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Hydrogen technology hmasawnna hi green economy bulpui ber a ni. Hydrogen dahkhawmna tihhlawhtlinna atana precondition atan hydrogenation (de)hydrogenation reaction atana active leh stable catalyst a ngai a ni. Tun thleng hian he hmun hi thir hlu tak tak hmannain a thunun a ni. Hetah hian, novel low-cost cobalt-based catalyst (Co-SAs/NPs@NC) kan rawt a, chutah chuan highly distributed single-metal sites te chu synergistically coupled with fine nanoparticles hmangin formic acid dehydrogenation tha tak a awm theih nan. Atomically dispersed CoN2C2 units leh encapsulated nanoparticles 7-8 nm size material tha ber hmangin, propylene carbonate chu solvent atan hmangin, gas production tha tak 1403.8 ml g-1 h-1 hmuh a ni a, cycle 5 hnuah pawh hlohna a awm lo. activity a ni a, hei hi sumdawnna lama Pd/C aiin a let 15 in a tha zawk a ni. In situ assay experiment-ah chuan, single metal atom leh nanoparticle catalyst inzawmte nena khaikhin chuan, Co-SAs/NPs@NC hian key monodentate intermediate HCOO* adsorption leh activation a tichak a, chu chuan a hnu lama CH bond cleavage a tichak tih a tarlang. Theoretical calculation chuan cobalt nanoparticles integration hian Co atom pakhat d-band center chu active site-ah a chantir a, chu chuan HCOO* intermediate-a carbonyl O leh Co center inkara coupling a tichak a, chu chuan energy barrier a tihhniam thu a tarlang.
Hydrogen hi tunlai khawvel chakna inthlak danglamna atana energy carrier pawimawh takah ngaih a ni a, carbon neutrality neih theihna tura thil pawimawh tak a ni thei bawk1. A physical property, flammability leh low density te avang hian hydrogen hi him leh efficient taka dahkhawm leh phurh chhuah hi hydrogen economy tihhlawhtlinna atana thil pawimawh tak a ni2,3,4. Chemical reaction hmanga hydrogen khawlkhawm leh chhuah thin, liquid organic hydrogen carrier (LOHCs) te chu solution atan an rawt a ni. Molecular hydrogen nena khaikhin chuan hetiang thil (methanol, toluene, dibenzyltoluene, etc.) te hi hman a awlsamin a awlsam hle5,6,7. Traditional LOHC hrang hrang zingah hian formic acid (FA) hian toxicity a nei tlem hle (LD50: 1.8 g/kg) a, H2 capacity chu 53 g/L emaw 4.4 wt% emaw a ni. Hriat tur pawimawh tak chu FA hi LOHC awmchhun a ni a, boruak lum tak hnuaiah pawh catalyst tha tak tak awmnaah hydrogen a dahkhawm thei a, a chhuah thei bawk a, chuvangin pawn lam atanga energy input lian tak tak a mamawh lo1,8,9. Dik tak chuan formic acid dehydrogenation atan noble metal catalyst tam tak siam a ni tawh a, entirnan, palladium-based catalyst te hi metal catalyst man tlawm zawk aiin a let 50-200 in an active zawk10,11,12. Mahse, entirnan, active metals man hi ngaihtuah chuan palladium hi a let 1000 aia tam a ni.
Cobalt, Heterogeneous base metal catalyst active leh stable tak zawn hian zirna leh industry lama zirchiangtu tam tak ngaihven a hlawh chhunzawm zel a ni13,14,15.
Mo leh Co hmanga siam catalyst man tlawm tak tak, chubakah noble/base metal alloy atanga siam nanocatalyst,14,16 te pawh FA dehydrogenation atan siam ni mahse, reaction chhunga an deactivation zawi zawi chu proton ten metal, CO2, leh H2O te active site an luah avangin pumpelh theih a ni lo. emaw formate anion (HCOO-), FA bawlhhlawh, particle aggregation leh CO poisoning awm thei17,18. Tun hnaiah keini leh midangte chuan active site anga CoIINx site dispersed sang tak nei single-atom catalysts (SACs) te hian nanoparticles nena khaikhin chuan formic acid dehydrogenation reactivity leh acid resistance a ti tha zawk tih kan hmuchhuak a ni17,19,20,21,22,23, Heng Co-NC materials-ah hian N atom te hian FA deprotonation tichak turin site lian ber an ni a, chutih rualin central Co atom nena coordination hmangin structural stability an tichak a, Co atom te hian H adsorption site an pe a, CH22 scission a tichak bawk, ​​25,26. Vanduaithlak takin heng catalyst te activity leh stability hi tunlai homogeneous leh heterogeneous noble metal catalyst te nen hian a la hla hle a ni (Fig. 1) 13 .
Ni emaw thli emaw atanga renewable source atanga energy tam lutuk chu tui electrolysis hmangin a siam chhuak thei a ni. Hydrogen siam chhuah chu LOHC hmanga dah theih a ni a, chu chu liquid a ni a, a hydrogenation leh dehydrogenation chu reversible a ni. Dehydrogenation step-ah chuan a siam chhuah awmchhun chu hydrogen a ni a, carrier liquid chu a dinhmun hmasaah a kir leh a, hydrogenated leh a ni. Hydrogen hi a tawpah chuan gas station-ah te, battery-ah te, industry building-ah te, leh thil dang dangah te hman theih a ni ta a ni.
Tun hnaiah chuan SAC bikte intrinsic activity chu metal atom hrang hrang emaw, nanoparticles (NPs) emaw nanoclusters (NCs)-in a pek metal site dang emaw awmnaah a tichak thei tih an sawi Hei hian substrate adsorption leh activation dang neih theihna tur kawng a hawng a, chubakah monatomic site-a geometry leh electronic structure modulation neih theihna tur kawng a hawng bawk. Chutiang chuan substrate adsorption/activation chu a tha thei ang bera siam theih a ni a, chu chuan overall catalytic efficiency tha zawk a pe thei a ni29,30. Hei hian hybrid active site nei catalytic material dik tak siam chhuah theihna tur ngaihtuahna min pe a ni. SAC siam \hatte hian catalytic application hrang hrangah theihna nasa tak nei mah se31,32,33,34,35,36, kan hriat dan chuan hydrogen dahkhawmna kawnga an chanvo hi a chiang lo hle. Hemi chungchangah hian, defined nanoparticles leh individual metal centers atanga siam cobalt-based hybrid catalysts (Co-SAs/NPs@NCs) siamna atana strategy versatile leh robust tak kan report a ni. Optimized Co-SAs/NPs@NC te hian formic acid dehydrogenation performance tha tak an nei a, hei hi non-noble nanostructured catalysts (CoNx, single cobalt atoms, cobalt@NC leh γ-Mo2N ang chi) leh noble metal catalysts te aiin a tha zawk a ni. Active catalyst-te in-situ characterization leh DFT calculation-ah chuan metal site hrang hrangte chu active site angin an thawk tih a tarlang a, he thil hmuhchhuah nanoparticle-te hian Co atom-te d-band center a tichak a, HCOO* adsorption leh activation a tichak a, chu chuan reaction-a energy barrier chu a tihhniam a ni. .
Zeolite imidazolate frameworks (ZIFs) hi three-dimensional precursors chiang taka tarlan a ni a, nitrogen-doped carbon materials (metal-NC catalysts) te tan metal chi hrang hrang thlawp turin catalyst a pe a ni Chuvangin Co(NO3)2 leh Zn(NO3)2 te chu methanol-a 2-methylimidazole nen an inzawm khawm a, solution-a metal complex inmil tak tak an siam a ni. Centrifugation leh drying hnuah CoZn-ZIF chu temperature hrang hrang (750–950 °C)-ah 6% H2 leh 94% Ar atmosphere-ah pyrolyzed a ni. A hnuaia figure-a kan hmuh ang hian, a chhuak thilte hian active site characteristic hrang hrang an nei a, Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750 tiin an vuah a ni (Figure 2a). ) . Synthesis process-a step pawimawh thenkhat experimental observation bikte chu Figure 1 leh 2-ah hian chipchiar takin tarlan a ni.C1-C3. Catalyst evolution enfiah nan Variable temperature X-ray diffraction (VTXRD) an ti a. Pyrolysis temperature 650 °C a thlen chuan ZIF-a ordered crystal structure a tlakchhiat avangin XRD pattern chu nasa takin a danglam thin (Fig. S4) 39 . Temperature a san chhoh zel chuan Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750 XRD pattern-ah 20–30° leh 40–50°-ah peak zau tak pahnih a lang a, hei hian amorphous carbon peak a entir a ni (Fig. C5). 40. Hriat tur chu 44.2°, 51.5° leh 75.8°-ah te characteristic peak pathum chauh hmuh a ni a, chu chu metallic cobalt (JCPDS #15-0806) ta a ni a, 26.2°-ah chuan graphitic carbon ta a ni (JCPDS # 41-1487). Co-SAs/NPs@NC-950 X-ray spectrum atanga a lan dan chuan catalyst-ah hian graphite ang chi encapsulated cobalt nanoparticles a awm tih a lang41,42,43,44. Raman spectrum atanga a lan dan chuan Co-SAs/NPs@NC-950 hian sample dang aiin D leh G peak a chak zawk leh a tawi zawk niin a lang a, hei hian graphitization degree sang zawk a lantir a ni ( Figure S6 ). Hei bakah hian Co-SAs/NPs@NC-950 hian sample dang aiin Brunner-Emmett-Taylor (BET) surface area leh pore volume (1261 m2 g-1 leh 0.37 cm3 g-1) a nei sang zawk a, ZIF tam zawk hi NC derivatives an ni. hmanrua (Figure S7 leh Table S1) te a ni. Atomic absorption spectroscopy (AAS) atanga a lan dan chuan Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 leh Co-SAs/NPs@ te cobalt awm zat chu 2.69 wt.%, 2.74 wt.% leh 2.73 wt.% a ni. NC-750 a ni (Table S2) a ni. Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750-a Zn awm zat hi a pung zauh zauh a, hei hi Zn unit tihtlem leh tihbuai tam vang a ni. Pyrolysis temperature sang (Zn, boiling point = 907 °C) 45.46. Elemental analysis (EA) atanga a lan dan chuan pyrolysis temperature a san chuan N percentage a tlahniam a, O tamna hi boruak atanga molecular O2 adsorption vang a ni thei bawk. (Table S3) a ni. Cobalt content engemaw zatah chuan nanoparticles leh isolated coatoms te chu an awm dun a, chu chuan catalyst activity nasa takin a tipung a, a hnuaia kan sawi ang hian.
Co-SA/NPs@NC-T siam dan schematic diagram, T chu pyrolysis temperature (°C) a ni. b TEM thlalak a ni. c Co-SAs/NPs@NC-950 AC-HAADF-STEM thlalak. Single Co atom te chu circle sen hmanga chhinchhiah a ni. d Co-SA/NPs@NC-950-a EDS spectrum hmanga siam a ni.
Hriat tur pawimawh tak chu transmission electron microscopy (TEM) hmangin Co-SAs/NPs@NC-950-ah chauh cobalt nanoparticles (NPs) a vaiin 7.5 ± 1.7 nm a awm tih hmuhchhuah a ni ( Figure 2 b leh S8). Heng nanoparticle te hi graphite ang chi carbon nitrogen doped hmanga encapsulated an ni. Lattice fringe spacing 0.361 leh 0.201 nm hi graphitic carbon (002) leh metallic Co (111) particle te nen a inmil a ni. Chu bakah, high-angle aberration-corrected annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) hmangin Co-SAs/NPs@NC-950-a Co NPs te chu atomic cobalt tam takin a hual vel tih hmuhchhuah a ni bawk (Fig. 2c). Mahse, sample dang pahnih support-ah chuan atomically dispersed cobalt atom chauh hmuh a ni (Fig. S9). Energy dispersive spectroscopy (EDS) HAADF-STEM image hmangin Co-SAs/NPs@NC-950-a C, N, Co leh segregated Co NPs te chu a insem darh dan inang tlangin a lang (Fig. 2d). Heng result zawng zawng hian atomically dispersed Co center leh N-doped graphite ang chi carbon-a encapsulated nanoparticles te chu Co-SAs/NPs@NC-950 ah NC substrate ah hlawhtling takin an inzawm tih a tarlang a, isolated metal center chauh an inzawm thung.
Thil hmuhchhuah te valence state leh chemical composition chu X-ray photoelectron spectroscopy (XPS) hmangin an zirchiang a. Catalyst pathumte XPS spectra-ah chuan element Co, N, C leh O a awm tih hmuhchhuah a ni a, mahse Zn hi Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750-ah chauh a awm thung (Fig. 2). ). C10) a ni. Pyrolysis temperature a san chuan nitrogen chi hrang hrangte chu a nghet lo a, temperature sang zawkah NH3 leh NOx gas-ah an inthen darh avangin nitrogen awm zawng zawng a tlahniam thin (Table S4) Chutiang chuan carbon awm zawng zawng chu Co-SAs/NPs@NC-750 atanga Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-950 ah te a pung zauh zauh a (Figure S11 leh S12). Temperature sang zawka pyrolyzed sample hian nitrogen atom a nei tlem zawk a, hei hian Co-SAs/NPs@NC-950-a NC carrier awm zat chu sample dang aiin a tlem zawk tur a ni tihna a ni. Hei hian cobalt particle te sintering chak zawk a thlen thin. O 1s spectrum-ah hian peak pahnih C=O (531.6 eV) leh C–O (533.5 eV) a awm a (Figure S13) 48 . Figure 2a-a kan hmuh angin N 1s spectrum hi pyridine nitrogen N (398.4 eV), pyrrole N (401.1 eV), graphite N (402.3 eV) leh Co-N (399.2 eV) te characteristic peak paliah resolve theih a ni. Sample pathumteah hian Co-N bonds a awm vek a, hei hian N atom thenkhat chu monometallic site-ah an inzawm tih a tilang a, mahse a ziarang erawh a danglam hle Pyrolysis temperature sang zawk hman hian Co-SA/NPs@NC-750-a Co-N chi hrang hrang awm zat chu nasa takin a tihhniam thei a, Co-SAs/NPs@NC-850 leh Co 17.6%@ NC-950-ah 27.0%-ah a tlahniam thei a ni. in -CA/NPs, chu chu C content tihpun nen a inmil a ni (Fig. 3a), hei hian an Co-N coordination number chu a danglam thei a, a then chu C50 atom-in a thlak thei tih a tilang a ni. Zn 2p spectrum atanga a lan dan chuan he element hi Zn2+ angin a awm tam ber a ni. (Figure S14) 51. Co 2p spectrum hian 780.8 leh 796.1 eV-ah peak langsar tak pahnih a nei a, chungte chu Co 2p3/2 leh Co 2p1/2 te avanga lo awm a ni (Figure 3b). Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750 te nena khaikhin chuan Co-SAs/NPs@NC-950-a Co-N peak chu positive lam hawiin a inthlak a, hei hian surface-SAs/NPs@NC-950-a Co atom pakhat chauh hian electron depletion a nei sang zawk tih a tilang a, chu chuan oxidation state a ti sang zawk a ni. Hriat tur chu Co-SAs/NPs@NC-950 chauh hian 778.5 eV-ah zero-valent cobalt (Co0) peak chak lo tak an nei a, hei hian temperature sang taka SA cobalt aggregation atanga lo chhuak nanoparticles awmna a tichiang a ni.
a N 1s leh b Co 2p spectra te chu Co-SA/NPs@NC-T a ni. c XANES leh d FT-EXAFS spectra te chu Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750 te Co-K-edge a ni. e WT-EXAFS contour plot-ah hian Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850, leh Co-SAs/NPs@NC-750 te contour plot siam a ni. f Co-SA/NPs@NC-950 tan FT-EXAFS fitting curve hman a ni.
Chumi hnuah Time-locked X-ray absorption spectroscopy (XAS) hmangin sample buatsaih a Co species te electronic structure leh coordination environment te chu an zirchiang leh a ni. Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750-a cobalt valence state awmte chu Co-K edge (XANES) spectrum-a normalized near-field X-ray absorption hmanga hmuhchhuah a ni. Figure 3c-a kan hmuh angin sample pathumte kil bula absorption chu Co leh CoO foil inkarah a awm a, hei hian Co species-te valence state chu 0 atanga +253 inkar a nih thu a tarlang. Tin, Co-SAs/NPs@NC-950 atanga Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750 ah energy hniam zawka inthlak danglamna hmuh a ni a, hei hian Co-SAs/ NPs@NC-750 hian oxidation state a nei hniam zawk tih a tilang bawk. Order inthlak danglam rawh. Linear combination fitting result atanga a lan dan chuan Co-SAs/NPs@NC-950 Co valence state chu +0.642 a ni a, hei hi Co-SAs/NPs@NC-850 (+1.376) Co valence state aiin a hniam zawk a ni. Co-SA/NP @NC-750 (+1.402) te an ni. Heng results te hian Co-SAs/NPs@NC-950-a cobalt particles oxidation state average chu nasa takin a tlahniam tih a tilang a, hei hi XRD leh HADF-STEM result nen a inmil a, cobalt nanoparticles leh single cobalt te awm dun a nih avangin sawifiah theih a ni. . Co atoms 41. Co K-edge-a Fourier transform X-ray absorption fine structure (FT-EXAFS) spectrum atanga a lan dan chuan 1.32 Å-a main peak chu Co-N/Co-C shell-a mi a ni a, metallic Co -Co-a scattering path chu /NPs@NC-950-a hmuh Co-SAs Å-ah chauh 2.18-ah a awm thung (Fig. 3d). Chubakah, wavelet transform (WT) contour plot-ah chuan Co-N/Co-C-a attribute 6.7 Å-1-a intensity sang ber a lang a, Co-SAs/NPs@NC-950 chauh hian 8.8-a attribute intensity sang ber a lantir thung. Intensity maximum dang chu Co–Co bond-ah Å−1-ah a ni (Fig. 3e). Chu bakah, lessor-in EXAFS analysis a tihah chuan pyrolysis temperature 750, 850 leh 950 °C-ah Co-N coordination number chu 3.8, 3.2 leh 2.3 a ni a, Co-C coordination number chu 0. 0.9 leh 1.8 a ni (Fig. 3f, S15 leh Table S1). A bik takin, result hnuhnung ber hi Co-SAs/NPs@NC-950-a atomically dispersed CoN2C2 unit leh nanoparticles awm vang a ni thei. Chumi danglamna chu Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750-ah te chuan CoN3C leh CoN4 unit chauh a awm a ni. Pyrolysis temperature a san chuan CoN4 unit-a N atom te chu C atom-in a thlak zauh zauh a, cobalt CA aggregate-in nanoparticle a siam tih a chiang hle.
Tun hmaa zirchian tawh reaction condition hmangin preparation condition-in material hrang hrangte property a nghawng dan zirchian a ni (Fig. S16)17,49. Figure 4 a-a kan hmuh angin Co-SAs/NPs@NC-950 te activity hi Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750 te activity aiin a sang zawk tih a chiang hle. Hriat tur pawimawh tak chu Co sample buatsaih pathumte hian standard commercial precious metal catalyst (Pd/C leh Pt/C) nena khaikhin chuan performance tha zawk an nei vek a ni. Tin, Zn-ZIF-8 leh Zn-NC sample te hi formic acid dehydrogenation lam hawia inactive an nih avangin Zn particle te hi active site an ni lo tih a tilang a, mahse activity-a an nghawng chu a tlem hle. Hei bakah hian Co-SAs/NPs@NC-850 leh Co-SAs/NPs@NC-750 te activity chu 950°C-ah darkar 1 chhung secondary pyrolysis an nei a, mahse Co-SAs/NPs@NC-750 aiin a hniam zawk thung. @NC-950 (Fig. S17) ah hian a awm a. Heng thilte structurel characterization-ah hian re-pyrolyzed sample-ah hian Co nanoparticles a awm tih hmuhchhuah a ni a, mahse specific surface area hniam leh graphite ang chi carbon awm lohna hian Co-SAs/NPs@NC-950 nena khaikhin chuan activity a hniam zawk a ni (Figure S18–S20). Co precursor zat hrang hrang nei sample te activity pawh an khaikhin a, activity sang ber chu 3.5 mol addition-ah a lang (Table S6 leh Figure S21). Metal center hrang hrang siam dan hi pyrolysis boruak a hydrogen awm zat leh pyrolysis hun chhung hian a nghawng tih a chiang hle. Chuvangin Co-SAs/NPs@NC-950 material dangte chu formic acid dehydrogenation activity an neih leh neih loh an zirchiang a. Material zawng zawng hian performance moderate atanga tha tak tak a lantir vek a; mahse, an zinga pakhat mah Co-SAs/NPs@NC-950 aia tha an awm lo (Figure S22 leh S23). Material structural characterization atanga a lan dan chuan pyrolysis time a san chuan monoatomic Co-N positions content chu a tlahniam zauh zauh a, hei hi metal atom te nanoparticles-a an inzawm khawm vang a ni a, hei hian pyrolysis time 100-2000 nei sample te activity danglamna a sawifiah a ni. danglamna. 0.5 h, 1 h, leh 2 h (Figure S24–S28 leh Table S7).
Catalyst hrang hrang hmanga fuel assembly dehydrogenation neih chhunga gas volume leh hun hmuh zat graph. Reaction awm dan: PC (10 mmol, 377 μl), catalyst (30 mg), PC (6 ml), Tback: 110 °C, Tactical: 98 °C, 4 parts b Co-SAs/NPs@NC-950 ( 30 mg), solvent hrang hrang. c Organic solvent-a heterogeneous catalyst-te gas evolution rate 85–110 °C-a tehkhin. d Co-SA/NPs@NC-950 hmanga recycle hmanga thil tih dan tur experiment. Reaction dinhmun: FA (10 mmol, 377 μl), Co-SAs/NPs@NC-950 (30 mg), solvent (6 ml), Tset: 110 °C, Tactual: 98 °C, reaction cycle tin hi darkar khat chhung a ni Error bars hian active test pathum atanga standard deviation chhut chhuah a entir a ni.
A tlangpuiin FA dehydrogenation catalyst te efficiency hi reaction condition ah a innghat nasa hle a, a bik takin solvent hman danah a innghat nasa hle8,49. Tui solvent atana hman a nih chuan Co-SAs/NPs@NC-950 hian initial reaction rate sang ber a nei a, mahse deactivation a awm a, hei hi proton emaw H2O18 emaw active sites luah vang pawh a ni thei. Catalyst hi organic solvent 1,4-dioxane (DXA), n-butyl acetate (BAC), toluene (PhMe), triglyme leh cyclohexanone (CYC)-a test-naah pawh hmasawnna a awm lo a, propylene carbonate (PC) )-ah pawh a tha zawk tih hmuhchhuah a ni bawk (Fig. 4b leh Table S8). Chutiang bawkin additives triethylamine (NEt3) emaw sodium formate (HCCONa) emaw te hian catalyst performance ah nghawng tha tak a nei leh tawh lo (Figure S29). Optimal reaction condition hnuaiah chuan gas yield chu 1403.8 mL g−1 h−1 (Fig. S30) a tling a, hei hi a hmaa Co catalyst report zawng zawng (SAC17, 23, 24 telin) aiin a sang zawk tih a chiang hle. Experiment hrang hrangah chuan tuiah leh formate additives nena reaction te chu telh lovin dehydrogenation leh dehydration selectivities 99.96% thleng hmuh a ni (Table S9). Activation energy chhut chu 88.4 kJ/mol a ni a, hei hi noble metal catalyst activation energy nen tehkhin theih a ni (Figure S31 leh Table S10).
Chu bakah, formic acid dehydrogenation atana heterogeneous catalyst dang engemaw zat chu hetiang dinhmunah hian kan khaikhin bawk (Fig. 4c, tables S11 leh S12). Figure 3c-a kan hmuh angin Co-SAs/NPs@NC-950 gas siam chhuah rate hian heterogeneous base metal catalyst hriat lar ber berte aiin a tam zawk a, sumdawnna atana hman tur 5% Pd/C leh 5% Pd/C aiin vawi 10-in a sang zawk a ni. % Pt/C hmanga tihchak a ni.
(de)hydrogenation catalyst hmanna eng pawha thil pawimawh tak chu an stability hi a ni. Chuvangin Co-SAs/NPs@NC-950 hmangin recycling experiment hrang hrang an nei a. Figure 4 d-a kan hmuh angin, a zawna run nga chhung chu a tir lama material activity leh selectivity chu a danglam lo (Table S13 pawh en bawk ang che). Hun rei tak chhung test neih a ni a, darkar 72 chhungin gas siamchhuahna chu linear takin a pung a ni (Figure S32). Co-SA/NPs@NC-950 hman tawha cobalt awm zat chu 2.5 wt% a ni a, hei hi catalyst thar nen a inhnaih hle a, hei hian cobalt leaching langsar tak a awm lo tih a tilang (Table S14). Reaction hma leh hnuah pawh metal particle-te rawng inthlak danglamna emaw, aggregation emaw chiang tak hmuh tur a awm lo ( Figure S33 ). Hun rei tak chhunga experiment-a hman material-te AC-HAADF-STEM leh EDS-ah chuan atomic dispersion site-ah retention leh uniform dispersion a awm tih hmuhchhuah a ni a, structural changes lian tham a awm lo (Figure S34 leh S35). Co0 leh Co-N characteristic peaks te hi XPS-ah hian a la awm reng a, hei hian Co NPs leh individual metal sites te hi an awm dun tih a finfiah a, hei hian Co-SAs/NPs@NC-950 catalyst stability a nemnghet bawk (Figure S36).
Formic acid dehydrogenation-a mawhphurtu hmun active ber berte hriat theih nan, zirchianna hmasa atanga metal center pakhat chauh nei (CoN2C2) emaw Co NP emaw nei thil thlan bikte siam a ni Condition inang hnuaia formic acid dehydrogenation activity order hmuh chu Co-SAs/NPs@NC-950 > Co SA > Co NP (Table S15) a ni a, hei hian atomically dispersed CoN2C2 sites te chu NPs aiin an active zawk tih a tilang a ni. Reaction kinetics atanga a lan dan chuan hydrogen evolution hian first-order reaction kinetics a zui a, mahse cobalt content hrang hranga curve engemaw zat slope chu a inang lo a, hei hian kinetics chu formic acid chauh ni lovin, active site-ah pawh a innghat tih a tilang a ni (Fig. 2). C37) a ni. Kinetic study dang atanga a lan dan chuan, X-ray diffraction analysis-a cobalt metal peaks awm lohna ngaihtuah chuan, cobalt awm zat atanga thlirin reaction kinetic order chu level hniam zawk (2.5% aia tlem)-ah 1.02 a ni tih hmuhchhuah a ni a, hei hian monoatomic cobalt center-te insem darh dan inang tlang tak a nih thu a tarlang. puiber. active site (fig. S38 leh S39) a ni. Co particle awm zat 2.7% a thlen chuan r chu a pung nghal a, hei hian nanoparticle te hian atom pakhat zel nen an inzawm tha hle a, activity sang zawk an nei tih a tilang a ni. Co particle awm zat a pun zel chuan curve chu nonlinear a lo ni ta a, hei hi nanoparticle tamna leh monatomic position tlahniam nen a inzawm a ni. Chutiang chuan Co-SA/NPs@NC-950 LC dehydrogenation performance tihchangtlun chu metal site hrang hrang leh nanoparticles te thawhhona atanga lo chhuak a ni.
In- situ diffuse reflectance Fourier transform (in situ DRIFT) hmangin in-depth study an nei a, chu chuan an process chhunga reaction intermediates te chu an hmuchhuak a ni. Formic acid dah hnua sample te chu reaction temperature hrang hranga tihlum hnuah frequency set hnih hmuh a ni (Fig. 5a). HCOOH* characteristic peak pathum 1089, 1217 leh 1790 cm-1-ah a lang a, chungte chu out-of-plane CH π (CH) stretching vibration, CO ν (CO) stretching vibration leh C=O ν (C=O) stretching vibration, 54, 55 vang a ni. 1363 leh 1592 cm-1-a peak set dang chu symmetric OCO vibration νs(OCO) leh asymmetric OCO stretching vibration νas(OCO)33.56 HCOO* te nen a inmil a ni. Reaction a kal zel chuan HCOOH* leh HCOO* chi hrang hrangte relative peaks chu a bo zauh zauh thin. A tlangpuiin formic acid tihchhiatna hian step lian pathum a huam a, chungte chu: (I) active site-a formic acid adsorption, (II) formate emaw carboxylate pathway hmanga H paih chhuah, leh (III) adsorbed H pahnih inzawmkhawma hydrogen siam chhuah te. HCOO* leh COOH* te hi formate emaw carboxylate emaw pathways tehna atana key intermediate an ni57. Kan catalytic system hmang hian characteristic HCOO* peak chauh a lo lang a, hei hian formic acid decomposition chu formic acid pathway kaltlangin chauh a thleng tih a tilang a ni58. Hetiang bawk hian temperature hniam zawk 78 °C leh 88 °C-ah pawh hmuhchhuah a ni (fig. S40).
Co-SAs/NPs@NC-950 leh b Co SAs-a HCOOH dehydrogenation in situ DRIFT spectra. Legend hian on-site reaction times a tarlang a. c Hun kal zelah isotope labeling reagent hrang hrang hmanga gas volume siam danglamna. d Kinetic isotope hmanga nghawng a neih dan data.
Co-SA/NPs@NC-950-a synergistic effect zirchian nan a kaihhnawih material Co NP leh Co SA-ah pawh in situ DRIFT experiment ang chiah hi an ti a ( Figure 5 b leh S41). Material pahnih hian trend inang an nei a, mahse HCOOH* leh HCOO* te characteristic peaks te chu a inthlak danglam deuh a, hei hian Co NPs rawn luh hian monoatomic center electronic structure a tidanglam tih a tilang a ni. Co-SAs/NPs@NC-950 leh Co SA-ah te characteristic νas(OCO) peak a lang a, Co NPs-ah erawh a lang lo a, hei hian formic acid dah belh a nih atanga intermediate lo awm chu plane salt surface-a perpendicular monodentate formic acid a nih thu a tilang lehzual a ni. leh SA-ah active site angin a adsorb a ni 59 . Hriat tur chu characteristic peaks π(CH) leh ν(C = O)-a vibrations nasa taka tihpun a ni a, hei hian HCOOH* distortion a thlen niin a lang a, reaction pawh a ti awlsam hle. Chumi avang chuan Co-SAs/NPs@NC-a HCOOH* leh HCOO* te characteristic peaks chu min 2 chhung reaction hnuah a bo mai mai a, hei hi monometallic (6 min) leh nanoparticle-based catalyst (12 min) aiin a rang zawk a ni. . Heng result zawng zawng hian nanoparticle doping hian intermediates adsorption leh activation a tichak tih a nemnghet a, chu chuan a chunga kan rawt reaction te hi a ti chak zawk a ni.
Reaction pathway zirchian belh leh rate determining step (RDS) hriat chian nan KIE effect chu Co-SAs/NPs@NC-950 awmnaah an ti a. Hetah hian KIE zirchianna atan formic acid isotope hrang hrang HCOOH, HCOOD, DCOOH leh DCOOD te hman a ni. Figure 5c a kan hmuh angin dehydrogenation rate hi a hnuaia mi ang hian a tlahniam a: HCOOH > HCOOD > DCOOH > DCOOD. Tin, KHCOOH/KHCOOD, KHCOOH/KDCOOH, KHCOOD/KDCOOD leh KDCOOH/KDCOOD te value te chu 1.14, 1.71, 2.16 leh 1.44 anga chhut a ni bawk (Fig. 5d). Chutiang chuan HCOO*-a CH bond cleavage hian kH/kD value >1.5 a lantir a, hei hian kinetic effect lian tak a nei tih a tilang60,61 a, Co-SAs/NPs@NC-950-a HCOOH dehydrogenation RDS a entir niin a lang.
Hei bakah hian Doped nanoparticles te hian Co-SA intrinsic activity a nghawng dan hriatthiam nan DFT calculation an nei bawk. Co-SAs/NPs@NC leh Co-SA model te hi experiment tarlan leh a hmaa hnathawh tawh (Figs. 6a leh S42)52,62 atanga siam a ni. Geometric optimization hnuah Co6 nanoparticle te tak te (CoN2C2) monoatomic unit nena awm dun te chu an hmuchhuak a, Co-SA/NPs@NC-a Co-C leh Co-N bond sei zawng chu 1.87 Å leh 1.90 Å a ni tih an hmuchhuak a ni. , chu chu XAFS result nen a inmil hle. Calculated partial density of states (PDOS) atanga a lan dan chuan Co metal atom pakhat leh nanoparticle composite (Co-SAs/NPs@NC) te hian CoN2C2 nena khaikhin chuan Fermi level bulah hybridization sang zawk an nei a, hei hian HCOOH a siam a ni. Decomposed electron transfer hi a tha zawk ( Figure 6b leh S43). Co-SAs/NPs@NC leh Co-SA-te d-band center inmil chu -0.67 eV leh -0.80 eV-ah chhut a ni a, chung zingah chuan Co-SAs/NPs@NC tihpun chu 0.13 eV a ni a, hei hian NP rawn luh hnuah CoN2C2-a adapted electronic structure-in HCOO* particle-te adsorption a thlen theihna tura puitu a ni. Charge density danglamna hian CoN2C2 block leh nanoparticle vel ah electron cloud lian tak a awm tih a tarlang a, hei hian electron exchange avanga an inkarah inzawmna nghet tak a awm tih a tilang a ni. Bader charge analysis nena khaikhin chuan atomically dispersed Co hian Co-SA/NPs@NC-ah 1.064e a hloh a, Co SA-ah 0.796e a hloh tih hmuhchhuah a ni ( Figure S44 ). Heng results te hian nanoparticles te inzawmkhawm hian Co sites electron depletion a thlen a, chu chuan Co valence a tisang tih a tilang a, hei hi XPS result nen a inmil hle (Fig. 6c). Co-SAs/NPs@NC leh Co SA-a HCOO adsorption-a Co-O interaction characteristics chu crystalline orbital Hamiltonian group (COHP)63 chhiarin an zirchiang a. Figure 6 d-a kan hmuh angin -COHP negative leh positive value te hi antibonding state leh binding state nen a inmil a ni. HCOO (Co-carbonyl O HCOO*)-in a adsorb Co-O bond strength chu -COHP value te inzawmkhawmin an zir chiang a, Co-SAs/NPs@NC leh Co-SA te tan 3.51 leh 3.38 a ni. HCOOH adsorption pawhin hetiang bawk hian result a nei a: nanoparticle doping hnua -COHP integral value a san chuan Co-O bonding a sang tih a tilang a, chu chuan HCOO leh HCOOH activation a tichak a ni ( Figure S45 ).
Co-SA/NPs@NC-950 lattice hmanga siam a ni. b PDOS Co-SA/NP@NC-950 leh Co SA te an ni. c Co-SA/NPs@NC-950 leh Co-SA-a HCOOH adsorption charge density inang lo 3D isosurface. (d) Co-SA/NPs@NC-950 (khawi lamah nge) leh Co-SA (dinglamah) HCOO-in a adsorb Co-O bonds pCOHP. e Co-SA/NPs@NC-950 leh Co-SA-a HCOOH dehydrogenation reaction pathway.
Co-SA/NPs@NC dehydrogenation performance tha zawk hriatthiam nan reaction path leh energy te chu an zirchiang a. A bik takin FA dehydrogenation hian step panga a huam a, chung zingah chuan HCOOH chu HCOOH*-ah, HCOOH* chu HCOO* + H*-ah, HCOO* + H* chu 2H* + CO2*-ah, 2H* + CO2* chu 2H* + CO2-ah, leh H2-ah 2H*-ah a chantir (Fig. 6e). Catalyst surface-a formic acid molecule-te adsorption energy chu carboxylic oxygen kaltlangin hydroxyl oxygen kaltlangin aiin a hniam zawk a ni (Figure S46 leh S47). Chumi hnuah chuan energy a hniam zawk avangin adsorbate hian CH bond cleavage hmanga COOH* siam ai chuan OH bond cleavage hmangin HCOO* a siam duh zawk. Chutih rual chuan HCOO* hian monodentate adsorption a hmang a, hei hian bonds breaking leh CO2 leh H2 siamna a tichak a ni. Heng results te hi in situ DRIFT-a νas(OCO) peak awmna nen a inmil a, hei hian kan zirchiannaah hian FA degradation hi formate pathway kaltlangin a thleng tih a tilang lehzual a ni. KIE tehna atanga a lan dan chuan CH dissociation hian reaction step dang aiin reaction energy barrier a nei sang zawk a, RDS a entir tih hriat a pawimawh hle. Optimal Co-SAs/NPs@NC catalyst system-a energy barrier chu Co-SA (1.2 eV) aiin 0.86 eV-in a hniam zawk a, hei hian dehydrogenation efficiency pumpui nasa takin a tichangtlung a ni. Hriat tur pawimawh tak chu nanoparticle awmna hian atomically dispersed coactive sites electronic structure a tidanglam a, hei hian intermediates adsorption leh activation a tichak zual a, chu chuan reaction barrier a tihhniam bakah hydrogen siamchhuahna a tipung a ni.
A tawi zawngin, a vawi khatna atan hydrogen siamchhuahna catalyst-te catalytic performance chu nasa taka tihchangtlun theih a nih thu kan lantir a, chu chu highly distributed monometallic center leh nanoparticle te tak te nei material hmangin a ni. He concept hi cobalt-based single-metal catalyst nanoparticles (Co-SAs/NPs@NC) hmanga siam danglam, chubakah a kaihhnawih materials single-metal center (CoN2C2) emaw Co NPs chauh nei te siam chhuah hmangin a dik tih a chiang a ni. Material zawng zawng hi one-step pyrolysis method awlsam tak hmanga siam a ni. Structural analysis atanga a lan dan chuan catalyst tha ber (Co-SAs/NPs@NC-950) chu atomically dispersed CoN2C2 unit leh nanoparticle te tak te (7-8 nm) nitrogen leh graphite ang chi carbon doped te a ni. Gas productivity tha tak 1403.8 ml g-1 h-1 (H2:CO2 = 1.01:1), H2 leh CO selectivity 99.96% thleng a nei a, ni engemaw zat chhung chu constant activity a nei thei bawk. He catalyst activity hian Co SA leh Pd/C catalyst thenkhat activity aiin a let 4 leh 15 in a sang zawk a ni. In situ DRIFT experiment-ah chuan Co-SA nena khaikhin chuan Co-SAs/NPs@NC-950 hian HCOO* monodentate adsorption chak zawk a lantir a, hei hi formate pathway atan a pawimawh a, dopant nanoparticles hian HCOO* activation leh C–H acceleration a tichak thei a ni. Bond cleavage chu RDS a ni tih hmuhchhuah a ni. Theoretical calculation atanga a lan dan chuan Co NP doping hian interaction hmangin Co atom pakhat d-band center chu 0.13 eV in a tisang a, hei hian HCOOH* leh HCOO* intermediate te adsorption a tichak a, chu chuan Co SA tan reaction barrier chu 1.20 eV atanga 0 .86 eV ah a tihhniam a ni. A performance ropui tak takah mawhphurtu a ni.
A zau zawkin, he zirchianna hian single-atom metal catalyst thar design dan tur ngaihtuahna a pe a, metal center lian leh te, a lian leh te synergistic effect hmanga catalytic performance tihchangtlun dan hriatthiamna a ti hmasawn bawk. Hetiang approach hi awlsam takin catalytic system dang tam takah pawh hman theih a ni tih kan ring.
Co(NO3)2 6H2O (AP, 99%), Zn(NO3)2 6H2O (AP, 99%), 2-methylimidazole (98%), methanol (99.5%), propylene carbonate (PC, 99% ) ethanol (AR, 99.7%) te chu McLean, China atangin lei a ni a, a man hi a to hle a ni. Formic acid (HCOOH, 98%) hi China ram Rhawn atangin an lei a ni. Reagent zawng zawng hi tihthianghlim belh ngai lovin direct-in hman a ni a, ultrapure purification system hmangin ultrapure water siam a ni bawk. Pt/C (5% mass loading) leh Pd/C (5% mass loading) te chu Sigma-Aldrich atangin lei a ni.
CoZn-ZIF nanocrystals siam dan hi a hmaa hmanraw hman tawhte hmanga siam a ni a, siamthatna engemaw zat a awm bawk23,64. A hmasa berin Zn(NO3)2·6H2O (8.925 g) 30 mmol leh Co(NO3)2·6H2O (1.014 g) 3.5 mmol te chu an pawlh a, methanol 300 ml-ah an hmin a. Tichuan, 2-methylimidazole (9.853 g) 120 mmol chu methanol 100 ml-ah a hmin a, a chunga kan sawi takah hian kan dah a. Chumi hnuah chuan room temperature-ah darkar 24 chhung an stir a. A tawpah chuan 6429 g-ah centrifugation hmangin min 10 chhung an inthen a, methanol hmangin vawi thum uluk takin an silfai a. Powder lo chhuak chu hman hmain 60°C-ah vacuum-ah zan khat chhung an vawt a.
Co-SAs/NPs@NC-950 siam chhuah nan Dry CoZn-ZIF powder chu 950 °C-ah 1 h chhung gas flow 6% H2 + 94% Ar-ah pyrolyzed a ni a, heating rate chu 5 °C/min a ni. Chumi hnuah sample chu room temperature-ah tihlum a ni a, Co-SA/NPs@NC-950 hmuh a ni. Co-SAs/NPs@NC-850 emaw Co-SAs/NPs@NC-750 emaw tan chuan pyrolysis temperature chu 850 leh 750 °C-ah tihdanglam a ni. Sample buatsaih tawhte chu acid etching ang chi tih belh ngai lovin hman theih a ni.
TEM (transmission electron microscopy) tehna chu Thermo Fisher Titan Themis 60-300 “cube” microscope hmangin image aberration corrector leh 300 kV probe shaping lens hmanga teh a ni. HAADF-STEM experiment hi FEI Titan G2 leh FEI Titan Themis Z microscope hmanga probe leh image corrector hmanga thuam, leh DF4 four-segment detector hmanga tih a ni. EDS elemental mapping images pawh FEI Titan Themis Z microscope hmangin an la bawk. XPS analysis chu X-ray photoelectron spectrometer (Thermo Fisher model ESCALAB 250Xi) hmangin an enfiah a. XANES leh EXAFS Co K-edge spectra te chu XAFS-500 table (China Spectral Instruments Co., Ltd.) hmangin an la khawm a ni. Co awm zat chu atomic absorption spectroscopy (AAS) (PinAAcle900T) hmangin an chhut a. X-ray diffraction (XRD) spectra chu X-ray diffractometer (Bruker, Bruker D8 Advance, Germany) hmangin an record a. Nitrogen adsorption isotherm chu physical adsorption apparatus (Micromeritics, ASAP2020, USA) hmangin an siam a ni.
Dehydrogenation reaction hi argon atmosphere-ah standard Schlenk method angin boruak lakchhuah a ni. Reaction vessel chu chhuahsan a ni a, argon vawi 6 dah leh a ni. Condenser tui supply on la, catalyst (30 mg) leh solvent (6 ml) te dah la. Thermostat hmangin container chu duh ang temperature-ah dah la, minute 30 chhung equilibrate turin dah rawh. Chumi hnuah argon hnuaiah formic acid (10 mmol, 377 μL) chu reaction vessel-ah dah a ni. Reactor depressurize turin three-way burette valve chu her la, khar leh la, manual burette hmangin gas siam chhuah volume chu teh tan rawh (Figure S16). Reaction zawh hun chhung a mamawh hnuah gas sample chu GC analysis atan gas-tight syringe argon hmanga tihthianghlim hmangin lakkhawm a ni.
In situ DRIFT experiment hi Fourier transform infrared (FTIR) spectrometer (Thermo Fisher Scientific, Nicolet iS50) hmanga mercury cadmium telluride (MCT) detector hmanga thuam hmangin an ti a. Catalyst powder chu reaction cell (Harrick Scientific Products, Praying Mantis) ah dah a ni. Catalyst chu room temperature-a Ar stream (50 ml/min) hmanga treat hnuah, sample chu temperature pek angin an vawt a, chutah chuan HCOOH solution-ah Ar (50 ml/min) hmangin bubbled-in in-situ reaction cell-ah an theh lut a ni. reaction atan. Heterogeneous catalytic process te hi model a ni. Infrared spectra chu second 3.0 atanga darkar 1 inkar inkar ah record a ni.
HCOOH, DCOOH, HCOOD leh DCOOD te hi propylene carbonate-ah hian substrate atan hman a ni. A bak zawng chu HCOOH dehydrogenation procedure nen a inmil a ni.
First principles chhut dan chu Vienna Ab initio modeling package chhunga density functional theory framework hmangin an ti a (VASP 5.4.4) 65,66. CoN2C2 leh CoN2C2-Co6 te tan substrate atan graphene surface (5 × 5) transverse dimension 12.5 Å vel nei superunit cell hman a ni. Substrate layer inhnaih tak takte inzawmna a awm loh nan vacuum distance 15 Å aia tam dah belh a ni. Ion leh electron inkara inzawmna chu projected amplified wave (PAW) method hmanga sawifiah a ni65,67. Grimm68,69-a’n van der Waals correction nena a rawt Perdue-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) function chu hman a ni. Energy leh force zawng zawng atana convergence criteria chu 10−6 eV/atom leh 0.01 eV/Å a ni. Energy cutoff chu Monkhorst-Pack 2 × 2 × 1 K-point grid hmangin 600 eV-ah dah a ni. He model-a pseudopotential hman hi electronic configuration atanga C 2s22p2 state, N 2s22p3 state, Co 3d74s2 state, H 1 s1 state, leh O 2s22p4 state-ah siam a ni. Adsorption energy leh electron density danglamna hi adsorption emaw interface model angin adsorbed system energy atanga gas phase leh surface species te energy lakchhuah atanga chhut a ni70,71,72,73, Gibbs free energy correction hi DFT energy chu Gibbs free energy-a chantir nan hman a ni a, entropy leh zero point energy-a vibrational contribution te ngaihtuah tel a ni75. Ascending image-nudging elastic band (CI-NEB) method hmangin reaction transition state an zawng a76.
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