔ emli yɛ nifeemɔ lɛ mli. Beni akɛ nɔkwɛmɔnii lɛ wo la mli kɛtee hulutsoo be srɔtoi amli yɛ formic acid ni akɛfata he lɛ sɛɛ lɛ, ana ŋmɛlɛtswai enyɔ ni afɔɔ feemɔ (Mfoniri 5a). 1089, 1217 kɛ 1790 cm-1, ni akɛtoɔ kponɔgbɛ CH π (CH) ni shwieɔ shi, CO ν (CO) ni shwieɔ shi kɛ C=O ν (C=O) ni shwieɔ shi respect,45 lɛ he. 1363 kɛ 1592 cm-1 lɛ mli ŋwɛi ŋsɔɔdoi krokomɛi ni yɔɔ 1363 kɛ 1592 cm-1 lɛ kɛ OCO ni hosoɔ ni ji νs(OCO) lɛ kɛ OCO ni hosoɔ ni νas(OCO)33.56 HCOO* lɛ kpãa gbee. Beni nɔ ni yaa nɔ lɛ yaa nɔ lɛ, HCOOH* kɛ HCOO* henɔi lɛ ayitsei ni yɔɔ ŋwɛi lɛ sɛɛ foɔ fiofio. Kɛ aawie he lɛ, formic acid lɛ mligbalamɔ lɛ kɔɔ gbɛi titrii etɛ he: (I) formic acid lɛ ni ajieɔ kɛjɛɔ hei ni tsuɔ nii yɛ lɛ, (II) H ni ajieɔ kɛjɛɔ mli kɛtsɔɔ formate loo carboxylate gbɛ lɛ nɔ, kɛ (III) H ni ajieɔ lɛ enyɔ ni akɛwoɔ mli lɛ ni akɛaafee hydrogen. HCOO* kɛ COOH* ji teŋgbɛ nibii ni he hiaa ni tsɔɔ formate loo carboxylate gbɛi lɛ, yɛ amɛteŋ57. Kɛtsɔ wɔ catalytic gbɛjianɔtoo lɛ nɔ lɛ, HCOO * yitso pɛ ji nɔ ni je kpo, ni tsɔɔ akɛ formic acid fitemɔ baa kɛtsɔɔ formic acid gbɛ lɛ pɛ nɔ58. Akwɛ nibii ni tamɔ nakai nɔŋŋ yɛ hulutsoo be ni baa shi ni ji 78 °C kɛ 88 °C (mfoniri S40).
Yɛ he ni eyɔɔ lɛ, HCOOH ni ajieɔ nu kɛjɛɔ mli lɛ mli yɛ Co-SAs/NPs@NC-950 kɛ b Co SAs nɔ. Abɛbua lɛ tsɔɔ be ni akɛtsuɔ nii yɛ he ni atsuɔ nii yɛ lɛ. c Gas falɛ sɔrɔtoi ni ajieɔ lɛ kpo kɛtsɔ isotope srɔtoi ni akɛwoɔ nibii amli lɛ nɔ yɛ be mli. d Kainetik isotop he saji.
Afee DRIFT kaai ni tamɔ nakai nɔŋŋ yɛ nibii ni kɔɔ he lɛ anɔ Co NP kɛ Co SA koni akɛkase bɔ ni Co-SA/NPs@NC-950 ( Mfoniri 5 b kɛ S41 ) lɛ tsuɔ nii amɛhaa lɛ he nii. Nibii enyɔ lɛ fɛɛ tsɔɔ nibii ni tamɔ amɛhe, shi HCOOH* kɛ HCOO* lɛ sui lɛ ayitsei lɛ tsakeɔ fioo, ni tsɔɔ akɛ Co NPs ni akɛba lɛ tsakeɔ tsɔne ni yɔɔ monoatomic center lɛ mli lɛ. νas(OCO) yitso ni yɔɔ su ko jeɔ kpo yɛ Co-SAs/NPs@NC-950 kɛ Co SA mli shi jeee yɛ Co NPs mli, ni etsɔɔ hu akɛ nɔ ni yɔɔ teŋgbɛ ni afeɔ kɛji akɛ akɛ formic acid fata he lɛ ji monodentate formic acid ni damɔ shi shiŋŋ yɛ ŋmei ni yɔɔ ŋwɛi lɛ nɔ. ni akɛwoɔ SA mli akɛ he ni tsuɔ nii 59 . E sa nɛ wa kai kaa a na kaa hɛ mi nyami nɛ ngɛ suhi nɛ a ji π(CH) kɛ ν(C = O) ɔ a hɛ mi yae wawɛɛ, nɛ e ngɛ kaa nɔ́ nɛ enɛ ɔ ha nɛ HCOOH * ɔ tsɔɔ hɛ mi nyami, nɛ e ha nɛ nɔ́ ɔ pee mlɛo. Nɔ ni jɛ mli ba ji akɛ, su ni ji HCOOH * kɛ HCOO * ni yɔɔ Co-SAs/NPs@NC lɛ mli lɛ shwɛ fioo ni ebaafite yɛ minitii 2 ni akɛtsuɔ nii lɛ sɛɛ, ni enɛ yaa oya fe nɔ ni yɔɔ monometallic (minitii 6) kɛ nanoparticle-based catalysts (minitii 12) lɛ mli lɛ. . Nibii nɛɛ fɛɛ maa nɔ mi akɛ, nanoparticle doping lɛ haa nibii ni yɔɔ teŋgbɛ lɛ shwieɔ shi ni amɛtsuɔ nii, ni no haa nibii ni awie he yɛ ŋwɛi nɛɛ yaa oya.
Kɛha gbɛ ni atsɔɔ nɔ atsuɔ nii lɛ mlipɛimɔ ni akɛnaa gbɛ ni atsɔɔ nɔ atsuɔ nii (RDS) lɛ, afee KIE hewalɛ lɛ yɛ Co-SAs/NPs@NC-950 hiɛ. Yɛ biɛ lɛ, akɛ formic acid isotopes srɔtoi tamɔ HCOOH, HCOOD, DCOOH kɛ DCOOD tsuɔ nii kɛhaa KIE nikasemɔi. Taakɛ atsɔɔ yɛ mfoniri 5c lɛ mli lɛ, nu ni ajieɔ kɛjɛɔ mli lɛ baa shi yɛ gbɛ ni nyiɛ sɛɛ nɛɛ nɔ: HCOOH > HCOOD > DCOOH > DCOOD. Kɛfata he lɛ, abu KHCOOH/KHCOOD, KHCOOH/KDCOOH, KHCOOD/KDCOOD kɛ KDCOOH/KDCOOD lɛ jara lɛ he akɔntaa akɛ 1.14, 1.71, 2.16 kɛ 1.44, yɛ gbɛ kome nɔ (Mfoniri 5d). No hewɔ lɛ, CH tsakpaa ni yɔɔ HCOO * mli lɛ jieɔ kH/kD sɛɛnamɔi >1.5 kpo, ni tsɔɔ nɔ ni jɛɔ mli baa 60,61, ni etamɔ nɔ ni edamɔ shi kɛha RDS ni ji HCOOH mligbalamɔ yɛ Co-SAs/NPs@NC-950 nɔ.
Kɛfata he lɛ, afee DFT akɔntaabuu koni anu bɔ ni nanoparticles ni akɛwoɔ mli lɛ tsuɔ nii ehaa yɛ Co-SA mli nitsumɔ lɛ nɔ lɛ shishi. Akɛ Co-SAs/NPs@NC kɛ Co-SA nɔkwɛmɔnii lɛ damɔ shikpamɔi ni atsɔɔ kɛ nitsumɔi ni eho lɛ anɔ (Figs. 6a kɛ S42)52,62. Yɛ jiomɛtri nitsumɔ lɛ sɛɛ lɛ, ana Co6 nanoparticles bibii (CoN2C2) ni kɛ monoatomic units lɛ feɔ ekome lɛ, ni ana Co-C kɛ Co-N tsakpaa ni yɔɔ Co-SA/NPs@NC lɛ mli lɛ akɛ eji 1.87 Å kɛ 1.90 Å, yɛ gbɛ kome nɔ. , ni kɛ XAFS hetooi lɛ kpãa gbee. Nibii ni abu he akɔntaa lɛ tsɔɔ akɛ Co dade atom kome kɛ nanoparticle composite (Co-SAs/NPs@NC) jieɔ hybridization ni nɔ kwɔ ni bɛŋkɛ Fermi ŋwɛigbɛ lɛ kpo kɛ akɛto CoN2C2 he, ni no haa HCOOH baa. Electron ni efite lɛ mlitsɔɔmɔ lɛ tsuɔ nii jogbaŋŋ fe tsutsu lɛ ( Mfoniri 6b kɛ S43 ). Akɛ d-band centers ni kɛ Co-SAs/NPs@NC kɛ Co-SA lɛ kpãa gbee lɛ bu he akɔntaa akɛ -0.67 eV kɛ -0.80 eV, yɛ gbɛ kome nɔ, ni Co-SAs/NPs@NC lɛ mliyaa lɛ ji 0.13 eV, ni no ye ebua ni beni ajie NP lɛ kpo lɛ sɛɛ lɛ, electronic structure ni CoO*N lɛ tsakeɔ lɛ ba. Srɔtofeemɔ ni yɔɔ charge density mli lɛ tsɔɔ electron atatu agbo ko ni bɔle CoN2C2 block lɛ kɛ nanoparticle lɛ he, ni tsɔɔ tsakpaa ni mli wa ni yɔɔ amɛteŋ yɛ electron tsakemɔ hewɔ. Kɛ akɛ Bader charge mlipɛimɔ fata he lɛ, ana akɛ Co ni gbɛ eshwa atomik lɛ laaje 1.064e yɛ Co-SA/NPs@NC mli kɛ 0.796e yɛ Co SA mli ( Mfoniri S44 ). Nibii nɛɛ tsɔɔ akɛ, nanoparticles lɛ ni akɛwoɔ mli lɛ haa electron ni yɔɔ Co hei lɛ amli lɛ baa shi, ni no haa Co valence lɛ yaa hiɛ, ni no kɛ XPS nibii ni jɛ mli ba lɛ kpãa gbee (Mfoniri 6c). Akwɛ Co-O nifeemɔ sui ni kɔɔ HCOO ni akɛwoɔ Co-SAs/NPs@NC kɛ Co SA mli lɛ mli kɛtsɔ kristalin ŋwɛi Hamiltonian kuu (COHP)63 lɛ he akɔntaabuu nɔ. Taakɛ atsɔɔ yɛ mfoniri 6 d lɛ mli lɛ, -COHP sɛɛnamɔi ni ehiii kɛ sɛɛnamɔi ni hi kɛ antibonding shihilɛ kɛ binding shihilɛ lɛ kpãa gbee, yɛ gbɛ kome nɔ. Akwɛ bɔ ni Co-O ni HCOO (Co-carbonyl O HCOO*) lɛ ŋmɛɔ lɛ mli hewalɛ yɔɔ ha lɛ mli kɛtsɔ -COHP sɛɛnamɔi ni akɛfata he lɛ nɔ, ni ji 3.51 kɛ 3.38 kɛha Co-SAs/NPs@NC kɛ Co-SA, yɛ gbɛ kome nɔ. HCOOH adsorption hu tsɔɔ nɔ ni jɛ mli ba ni tamɔ nakai nɔŋŋ: -COHP sɛɛnamɔ ni yɔɔ mli lɛ mliyaa yɛ nanoparticle doping sɛɛ tsɔɔ Co-O bonding lɛ mliyaa, ni no haa HCOO kɛ HCOOH nitsumɔ yaa hiɛ ( Mfoniri S45 ).
950 ŋwɛi ŋtayaa gbɛjianɔtoo. b PDOS Kuu-SA/NP@NC-950 kɛ Kuu-SA. 3D isosurface ni tsɔɔ srɔtofeemɔ ni yɔɔ HCOOH ni akɛwoɔ mli lɛ mli lɛ mli yɛ Co-SA/NPs@NC-950 kɛ Co-SA nɔ. (d) pCOHP ni ji Co-O nibii ni HCOO ŋmɛɔ yɛ Co-SA/NPs@NC-950 (abɛkugbɛ) kɛ Co-SA (ninejurɔgbɛ) lɛ nɔ. e Gbɛ ni HCOOH ni ajieɔ kɛjɛɔ nu mli lɛ tsuɔ nii yɛ Co-SA/NPs@NC-950 kɛ Co-SA nɔ.
Kɛha Co-SA/NPs@NC lɛ dehydrogenation nitsumɔ ni nɔ kwɔ lɛ shishinumɔ jogbaŋŋ lɛ, atsɔɔ gbɛ ni atsɔɔ nɔ atsuɔ nii kɛ hewalɛ ni eyɔɔ lɛ mli. Yɛ gbɛ pɔtɛɛ ko nɔ lɛ, FA mli nu ni ajieɔ kɛjɛɔ mli lɛ kɔɔ gbɛi enumɔ nɔ, ni nɔ ni fata he ji HCOOH tsakemɔ kɛmiiya HCOOH*, HCOOH* kɛmiiya HCOO* + H*, HCOO* + H* kɛmiiya 2H* + CO2*, 2H* + CO2* kɛmiiya 2H* + CO2, kɛ 2H* ni yɔɔ H2 mli lɛ mli (Mfoniri 6e). Nibii ni haa mɔ tsui nyɔɔ emli lɛ ahewalɛ ni yɔɔ tsɔne ni haa wala yibii lɛ yaa hiɛ lɛ nɔ kɛtsɔɔ carboxylic kɔɔyɔɔ lɛ nɔ lɛ baa shi fe hydroxyl kɔɔyɔɔ lɛ (Mfoniri S46 kɛ S47). No sɛɛ lɛ, yɛ hewalɛ ni baa shi lɛ hewɔ lɛ, adsorbate lɛ sumɔɔ ni etsɔ OH bond cleavage mli ni efee HCOO* moŋ fe CH bond cleavage ni ekɛfee COOH*. Yɛ nakai beaŋ nɔŋŋ lɛ, HCOO* kɛ monodentate adsorption tsuɔ nii, ni no haa bɔɔnd lɛ mligbalamɔ kɛ CO2 kɛ H2 feemɔ yaa hiɛ. Nɛkɛ yibii nɛɛ kɛ νas(OCO) yitso ni yɔɔ in situ DRIFT lɛ kpãa gbee, ni etsɔɔ hu akɛ FA fitemɔ baa kɛtsɔɔ formate gbɛ lɛ nɔ yɛ wɔ nikasemɔ lɛ mli. Ehe miihia ni wɔkadi akɛ taakɛ KIE susumɔi lɛ tsɔɔ lɛ, CH dissociation lɛ yɛ hewalɛ ni haa mɔ tsui nyɔɔ emli lɛ he gbɛtsii nii ni nɔ kwɔ fe nɔ ni haa mɔ tsui nyɔɔ emli lɛ gbɛi krokomɛi ni edamɔ shi kɛha RDS. Hewalɛ gbɛtsii nii ni yɔɔ Co-SAs/NPs@NC tsɔne ni hi fe fɛɛ lɛ mli lɛ ji 0.86 eV ni baa shi fe Co-SA (1.2 eV) lɛ, ni no haa tsɔne ni haa nu mli tseɔ lɛ fɛɛ yaa hiɛ jogbaŋŋ. Nɔ ni sa kadimɔ ji akɛ, nanoparticles ni yɔɔ lɛ kudɔɔ electronic gbɛjianɔtoo ni yɔɔ atomic dispersed coactive hei lɛ, ni haa sɛɛgbɛ nibii ni yɔɔ teŋgbɛ lɛ mlibotemɔ kɛ nitsumɔ yaa hiɛ, ni no haa nɔ ni tsiɔ nii anaa lɛ baa shi ni ehaa hydrogen feemɔ yaa hiɛ.
Yɛ kukufoo mli lɛ, wɔtsɔɔ klɛŋklɛŋ kwraa akɛ, abaanyɛ aha tsɔne ni haa hydrogen feɔ nii lɛ aya hiɛ jogbaŋŋ kɛtsɔ nibii ni yɔɔ monometallic centers ni aja waa kɛ nanoparticles bibii ni akɛtsuɔ nii lɛ nɔ. Nɛkɛ susumɔ nɛɛ ji nɔ ni ama nɔ mi kɛtsɔ dade kome ni akɛ cobalt tsuɔ nii ni akɛ nanoparticles (Co-SAs/NPs@NC) tsakeɔ lɛ nɔ, kɛ agbɛnɛ hu nibii ni kɔɔ he ni dade kome pɛ yɔɔ mli (CoN2C2) loo Co NPs lɛ. Akɛ pyrolysis gbɛ ni yɔɔ mlɛo ni akɛtsuɔ nii yɛ gbɛ kome nɔ lɛ saa nibii fɛɛ ahe. Nibii ni atsɔɔ mli lɛ amlipɛimɔ tsɔɔ akɛ nɔ ni hi fe fɛɛ ni haa mɔ tsui nyɔɔ emli (Co-SAs/NPs@NC-950) lɛ ji CoN2C2 ni gbɛ eshwa atomik kɛ nanoparticles bibii (7-8 nm) ni akɛ nitrogen kɛ carbon ni tamɔ graphite ewo mli lɛ. 1403.8 ml g-1 h-1 (H2:CO2 = 1.01:1), H2 kɛ CO nihalamɔ ni ji 99.96% ni ebaanyɛ ekwɛ nitsumɔ nɔ daa gbii babaoo. Nitsumɔ ni nɛkɛ tsɔne nɛɛ tsuɔ lɛ feɔ Co SA kɛ Pd/C tsɔnei komɛi anitsumɔ lɛ shii 4 kɛ 15, yɛ amɛteŋ. Yɛ he ni DRIFT shikpamɔi tsɔɔ akɛ kɛ akɛto Co-SA he lɛ, Co-SAs/NPs@NC-950 jieɔ HCOO* ni mli wa waa lɛ kpo, ni he hiaa waa kɛha formate gbɛ lɛ, ni dopant nanoparticles baanyɛ aha HCOO * nitsumɔ kɛ C–H oyaiyeli aya hiɛ. Ayoo bond mligbalamɔ lɛ akɛ RDS. Nibii ni atsɔɔ mli lɛ tsɔɔ akɛ, Co NP doping lɛ haa d-band center ni yɔɔ Co atom kome mli lɛ yaa hiɛ kɛ 0.13 eV kɛtsɔ nifeemɔ nɔ, ni ehaa HCOOH * kɛ HCOO * teŋgbɛ nibii lɛ agbɛɛmɔ yaa hiɛ, ni no haa nɔ ni haa mɔ tsui nyɔɔ emli lɛ baa shi kɛjɛɔ 1.20 eV kɛha Co SA kɛyaa 0 .86 eV. Lɛ ji mɔ ni tsuɔ nitsumɔ ni sa kadimɔ waa he nii.
Yɛ gbɛ ni da nɔ lɛ, nɛkɛ niiamlipɛimɔ nɛɛ haa susumɔi kɛha dade ni atom kome yɔɔ mli lɛ he gbɛjianɔtoo ni ehaa shishinumɔ yaa hiɛ yɛ bɔ ni aaafee aha dade nitsumɔ aya hiɛ kɛtsɔ dade ni dalɛi srɔtoi yɔɔ mli lɛ nitsumɔ nɔ. Wɔheɔ wɔyeɔ akɛ abaanyɛ atsɔ gbɛ nɛɛ nɔ ashɛ tsɔnei krokomɛi babaoo ni haa tsɔne lɛ tsuɔ nii jogbaŋŋ lɛ ahe oya.
Akɛ tsofai ni haa mɔ he jɔɔ lɛ tsuɔ nii yɛ McLean, China. Ahe tsofa ni haa mɔ he jɔɔ lɛ (HCOOH, 98%) kɛjɛ Rhawn, China. Akɛ nibii fɛɛ ni akɛtsuɔ nii lɛ tsu nii tɛ̃ɛ ni akɛ hetsemɔ kroko fataaa he, ni akɛ ultrapure hetsemɔ gbɛjianɔtoo tsu nii kɛsaa nu ni mli tse waa. Akɛ Pt/C (5% ni akɛwoɔ mli) kɛ Pd/C (5% ni akɛwoɔ mli) lɛ he kɛjɛ Sigma-Aldrich dɛŋ.
Akɛ CoZn-ZIF nanocrystals lɛ afee ekome yɛ gbɛi ni eho lɛ anɔ kɛ tsakemɔi komɛi23,64. Klɛŋklɛŋ lɛ, akɛ 30 mmol Zn(NO3)2·6H2O (8.925 g) kɛ 3.5 mmol Co(NO3)2·6H2O (1.014 g) futu mli ni akɛwo methanol 300 ml mli. No sɛɛ lɛ, akɛ 2-methylimidazole (9.853 g) ni ji mmol 120 wo methanol ml 100 mli ni akɛfata ŋwɛi tsofa lɛ he. Akɛ nɔ ni akɛfutu lɛ shwie shi yɛ tsu mli dɔlɛ mli ŋmɛlɛtswai 24 sɔŋŋ. Yɛ naagbee lɛ, ajie nɔ ni afee lɛ mli kɛtsɔ centrifugation nɔ yɛ 6429 g kɛha minitii 10 ni akɛ methanol tsu he jogbaŋŋ shii etɛ. Akɛ powda ni jɛ mli ba lɛ gĩ yɛ he ko ni hulutsoo be bɛ mli yɛ 60°C mli gbɛkɛ kome dani akɛtsu nii.
Kɛha Co-SAs/NPs@NC-950 lɛ feemɔ lɛ, akɛ CoZn-ZIF powda ni egbi lɛ wo la mli yɛ 950 °C mli kɛha ŋmɛlɛtswaa kome yɛ la ni hoɔ ni ji 6% H2 + 94% Ar mli, ni la ni tsoɔ lɛ ji 5 °C/min. No sɛɛ lɛ, ajie nɔkwɛmɔnɔ lɛ kpo kɛyashɛ tsu mli dɔlɛ mli koni ana Co-SA/NPs@NC-950. Kɛha Co-SAs/NPs@NC-850 loo Co-SAs/NPs@NC-750 lɛ, atsake hulutsoo be lɛ mli la ni tsoɔ lɛ 850 kɛ 750 °C, yɛ gbɛ kome nɔ. Abaanyɛ akɛ nɔkwɛmɔnii ni asaa he lɛ atsu nii ni atsuuu he nii dɔŋŋ, tamɔ acid etching.
Akɛ TEM (ni ji tsɔne ni akɛkwɛɔ nibii bibii amli) susumɔi lɛ tsu nii yɛ Thermo Fisher Titan Themis 60-300 “cube” nibii bibii ni akɛkwɛɔ nibii bibii ni yɔɔ mfoniri mli lɛ ahe tsɔne ko ni akɛtsakeɔ mfoniri ni ejaaa kɛ 300 kV tsɔne ni akɛkwɛɔ nibii amli lɛ nɔ. Akɛ FEI Titan G2 kɛ FEI Titan Themis Z nibii bibii ni akɛ nibii ni akɛtaoɔ nibii amli kɛ mfonirifeemɔ nibii, kɛ DF4 nibii ni akɛtaoɔ nibii amli ni yɔɔ fãi ejwɛ lɛ tsu nii kɛfee HAADF-STEM kaai lɛ. Ana EDS nibii ahe mfoniri hu yɛ FEI Titan Themis Z nibii bibii akwɛmɔ nɔ. Afee XPS mlipɛimɔ yɛ X-ray fotoelektrɔn ŋwɛi ŋta (Thermo Fisher nɔkwɛmɔnɔ ESCALAB 250Xi) nɔ. Akɛ XANES kɛ EXAFS Co K-edge ŋwɛi ŋtayaai lɛ tsu nii kɛbua XAFS-500 okpɔlɔ (China ŋtayaai ahe nibii ni akɛtsuɔ nii Co., Ltd.) lɛ naa. Akɛ atomik nibii ni ajieɔ kɛjɛɔ mli lɛ (AAS) (PinAAcle900T) tsɔɔ nɔ ni yɔɔ mli lɛ. Akɛ X-ray nibii ni tsɔɔ ŋwɛi ŋta (XRD) lɛ wo X-ray ŋta ni tsɔɔ ŋwɛi ŋta (Bruker, Bruker D8 Advance, Germany) lɛ nɔ. Akɛ nibii ni haa mɔ he jɔɔ lɛ tsuɔ nii kɛnaa nibii ni haa mɔ he jɔɔ lɛ (Micromeritics, ASAP2020, USA).
Afee dehydrogenation nifeemɔ lɛ yɛ argon kɔɔyɔɔ mli ni ajie kɔɔyɔɔ kɛjɛ mli yɛ Schlenk gbɛ ni atsɔɔ nɔ atsuɔ nii lɛ naa. Ajie tsɔne ni haa mɔ tsui nyɔɔ emli lɛ mli ni akɛ argon wo mli shii 6 ekoŋŋ. Sumɔ nu ni akɛwoɔ tsɔne mli lɛ ni okɛ nɔ ni haa nu lɛ yaa hiɛ (30 mg) kɛ nɔ ni haa nu lɛ mli nu (6 ml) afata he. Okɛ thermostat lɛ atsu nii ni okɛha tsɛnsi lɛ mli adɔ kɛyashɛ he ni otaoɔ lɛ ni oha ekɛ minitii 30 afee ekome. No sɛɛ lɛ, akɛ formic acid (10 mmol, 377 μL) fata tsɔne ni akɛtsuɔ nii yɛ argon shishi lɛ he. Tsɔmɔmɔ gbɛi etɛ burette valve lɛ koni ekɛjie reactor lɛ mli hewalɛ, ni oŋa ekoŋŋ, ni obɔi gas ni ajieɔ lɛ falɛ susumɔ kɛtsɔ burette ni akɛ niji tsuɔ nii yɛ nɔ lɛ nɔ (Mfoniri S16). Yɛ be ni he hiaa koni nifeemɔ lɛ agbe naa lɛ sɛɛ lɛ, abua gas nɔkwɛmɔnɔ ko naa kɛha GC mlipɛimɔ kɛtsɔ gas-tight syringe ni akɛ argon tsuɔ he nii lɛ nɔ.
Afee DRIFT shikpamɔi yɛ Fourier tsakemɔ infrared (FTIR) ŋwɛi ŋta (Thermo Fisher Scientific, Nicolet iS50) ni akɛ mercury cadmium telluride (MCT) ni akɛtaoɔ nibii amli lɛ ewo mli lɛ nɔ. Akɛ powda ni haa tsɔne lɛ tsuɔ nii lɛ wo tsɔne ko ni haa tsɔne lɛ tsuɔ nii lɛ mli (Harrick Jeŋ Nilee Nibii, Praying Mantis). Beni akɛ Ar (50 ml/min) ni hoɔ yɛ tsu mli latsaa mli lɛ tsu nii ni haa tsɔne lɛ tsuɔ nii lɛ sɛɛ lɛ, akɛ nɔkwɛmɔnɔ lɛ wo la mli kɛyashɛ latsaa ni ato he gbɛjianɔ lɛ mli, no sɛɛ lɛ akɛ Ar (50 ml/min) wo HCOOH mli nu mli ni afɔse awo in-situ reaction cell lɛ mli. kɛha hetoo. Nɔkwɛmɔnɔ ni yɔɔ srɔtoi ni haa mɔ tsui nyɔɔ emli. Akɛ infrared spectra lɛ wo mli yɛ be ni jeɔ shishi kɛjɛɔ sɛkɛndii 3.0 kɛyashiɔ ŋmɛlɛtswaa kome mli.
Akɛ HCOOH, DCOOH, HCOOD kɛ DCOOD tsuɔ nii akɛ shishitoo nibii ni akɛwoɔ tsɔne mli lɛ mli. Shihilɛi ni eshwɛ lɛ kɛ HCOOH dehydrogenation gbɛjianɔtoo lɛ kpãa gbee.
Akɛ klɛŋklɛŋ shishitoo mlai ahe akɔntaabuu tsu nii kɛtsɔ tsɔne ni akɛtsuɔ nii yɛ Vienna Ab initio nɔkwɛmɔnɔ nibii amli lɛ nɔ (VASP 5.4.4) 65,66. Akɛ wala yibii ni yɔɔ graphene hiɛ (5 × 5) ni sɛɛ tsɛɔ aaafee 12.5 Å tsu nii akɛ nɔ ni akɛtoɔ CoN2C2 kɛ CoN2C2-Co6 he. Akɛ vacuum distance ni fe 15 Å fata he koni akafee nɔ ko yɛ substrate layers ni bɛŋkɛ amɛhe lɛ ateŋ. Atsɔɔ tsakpaa ni yɔɔ ions kɛ electrons ateŋ lɛ mli kɛtsɔ wave ni ajieɔ lɛ kpo (PAW) gbɛ nɔ65,67. Akɛ Perdue-Burke-Ernzerhof (PBE) nitsumɔ ni kɛ van der Waals tsakemɔ ni Grimm68,69 kɛba lɛ tsu nii. Hewalɛ kɛ hewalɛ fɛɛ ni akɛtoɔ he lɛ ji 10−6 eV/atom kɛ 0.01 eV/Å. Akɛ hewalɛ ni afoɔ lɛ to 600 eV kɛtsɔ Monkhorst-Pack 2 × 2 × 1 K-point grid nɔ. Akɛ pseudopotential ni akɛtsuɔ nii yɛ nɛkɛ nɔkwɛmɔnɔ nɛɛ mli lɛ tsuɔ nii kɛjɛɔ tsɔne ni akɛtsuɔ nii yɛ tsɔne mli lɛ mli kɛyaa C 2s22p2 shihilɛ, N 2s22p3 shihilɛ, Co 3d74s2 shihilɛ, H 1 s1 shihilɛ, kɛ O 2s22p4 shihilɛ mli. Akɛ hewalɛ ni jɛɔ mli baa kɛ electron density srɔtofeemɔ lɛ buɔ he akɔntaa kɛtsɔ hewalɛ ni ajieɔ kɛjɛɔ kɔɔyɔɔ mli kɛ ŋwɛi nibii kɛjɛɔ hewalɛ ni jɛɔ mli baa lɛ mli taakɛ hewalɛ ni jɛɔ mli baa loo interface models70,71,72,73,74. Akɛ Gibbs hewalɛ ni aheee nɔ ko lɛ tsakemɔ tsuɔ nii koni akɛtsake DFT hewalɛ awo Gibbs hewalɛ ni aheee nɔ ko mli ni esusuɔ vibrational yelikɛbuamɔ kɛha entropy kɛ zero point hewalɛ75 he. Akɛ mfoniri ni yaa ŋwɛi-nudging elastic band (CI-NEB) gbɛ lɛ tsu nii koni akɛtao tsakemɔ shihilɛ ni yɔɔ hetoo lɛ mli76.
Akɛ saji fɛɛ ni ana ni apɛi mli yɛ nikasemɔ nɛɛ mli lɛ fata sane lɛ kɛ nibii krokomɛi ni fata he lɛ ahe loo abaanyɛ ana kɛjɛ woloŋmalɔ ni kɛ lɛ kpãa gbee lɛ ŋɔɔ kɛji abi ni jwɛŋmɔ yɔɔ mli. Akɛ saji ni jɛ mli ba lɛ eha kɛha niŋmaa nɛɛ.
Kod fɛɛ ni akɛtsu nii yɛ simulations ni fata sane nɛɛ he lɛ yɛ niŋmalɔi ni kɛ amɛhe kpãa gbee lɛ adɛŋ kɛji abi.
Dutta, I. kɛ ekrokomɛi. Formic acid yeɔ ebuaa nibii ni haa kɔɔyɔɔ fɔŋ baa shi lɛ. mligbalalɔi. Hewalɛ nibii. 12, 2103799 (2022).
Wei, D., Sang, R., Sponholz, P., Junge, H. kɛ Beller, M. Nibii ni haa kɔɔyɔɔ ni ji carbon dioxide lɛ feɔ formic acid ni akɛ Mn-claw complexes tsuɔ nii yɛ lysine hiɛ lɛ. Nat. Hewalɛ 7, 438-447 (2022).
Wei, D. kɛ ekrokomɛi. Kɛya hydrogen shika helɛtemɔ nɔ: nibii sɔrɔtoi ni haa hydrogen toɔ kɛ tsofai ni ajieɔ lɛ kpo lɛ ahe nitsumɔ. ACS Hewalɛ Woji. 7, 3734-3752 (2022).
Modisha PM, Ouma SNM, Garijirai R., Wasserscheid P. kɛ Bessarabov D. Gbɛkpamɔi kɛha hydrogen ni akɛtoɔ kɛtsɔ nu ni wala yɔɔ mli ni akɛwoɔ hydrogen mli lɛ nɔ. Hewalɛ Fuels 33, 2778-2796 (2019).
Niermann, M., Timmerberg, S., Drunert, S. kɛ Kaltschmitt, M. Nu ni wala yɔɔ mli ni akɛwoɔ nu mli kɛ gbɛi krokomɛi ni atsɔɔ nɔ akɛ nu ni wala yɔɔ mli ni anyɛɔ atsakeɔ lɛ yaa majimaji ateŋ. tsakemɔ. wamɔ. hewalɛ. Gbelemɔ 135, 110171 (2021).
Preister P, Papp K kɛ Wasserscheid P. Nu ni wala yɔɔ mli ni akɛwoɔ nu mli (LOHC): kɛmiiya nu mli nu ni bɛ mli shika helɛtemɔ mli. aplikashiŋ. Tsofa. nibii ni akɛtsuɔ nii. 50, 74-85 (2017).
Chen, Z. kɛ ekrokomɛi. Palladium nibii ni anyɛɔ akɛ he fɔ̃ɔ nɔ kɛha formic acid nibii ni haa nu mli tseɔ lɛ ahe nitsumɔ. AKS wolo lɛ. 13, 4835-4841 (2023).
Sun, Q., Wang, N., Xu, Q. kɛ Yu, J. Nanopore-fiɔ dade nanocatalysts sɛɛ kɛha hydrogen nitsumɔ ni tsuɔ nii jogbaŋŋ kɛjɛɔ nu-fase hydrogen nitoo tsofai amli. mligbalalɔi. Mat. 32, 2001818 (2020).
Seraj, JJA, kɛ ekrokomɛi. Nɔ ni tsuɔ nii jogbaŋŋ kɛha formic acid krɔŋŋ lɛ mli nu ni ajieɔ kɛjɛɔ mli lɛ. Nat. gbaa sane. 7, 11308 (2016).
Kar S, Rauch M, Leitus G, Ben-David Y. kɛ Milstein D . Formic acid krɔŋŋ ni akɛ nibii fataaa he lɛ mli nu ni ajieɔ kɛjɛɔ mli lɛ tsuɔ nii jogbaŋŋ. Nat. Gatar. 4, 193-201 (2021).
Li, S. kɛ ekrokomɛi. Shishitoo mlai ni yɔɔ mlɛo ni tsuɔ nii jogbaŋŋ kɛha jwɛŋmɔŋ gbɛjianɔtoo ni kɔɔ formic acid ni haa nu mli tseɔ lɛ he. mligbalalɔi. Mat. 31, 1806781 (2019).
Liu, M. kɛ ekrokomɛi. Nɔ ni haa kɔɔyɔɔ ni ji carbon dioxide hydrogen lɛ toɔ formic acid lɛ he tɛknɔlɔji. mligbalalɔi. Hewalɛ nibii. 12, 2200817 (2022).