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Hydrogen thiamnak tthanchonak cu a hringmi sipuazi hrampi ah a um. Hydrogen chiahnak tuah khawhnak ding caah a herhmi thil pakhat in, hydrogenation (de)hydrogenation reaction caah a cawlcangmi le a fekmi thilri pawl an herh. Atu tiang ahcun, hi hmun hi a man a fakmi thir mansung hmannak nih a uk. Hika ah, a man a fawimi cobalt-based catalyst (Co-SAs/NPs@NC) thar pakhat kan chuahpi i cu ah cun a ttha ngaimi formic acid dehydrogenation hmuh khawhnak ding caah a ttha ngaimi thir pakhat lawng a ummi hmun pawl cu a ttha ngaimi nanoparticles he fonh an si. Atom in aa ṭhekmi CoN2C2 units le 7-8 nm a nganmi nanoparticles a ṭha bikmi thilri hmangin, propylene carbonate kha cawhmi ah hmangin, 1403.8 ml g-1 h-1 a ṭha tukmi gas chuah khawh a si, cun 5 cycle hnu ah sunghnak a um lo. cawlcanghnak, cucu chawlehnak Pd/C nakin a let 15 in a ttha deuh. In situ hneksaknak hneksaknak nih a langhter mi cu, aa pehtlaimi thir atom pakhat le nanoparticle catalysts he tahchunh tikah, Co-SAs/NPs@NC nih a biapi mi monodentate karlak HCOO* laknak le riantuannak a thanchoter, cucaah a hnu ah CH pehtlaihnak tthennak a thanchoter. Theory tuaktannak nih a langhter ning ahcun cobalt nanoparticles fonhnak nih Co atom pakhat i d-band center kha a cawlcangmi hmun ah a thlen, cucaah HCOO* karlak i carbonyl O le Co center karlak i pehtlaihnak a ṭhanchoter, cucaah thazaang dawnkhantu kha a zorter.
Hydrogen cu a tu lio vawleicung thazaang thlennak caah a biapi mi thazaang phurtu ah ruah a si i carbon neutrality hmuh khawhnak caah a biapi mi hruaitu a si kho1. A kang khomi le a tlawmmi a si caah, a himmi le ttha tein hydrogen chiahnak le phurhnak cu hydrogen sipuazi tuah khawhnak ah a biapi tukmi thil an si2,3,4. Chemical reaction hmangin hydrogen a chiah i a chuahtertu ti bantuk organic hydrogen carriers (LOHCs) cu a phichuak ah an chuahpi. Molecular hydrogen he tahchunh ahcun, cu bantuk thilri (methanol, toluene, dibenzyltoluene, tbk.) cu hman a fawi i a fawi5,6,7. Hlanlio LOHC phunphun lakah, formic acid (FA) cu a tlawm deuhmi fahnak (LD50: 1.8 g/kg) le H2 tthawnnak 53 g/L asiloah 4.4 wt% a ngei. Hngalh awk ngai a simi cu, FA lawnglawng hi aa tlakmi catalysts a um tikah a nemmi thil sining tangah hydrogen a chiah khawhmi le a chuahter khomi LOHC a si, cucaah lenglei thazaang luhternak nganpi a herh lo1,8,9. A ngaingai ti ahcun, formic acid ti chuahnak caah thir ttha tampi an ser cang, tahchunhnak ah, palladium-based catalys cu a man a fawimi thir catalys nakin a let 50-200 in a cawlcang deuh10,11,12. Sihmanhsehlaw, a cawlcangmi thir man kha na tuak ahcun, tahchunhnak ah, palladium cu a let 1000 nak tam a man a fak deuh.
Cobalt, A cawlcang tukmi le a fekmi aa dangmi thir thlennak kawlnak nih sianginn le riantuannak ah hlathlaitu tampi lungthin a lak peng hna13,14,15.
Mo le Co cung ah hram bunhmi a man a fawimi catalysts, cun noble/base metal alloys,14,16 in sermi nanocatalysts hna cu FA dehydrogenation caah sermi an si ko nain, an i thlennak chungah tlawmpal in an riantuan lonak cu thir, CO2, le H2O hna i an riantuannak hmun kha proton nih a lak caah hrial khawh a si lo. asiloah formate anions (HCOO-), FA thurhnawmhnak, thil hme tete i fonhnak le CO fahnak a chuahter khomi17,18. Kanmah le midang nih naite ah khan single-atom catalysts (SACs) cu a tthawngmi CoIINx hmunhma hna he a cawlcangmi hmunhma hna he nanoparticles17,19,20,21,22,23,24 he tahchunh tikah formic acid dehydrogenation i a tthatnak le acid doh khawhnak a tthanchoter ti kha kan langhter. Hi Co-NC thilri hna ah hin, N atoms nih FA deprotonation thanchoternak caah hmunpi ah rian an ttuan i cu lio ah Co atom laifang he i bawmhnak thawngin dirhmun tthatnak an thanchoter, cu lio ah Co atoms nih H laknak hmun an pek i CH22 tthencheunak an thanchoter, 25,26. Vanchiat ah, hi thilri hna i an cawlcanghnak le an fekmi cu chanthar aa khatmi le aa khat lomi thir thilri hna he an i hlat rih (Fig. 1) 13 .
Ni ceunak asiloah thli tibantuk tharchuah khawhmi thilri hna in a chuakmi thazaang tam deuh cu ti electrolysis in chuah khawh a si. A chuakmi hydrogen cu LOHC hmangin chiah khawh a si, a hydrogenation le dehydrogenation cu a kir khawhmi ti a si. Dehydrogenation step ah, a chuakmi cu hydrogen lawng a si, cun a phorhtu ti cu a hramthawk dirhmun ah a kir tthan i hydrogenated a si tthan. Hydrogen cu a donghnak ah gas dawr, battery, riantuannak inn le a dangdang ah hman khawh a si.
Nai ah, SACs tthenkhat hna i an chunglei cawlcanghnak cu thir atom phunphun asiloah nanoparticles (NPs) asiloah nanoclusters (NCs) nih a pekmi thir hmun dangdang hna an um tikah a tthancho khawh tiah report an tuah27,28. Mah nih hin a tanglei thilri hna kha a hnu deuh in a lak khawh hna i a cawlcangter khawh hna, cun monotomic hmunhma hna i an geometry le electronic sining hna kha a thlen khawh hna. Cuticun, substrate laknak/riantuannak cu a ttha bik in tuah khawh a si, a ttha deuhmi a dihlak in catalytic tthatnak a pek29,30. Mah nih hin hybrid active sites he aa tlakmi catalytic thilri sernak ruahnak a kan pek. A tthanchomi SACs nih catalytic hmannak phunphun ah thil ti khawhnak nganpi an langhter ko nain31,32,33,34,35,36, kan theih khawh tawk ahcun, hydrogen chiahnak ah an riantuannak cu a fiang lo. Hi kong he pehtlai in, a fiangmi nanoparticles le thir center pakhat cio aa telmi cobalt-based hybrid catalysts (Co-SAs/NPs@NCs) sernak caah a phunphun le a fekmi strategy pakhat kan thanh. A ttha bikmi Co-SAs/NPs@NC nih a ttha tukmi formic acid dehydrogenation riantuannak an langhter, cucu non-noble nanostructured catalysts (CoNx, single cobalt atoms, cobalt@NC le γ-Mo2N tibantuk) le noble metal catalysts hmanh nakin a ttha deuh. Active catalysts hna i an hmunhma sining le DFT tuaktannak nih a langhter mi cu thir hmunhma pakhat cio nih active hmunhma ah rian an ttuan, cun atu lio thil sernak i nanoparticles nih Co atoms d-band center kha a ṭhanchoter, HCOO* i laknak le riantuannak kha a ṭhanchoter, cucaah lehrulhnak i thazaang khamnak kha a zorter. .
Zeolite imidazolate frameworks (ZIFs) cu thir phunphun bawmhchanhnak caah nitrogen-doped carbon thilri (metal-NC catalysts) caah a ttha tein a fiantermi a tthenthum a ngeimi a hramthawknak a si37,38. Cucaah, Co(NO3)2 le Zn(NO3)2 cu methanol chung i 2-methylimidazole he an i fonh i aa tlakmi thir phunphun an ser. Centrifugation le hnimh hnu ah, CoZn-ZIF cu 6% H2 le 94% Ar thli lakah lumternak aa dangmi (750-950 °C) ah pyrolyze a si. A tanglei hmanthlak ah langhter bantuk in, a chuakmi thilri hna cu a cawlcangmi hmun sining aa dangmi an ngei i Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 tiah min an sak hna (Figure 2a). ) . Synthesis tuahnak ah a biapi mi step cheukhat hna i a bik in hneksaknak zohfelnak hna cu hmanthlak 1 le 2 ah fiang tein langhter an si. C1-C3. Catalyst a tthanchonak zohfel awkah aa thleng khomi lumnak X-ray thlennak (VTXRD) tuah a si. Pyrolysis lumnak nih 650 °C a phak tikah, ZIF (Fig. S4) 39 i a tlarimi crystal sining a rawhnak ruangah XRD pattern cu a thlen ngaingai. Lungthawhnak a karh chin lengmang tikah, Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 XRD pattern ah 20–30° le 40–50° ah a kau ngaimi tlang pahnih an lang, cu nih cun amorphous carbon sang bik a aiawh (Fig. C5). 40. 44.2°, 51.5° le 75.8°, metallic cobalt (JCPDS #15-0806) ah aa telmi, le 26.2°, graphic carbon (JCPDS # 41-1487) ah aa telmi sining sang bik pathum lawng hmuh a si ti kha hngalh awk tlak a si. Co-SAs/NPs@NC-950 X-ray spectrum nih catalyst cung ah graphite-like encapsulated cobalt nanoparticles a um ti a langhter41,42,43,44. Raman spectrum nih a langhter mi cu Co-SAs/NPs@NC-950 cu a dang sample nakin a tthawng deuhmi le a kau deuhmi D le G tlangpar a ngeimi a lo, cu nih cun graphitization a sang deuhmi a langhter ( Figure S6 ). Cun, Co-SAs/NPs@NC-950 nih a dang sample nakin a sang deuhmi Brunner-Emmett-Taylor (BET) cunglei kauhnak le pore volume (1261 m2 g-1 le 0.37 cm3 g-1) a langhter i ZIF tam deuh cu NC chuahkehnak an si. thilri (Figure S7 le Table S1). Atomic absorption spectroscopy (AAS) nih Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 le Co-SAs/NPs@ hna i cobalt dat cu 2.69 wt.%, 2.74 wt.% le 2.73 wt.% a si ti a langhter. NC-750 ciocio (Table S2). Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 chung i Zn dat cu zaangfah tein a karh, cucu Zn units tlawmternak le tthawnnak a karhmi ruangah a si. Pyrolysis lumternak (Zn, a linnak hmun = 907 °C) 45.46. Elemental hlathlainak (EA) nih a langhter ning ahcun N zatuak cu pyrolysis lumnak a karh tikah a zor, cun O a tammi cu thli he aa tongmi molecular O2 nih a lakmi ruangah a si kho men. (Table S3). Cobalt tlawmpal ah, nanoparticles le a dang tein a ummi coatoms pawl cu an um tti, cu nih cun a tanglei ah kan i ruahmi bantukin catalyst cawlcanghnak a karhter ngaingai.
Co-SA/NPs@NC-T sernak hmanthlak, T cu pyrolysis lumternak (°C) a si. b TEM hmanthlak. c Co-SAs/NPs@NC-950 AC-HAADF-STEM hmanthlak. Co atom pakhat lawng cu a senmi kuang in hmelchunh an si. d Co-SA/NPs@NC-950 EDS spectrum.
A hlei in, transmission electron microscopy (TEM) nih Co-SAs/NPs@NC-950 ( Figures 2 b le S8) lawng ah a tlangpi in 7.5 ± 1.7 nm a simi cobalt nanoparticles (NPs) phunphun an um ti a langhter. Hi nanoparticles pawl cu nitrogen he cawhmi graphite bantuk carbon in an khumh hna. Lattice fringe spacing 0.361 le 0.201 nm cu graphitic carbon (002) le metallic Co (111) particles he aa tlak. Cun, high-angle aberration-corrected annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) nih Co-SAs/NPs@NC-950 chung i Co NPs cu a tammi atomic cobalt nih a kulh hna ti a langhter (Fig. 2c). Sihmanhsehlaw, a dang sample pahnih dirkamhnak ah atom in aa ṭhekmi cobalt atom lawng hmuh khawh a si (Fig. S9). Energy dispersive spectroscopy (EDS) HAADF-STEM hmanthlak nih Co-SAs/NPs@NC-950 (Fig. 2d) ah C, N, Co le tthencheuhmi Co NPs hna i aa khatmi phawtzamhnak a langhter. Hi hmuhmi vialte nih hin atom in aa ṭhekmi Co center le N-doped graphite-bantuk carbon ah aa khumhmi nanoparticles hna cu Co-SAs/NPs@NC-950 chung i NC substrates ah hlawhtling tein an i peh, cu lioah thir center lawng aa ṭhen.
Hmuhchuahmi thilri hna i an valence dirhmun le chemical composition cu X-ray photoelectron spectroscopy (XPS) in hlathlainak an tuah. Catalysts pathum hna i XPS spectra nih Co, N, C le O timi thilri an um ti a langhter, asinain Zn cu Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 lawng ah a um (Fig. 2). ). C10). Pyrolysis lumnak a karh tikah, nitrogen phun pawl cu an dirhmun a fek lo i lumnak sang deuh ah NH3 le NOx gas ah an rawk tikah nitrogen dihlak a zor (Table S4) 47 . Cucaah, carbon dihlak cu Co-SAs/NPs@NC-750 in Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-950 tiang zaangfah tein a karh (Figure S11 le S12). Lungthawhnak sang deuh ah pyrolyze tuahmi sample nih nitrogen atoms a tlawm deuh, cucu Co-SAs/NPs@NC-950 chung i NC carriers zat cu sample dang nakin a tlawm deuh awk a si tinak a si. Mah nih hin cobalt tlawmpal hna kha a tthawng deuhmi sintering a chuahter. O 1s spectrum nih C=O (531.6 eV) le C–O (533.5 eV) sangbik pahnih a langhter, pakhat hnu pakhat (Figure S13) 48 . Figure 2a ah langhter bantuk in, N 1s spectrum cu pyridine nitrogen N (398.4 eV), pyrrole N (401.1 eV), graphite N (402.3 eV) le Co-N (399.2 eV) timi sining sangbik pali ah tthen khawh a si. Co-N bonds cu sample pathum ah an um, cu nih cun N atom cheukhat cu monometallic hmun ah an i pehtlaih ti a langhter, asinain an sining cu aa dang ngaingai49. Pyrolysis lumnak sang deuh hmannak nih Co-N phun pawl kha Co-SA/NPs@NC-750 ah 43.7% in Co-SAs/NPs@NC-850 le Co 17.6%@ NC-950 ah 27.0% tiang a zorter khawh. -CA/NPs ah, cucu C dat a karhmi he aa tlak (Fig. 3a), an Co-N pehtlaihnak nambar cu aa thleng kho i C50 atoms nih a cheuchum in a thlen khawh ti a langhter. Zn 2p spectrum nih a langhter mi cu hi thilri hi Zn2+ phun in a um deuh. (Figure S14) 51. Co 2p spectrum nih 780.8 le 796.1 eV ah a langmi tlang sang pahnih a langhter, cu hna cu Co 2p3/2 le Co 2p1/2 ah an i tel (Figure 3b). Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 he tahchunh tikah, Co-SAs/NPs@NC-950 chung i Co-N sangbik cu a ttha lei ah aa thlen, cu nih cun -SAs/NPs@NC-950 cunglei ah Co atom pakhat lawng nih electron tlawmternak a sang deuh ti a langhter, cu nih cun oxition dirhmun sang deuh a chuahter. Co-SAs/NPs@NC-950 lawng nih 778.5 eV ah zero-valent cobalt (Co0) a derthawmmi a langhter ti kha hngalh awk tlak a si, cucu lumnak sang ah SA cobalt fonhnak in a chuakmi nanoparticles a um ti a langhter.
a N 1s le b Co 2p Co-SA/NPs@NC-T spectra. c XANES le d FT-EXAFS spectra of Co-K-edge of Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750. e WT-EXAFS contour plots of Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850, le Co-SAs/NPs@NC-750. f FT-EXAFS Co-SA/NPs@NC-950 caah aa tlakmi tlukruannak.
Time-locked X-ray absorption spectroscopy (XAS) cu timhcia mi sample chung i Co phun hna i electronic sining le pehtlaihnak pawngkam hlathlainak caah hman a si. Co-SAs/NPs@NC-950, Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 ah Cobalt valence dirhmun cu Co-K edge (XANES) spectrum ah a tlarimi near-field X-ray laknak nih a langhtermi a kam sining. Figure 3c ah hmuh khawhmi bantuk in, sample pathum hna i an kam pawng i laknak cu Co le CoO foil karlak ah a um, cucu Co phun hna i an valence dirhmun cu 0 in +253 karlak a si ti a langhter. Cun, Co-SAs/NPs@NC-950 in Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 ah a niam deuhmi thazaang lei thlennak hmuh a si, cucu Co-SAs/ NPs@NC-750 nih a niam deuhmi oxidation dirhmun a ngeih ti a langhter. A hnulei zulhnak. Linear combination fitting results ning in, Co-SAs/NPs@NC-950 i Co valence dirhmun cu +0.642 a si lai tiah an ruah, cucu Co-SAs/NPs@NC-850 i Co valence dirhmun (+1.376) nakin a niam deuh. Co-SA/NP @NC-750 (+1.402). Hi hmuhmi nih hin Co-SAs/NPs@NC-950 chung i cobalt particles hna i a tlangpi in oxidation dirhmun cu a zor ngaingai ti a langhter, cucu XRD le HADF-STEM hmuhmi he aa tlak i cobalt nanoparticles le cobalt pakhat lawng an umttinak in a fianter khawh. . Co atoms 41. Co K-edge i Fourier transform X-ray absorption fine structure (FT-EXAFS) spectrum nih a langhter mi cu 1.32 Å ah a ummi a sang bik cu Co-N/Co-C shell ah aa tel, cu lio ah thir Co -Co a tthencheunak lam cu 2.18 ah a um i Co-SAs Å@NPs lawng ah hmuh khawh a si (Fig.5s. 3d). Cun, wavelet thlennak (WT) contour plot nih Co-N/Co-C he aa pehtlaimi 6.7 Å-1 ah a sang bik thazaang a langhter, cu lio ah Co-SAs/NPs@NC-950 lawng nih 8.8 ah aa hngatmi a sang bik thazaang a langhter. A dang thazaang sangbik cu Co-Co pehtlaihnak (Fig. 3e) ah Å−1 ah a si. Cun, EXAFS hlathlainak nih lessor nih a tuahmi nih a langhter mi cu pyrolysis lumnak 750, 850 le 950 °C ah, Co-N pehtlaihnak nambar cu 3.8, 3.2 le 2.3 an si, cun Co-C pehtlaihnak nambar cu 0. 0.9 le 1.8 an si (Fig. 3. Sf3, Table 15). A bik in, a donghnak bik hmuhmi cu Co-SAs/NPs@NC-950 ah atom in aa ṭhekmi CoN2C2 unit le nanoparticles an um caah a si kho. Cu he aa dang in, Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 ah, CoN3C le CoN4 unit lawng an um. Pyrolysis lumnak a karh tikah, CoN4 unit chung i N atom pawl cu C atom nih zaangfah tein an thlen hna, cun cobalt CA fonh in nanoparticles an ser ti cu a fiang ko.
A hlan ah hlathlainak tuahmi lehrulhnak dirhmun hna cu thilri phunphun sining cung ah timhtuahnak dirhmun nih a chuahpimi thil sining hlathlainak caah hman a si (Fig. S16)17,49. Figure 4 a ah hmuh khawhmi bantuk in, Co-SAs/NPs@NC-950 cawlcanghnak cu Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 nakin a sang deuh ngaingai. Hngalh awk ngai a simi cu, timhcia mi Co sample pathum vialte nih chawlehnak ah hmanmi thir mansung catalysts (Pd/C le Pt/C) he tahchunh tikah a ttha deuhmi riantuannak an langhter. Cun, Zn-ZIF-8 le Zn-NC sample pawl cu formic acid dehydrogenation lei ah an cawlcang lo, cu nih cun Zn particles cu a cawlcangmi hmun an si lo ti a langhter, asinain an cawlcanghnak cungah an thlennak cu zeihmanh a si lo. Cun, Co-SAs/NPs@NC-850 le Co-SAs/NPs@NC-750 cawlcanghnak cu 950°C ah suimilam 1 chung a pahnihnak pyrolysis an tuah, asinain Co-SAs/NPs@NC-750 nakin a niam deuh. @NC-950 (Fig. S17). Hi thilri hna i an sining zohfelnak nih re-pyrolyzed sample ah Co nanoparticles a um ti a langhter, asinain a tlawmmi a hleiin a cunglei hmunhma le graphite-bantuk carbon a um lonak nih Co-SAs/NPs@NC-950 he tahchunh tikah cawlcanghnak a niam deuhmi a chuahter (Figure S18–S20). Co precursor zat aa dangmi sample hna cawlcanghnak zong tahchunh a si, a sang bik cawlcanghnak cu 3.5 mol chapnak ah langhter a si (Table S6 le Figure S21). Thir center phunphun sernak cu pyrolysis thli chung i hydrogen dat le pyrolysis caan nih a thlen ti cu a fiang ko. Cucaah, a dang Co-SAs/NPs@NC-950 thilri pawl cu formic acid dehydrogenation cawlcanghnak caah an zohfel hna. Thilri vialte nih a tlawm in a ttha tukmi riantuannak an langhter; sihmanhsehlaw, pakhat hmanh Co-SAs/NPs@NC-950 nakin an ttha deuh lo (Figure S22 le S23). Thilri sining langhternak nih a langhter mi cu, pyrolysis caan a karh tikah, monoatomic Co-N dirhmun hna cu thir atom pawl kha nanoparticles ah an i fonh caah a zor thluahmah, cucu pyrolysis caan 100-2000 a ngeimi sample karlak cawlcanghnak aa dannak kha a fianter. dannak. 0.5 h, 1 h, le 2 h (Hmanthlak S24-S28 le Table S7).
Catalyst phunphun hmangin meihol fonhmi ti chuahnak ah hmuhmi gas zat le caan hmanthlak. Reaction dirhmun: 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), thilri phunphun. c 85-110 °C ah a ummi thilnung hna ah aa dangmi thilri hna i gas thlennak rate tahchunhnak. d Co-SA/NPs@NC-950 hman tthannak hneksaknak. Reaction dirhmun: FA (10 mmol, 377 μl), Co-SAs/NPs@NC-950 (30 mg), solvent (6 ml), Tset: 110 °C, Tactual: 98 °C, reaction cycle pakhat cio cu suimilam pakhat a rau. Palhnak tlawmpal nih a cawlcangmi hneksaknak pathum in tuakmi tlukruannak a langhter.
A tlangpi in, FA dehydrogenation catalysts hna an tthatnak cu thlennak dirhmun cungah aa hngat ngaingai, a hlei in hmanmi thlennak thilri cungah aa hngat8,49. Ti kha cawhmi ah hman tikah, Co-SAs/NPs@NC-950 nih a hramthawk ah a sang bikmi lehrulhnak a langhter, asinain riantuan lonak a chuak, protons asiloah H2O18 nih a cawlcangmi hmun a lak caah a si kho men. 1,4-dioxane (DXA), n-butyl acetate (BAC), toluene (PhMe), triglyme le cyclohexanone (CYC) tibantuk organic solvents ah catalyst hneksaknak zong nih tthanchonak zeihmanh a langhter lo, cun propylene carbonate (PC) zongah (Fig. 4b le Table S8). Cu bantuk cun, triethylamine (NEt3) asiloah sodium formate (HCCONa) tibantuk chapmi hna nih catalyst riantuan ning ah a ttha mi thlennak an ngei ti lo (Figure S29). A ttha bikmi thlennak dirhmun tangah, gas chuahmi cu 1403.8 mL g−1 h−1 (Fig. S30) a phan, cucu a hlan ah report tuahmi Co catalysts vialte (SAC17, 23, 24 telh chih in) nakin a sang deuh ngaingai. Hneksaknak phunphun ah, ti le formate chapmi he aa pehtlaimi thil hna telh loin, ti tlawmternak le ti tlawmternak thimnak 99.96% tiang hmuh khawh a si (Table S9). Tuakmi riantuannak thazaang cu 88.4 kJ/mol a si, cucu thir sunglawi thlennak thazaang he tahchunh khawh a si (Figure S31 le Table S10).
Cun, aa lo ngaimi thil sining tangah formic acid dehydrogenation caah a dang aa dangmi thilri tampi kan tahchunh hna (Fig. 4c, tables S11 le S12). Figure 3c ah langhter bantuk in, Co-SAs/NPs@NC-950 i gas chuah khawhnak rate cu theihmi heterogeneous base metal catalysts tam deuh nakin a tam deuh i chawlehnak 5% Pd/C le 5% Pd/C nakin a let 15 le a let 15 in a sang deuh, pakhat cio in, voikhat ah 10 in. % Pt/C catalyst.
(De)hydrogenation catalysts hmannak ah a biapi mi thil pakhat cu an fekmi a si. Cucaah, Co-SAs/NPs@NC-950 hmangin hman tthannak hneksaknak phunphun an tuah. Figure 4 d ah hmuh khawhmi bantuk in, thilri i a hramthawk cawlcanghnak le thim khawhnak cu a pehzulhmi panga chung ah aa thleng lo (Table S13 zong zoh). Caan saupi hneksaknak an tuah i suimilam 72 chung ah gas chuahmi cu a tlarimi in a karh (Figure S32). Co-SA/NPs@NC-950 hmanmi ah cobalt a ummi cu 2.5 wt% a si, cucu a thar in catalyst he aa naih tuk, cu nih cun cobalt a chuahnak a um lo ti a langhter (Table S14). Reaction tuah hlan le tuah hnu ah a fiangmi rong thlennak asiloah thir tlawmpal aa fonhmi hmuh a si lo ( Figure S33 ). Caan saupi hneksaknak ah hmanmi thilri hna i AC-HAADF-STEM le EDS nih atom tthencheunak hmun hna i tlaih pengnak le aa khatmi tthencheunak le a biapi mi sining thlennak a langhter lo (Figures S34 le S35). Co0 le Co-N i an sining sangbik hna cu XPS ah an um rih, Co NPs le thir hmun pakhat cio an um ti a langhter, cu nih cun Co-SAs/NPs@NC-950 catalyst a fekmi zong a fehter (Figure S36).
Formic acid dehydrogenation caah tuanvo a ngeimi a cawlcang bikmi hmun pawl hngalh khawhnak ding caah, thir center pakhat lawng a ngeimi thilri thim (CoN2C2) asiloah Co NP cu a hlan hlathlainak17 cung ah hram bunh in timhtuahnak an ngei. Cu bantuk thil sining tangah hmuhmi formic acid dehydrogenation cawlcanghnak ningcang cu Co-SAs/NPs@NC-950 > Co SA > Co NP (Table S15) a si, cucu atom in aa ṭhekmi CoN2C2 hmun pawl cu NPs nakin an cawlcang deuh ti a langhter. Reaction kinetics nih a langhter mi cu hydrogen evolution nih a hmasa bik reaction kinetics a zulh, asinain cobalt aa dangmi ah a ummi curve zeimawzat i an tliknak cu aa khat lo, cu nih cun kinetics cu formic acid lawng si loin a cawlcangmi hmun cungah aa hngatmi a si ti a langhter (Fig. 2). C37). A dang kinetic hlathlainak nih a langhter mi cu, X-ray diffraction hlathlainak ah cobalt thir sangbik a um lo caah, cobalt dat he pehtlai in thlennak i kinetic order cu a niam deuhmi (2.5% nak tlawm deuh) ah 1.02 a si ti hmuh a si, cucu monoatomic cobalt center hna i aa khat dihmi tthencheunak a langhter. a biapimi. a cawlcangmi hmun (figs. S38 le S39). Co particles a tlawmtam nih 2.7% a phak tikah, r cu ruahlopi in a karh, cucu nanoparticles nih atom pakhat cio he ttha tein an i pehtlaih i cawlcanghnak sang deuh an hmuh ti a langhter. Co particles a karh chin lengmang tikah, a tliknak cu a tlarimi a si lo, cucu nanoparticles a karh i monotomic dirhmun a zor he aa pehtlai. Cucaah, Co-SA/NPs@NC-950 i a tthanchomi LC dehydrogenation riantuannak cu thir hmun pakhat cio le nanoparticles hna i bawmhnak ziaza in a chuakmi a si.
A thukmi hlathlainak cu in situ diffuse reflectance Fourier transform (in situ DRIFT) hmangin tuah a si i, cu nih cun a kalning ah a chuakmi thil karlak thilri pawl kha a hngalh khawh. Formic acid chap hnu ah sample pawl kha aa dangmi thlennak lumnak ah lumter hnu ah, frequency phun hnih hmuh a si (Fig. 5a). HCOOH* i a sining sang bik pathum cu 1089, 1217 le 1790 cm-1 ah an lang, cu hna cu lenglei CH π (CH) hlernak hninhnak, CO ν (CO) hlernak hninhnak le C=O ν (C=O) hlernak hninhnonak, 54, 54 ah an si. A dang 1363 le 1592 cm-1 ah a ummi tlang sang hna cu aa tlukmi OCO hninhnak νs(OCO) le aa tluk lomi OCO hninhnak νas(OCO)33.56 HCOO* he aa tlak. Reaction a kal tikah, HCOOH* le HCOO* phun hna i an i pehtlaihnak sangbik hna cu zaangfah tein an tlau. A tlangpi in chim ahcun, formic acid rawhnak ah hin a biapi bikmi step pathum aa tel: (I) a cawlcangmi hmun ah formic acid laknak, (II) formate asiloah carboxylate lam in H chuahnak, le (III) hydrogen chuahternak caah H pahnih fonhnak. HCOO* le COOH* cu formate asiloah carboxylate lamthluan hngalh khawhnak ah a biapi mi karlak thilri an si, anmah le anmah57. Kan catalytic system hmangin, sining HCOO* peak lawng a lang, cu nih cun formic acid rawhnak cu formic acid lam58 lawng in a cang ti a langhter. Cu bantuk hmuhtonnak cu 78 °C le 88 °C a niam deuhmi lumnak ah tuah a si (fig. S40).
Co-SAs/NPs@NC-950 le b Co SAs cung i HCOOH ti tlawmternak in situ DRIFT spectra. Tuanbia nih hmunhma ah lehrulhnak caan a langhter. c Caan karlak ah isotope hmelchunhnak reagents phunphun hmangin chuahmi gas zat thlennak. d Kinetic isotope thlennak data.
Co-SA/NPs@NC-950 (Hmanthlak 5 b le S41) ah aa pehtlaimi thilri Co NP le Co SA cungah aa lo ngaimi in situ DRIFT hneksaknak an tuah. Thilri pahnih nih aa khatmi sining an langhter, asinain HCOOH* le HCOO* sining sang bik hna cu tlawmpal an i thlen, cucu Co NPs luhternak nih monoatomic center i electronic sining a thlen ti a langhter. A sining νas(OCO) peak cu Co-SAs/NPs@NC-950 le Co SA ah a lang nain Co NPs ah a lang lo, cu nih cun formic acid chap tikah a chuakmi a karlak cu a tlarimi chiti cunglei he aa tlakmi monodentate formic acid a si ti kha a langhter chin. cun SA cungah a cawlcangmi hmun 59 ah aa hngat. Hngalh awk ngai a simi cu, sining sang bik π(CH) le ν(C = O) hna i an hninhnak ah a karh tukmi hmuh a si, cu nih cun HCOOH* a thlennak a chuahter i, lehrulhnak a bawmh. Cu ruangah, Co-SAs/NPs@NC chung i HCOOH* le HCOO* sining sangbik hna cu 2 min chung an i pehtlaih hnu ah an tlau dengmang, cucu monometallic (6 min) le nanoparticle-based catalysts (12 min) nakin a rang deuh. . Hi hmuhmi vialte nih hin nanoparticle doping nih hin a karlak thilri pawl laknak le riantuannak a thanchoter ti kha a fehter, cucaah a cunglei ah langhtermi thil sining hna kha a rangter.
Reaction lamthluan kha hlathlainak tuah chin awk le rate tuaktannak step (RDS) hngalh khawhnak ding caah, KIE effect cu Co-SAs/NPs@NC-950 a um lio ah tuah a si. Hika ah, KIE hlathlainak caah HCOOH, HCOOD, DCOOH le DCOOD tibantuk formic acid isotopes phunphun kha hman an si. Figure 5c ah hmuh khawhmi bantuk in, ti tlawmternak rate cu a tanglei ning in a zor: HCOOH > HCOOD > DCOOH > DCOOD. Cun, KHCOOH/KHCOOD, KHCOOH/KDCOOH, KHCOOD/KDCOOD le KDCOOH/KDCOOD man hna cu 1.14, 1.71, 2.16 le 1.44, ciocio in tuak an si (Fig. 5d). Cucaah, HCOO* chung i CH pehtlaihnak tthencheunak nih kH/kD man >1.5 a langhter, cucu a nganmi cawlcanghnak tthatnak a langhter60,61, cun Co-SAs/NPs@NC-950 cung i HCOOH ti tlawmternak RDS a aiawhmi a lo.
Cun, Co-SA chunglei cawlcanghnak cung ah cawhmi nanoparticles nih a chuahpimi thil hngalhthiam awkah DFT tuaktannak an tuah. Co-SAs/NPs@NC le Co-SA model pawl cu langhtermi hneksaknak le a hlan riantuannak (Figs. 6a le S42)52,62 cungah hram bunh in sermi an si. Geometric tthatnak tuah hnu ah, monoatomic units he aa pehtlaimi Co6 nanoparticles (CoN2C2) hmete pawl kha an hmuh hna, cun Co-SA/NPs@NC ah Co-C le Co-N pehtlaihnak saunak cu 1.87 Å le 1.90 Å, ciocio ah an khiah. , cucu XAFS hmuhmi he aa tlak. Tuakmi tthencheunak dirhmun (PDOS) nih a langhter mi cu Co thir atom pakhat le nanoparticle fonhmi (Co-SAs/NPs@NC) nih CoN2C2 he tahchunh tikah Fermi level pawng ah a sang deuhmi cawhnak an langhter, cu nih cun HCOOH a chuahter. A rawkmi electron thlennak cu a ttha deuh (Hmanthlak 6b le S43). Co-SAs/NPs@NC le Co-SA i aa pehtlaimi d-band center pawl cu -0.67 eV le -0.80 eV ah an tuak, cu hna lakah Co-SAs/NPs@NC karhnak cu 0.13 eV a si, cu nih cun NP luhternak hnu ah, HCOO* particles nih Co-2C2 C2 electronic sining aa remhmi nih a lakmi kha a chuahter. Charge density aa dannak nih CoN2C2 block le nanoparticle pawngkam ah electron cloud nganpi a langhter, electron i thlennak ruangah an karlak ah pehtlaihnak fek a um ti a langhter. Bader charge hlathlainak he fonh tikah, atom in aa ṭhekmi Co nih Co-SA/NPs@NC ah 1.064e le Co SA ah 0.796e a sungh ti kha hmuh a si ( Figure S44 ). Hi hmuhmi nih hin nanoparticles fonhnak nih Co hmunhma hna i electron tlawmternak a chuahter, cu nih cun Co valence a karhter, cucu XPS hmuhmi he aa tlak (Fig. 6c). Co-O pehtlaihnak sining hna cu HCOO nih Co-SAs/NPs@NC le Co SA cung ah a luh hnawhmi hna cu crystalline orbital Hamiltonian group (COHP)63 tuaktannak in an hlathlai. Figure 6 d ah langhter bantuk in, -COHP i a ttha lomi le a ttha lomi man hna cu an i pehtlaihnak dirhmun le pehtlaihnak dirhmun he aa tlak. HCOO (Co-carbonyl O HCOO*) nih a lakmi Co-O i pehtlaihnak thazaang cu -COHP man pawl fonh in tuaktan a si, cu hna cu Co-SAs/NPs@NC le Co-SA caah 3.51 le 3.38 an si. HCOOH laknak zong nih aa khatmi phichuak a langhter: nanoparticle doping hnu ah -COHP i a dihlak man a karhmi nih Co-O pehtlaihnak a karhmi a langhter, cucaah HCOO le HCOOH riantuannak a thanchoter ( Figure S45 ).
Co-SA/NPs@NC-950 lattice sining. b PDOS Co-SA/NP@NC-950 le Co SA. c Co-SA/NPs@NC-950 le Co-SA cung i HCOOH laknak i a ritmi aa dannak 3D isosurface. (d) Co-SA/NPs@NC-950 (orhlei) le Co-SA (orhlei) ah HCOO nih a lakmi Co-O pehtlaihnak pCOHP. e Co-SA/NPs@NC-950 le Co-SA cung i HCOOH ti tlawmternak i a lehrulhnak lam.
Co-SA/NPs@NC i a ttha deuhmi ti chuahnak riantuannak hngalhthiam deuh awkah, a lehrulhnak lam le thazaang kha an khiah. A bik in, FA dehydrogenation nih hin step panga aa tel, cu hna ah cun HCOOH in HCOOH*, HCOOH* in HCOO* + H*, HCOO* + H* in 2H* + CO2*, 2H* + CO2* in 2H* + CO2, le 2H* in H2 (Fig. 6e) aa tel. Carboxylic oxygen hmangin catalyst cunglei ah formic acid molecule hna i an i hnim khawhnak thazaang cu hydroxyl oxygen hmangin nakin a niam deuh (Figure S46 le S47). Cu hnu ah, thazaang a niam deuh caah, adsorbate nih COOH* sernak caah CH pehtlaihnak tthennak nakin HCOO* sernak caah OH pehtlaihnak tthennak kha a duh deuh. Cu caan te ah cun, HCOO* nih monodentate adsorption a hman, cu nih cun pehtlaihnak hrawhnak le CO2 le H2 sernak a bawmh. Hi hmuhmi hna hi in situ DRIFT ah νas(OCO) peak a ummi he aa tlak, cu nih cun kan hlathlainak ah FA rawhnak cu formate lam in a cang ti a langhter chin. KIE tahnak ning in, CH tthencheunak nih a dang lehrulhnak tthanchonak nakin a sang deuhmi lehrulhnak thazaang khamnak a ngei i RDS a aiawh ti kha hngalh a biapi. A ttha bikmi Co-SAs/NPs@NC catalyst system i thazaang khamnak cu Co-SA (1.2 eV) nakin 0.86 eV in a niam deuh, cucu a dihlak in ti chuahnak tthatnak kha a tthanter ngaingai. A hlei in, nanoparticles a ummi nih atom in aa ṭhekmi coactive hmun hna i electronic sining kha a uk, cu nih cun a karlak thilri hna i an laknak le an cawlcangh khawhnak kha a ṭhanchoter chin, cucaah lehrulhnak khamnak kha a zorter i hydrogen chuahternak kha a ṭhanchoter.
A tawinak in chim ahcun, a voikhatnak bik ah hydrogen chuahternak catalysts hna i an catalytic riantuan ning cu a ttha ngaimi monometallic center le nanoparticles hmete a ngeimi thilri hmannak in tampi tthanchoter khawh a si ti kha kan langhter. Hi ruahnak cu nanoparticles (Co-SAs/NPs@NC) in remhmi cobalt-based single-metal catalysts sernak in fehter a si, cun single-metal center (CoN2C2) asiloah Co NPs lawng a ngeimi aa pehtlaimi thilri hna zong an si. Thilri vialte cu a sawhsawh mi pakhat-step pyrolysis phunglam in timhtuahnak an ngei. A sining hlathlainak nih a langhter mi cu a ttha bikmi thlennak (Co-SAs/NPs@NC-950) cu atom in aa ṭhekmi CoN2C2 unit le nitrogen le graphite bantuk carbon he aa cawhmi nanoparticle hmete (7-8 nm) hna an si. 1403.8 ml g-1 h-1 (H2:CO2 = 1.01:1) tiang a ttha tukmi gas chuah khawhnak a ngei, H2 le CO thim khawhnak 99.96% a si i ni zeimawzat chung a cawlcang peng kho. Hi catalyst cawlcanghnak nih hin Co SA le Pd/C catalysts cheukhat hna cawlcanghnak kha a let 4 le let 15 in a lonh. In situ DRIFT hneksaknak nih Co-SA he tahchunh ahcun, Co-SAs/NPs@NC-950 nih HCOO* a tthawng deuhmi monodentate laknak a langhter, cucu formate lam caah a biapi, cun dopant nanoparticles nih HCOO* riantuannak le C–H rangternak a thanchoter khawh. Bond tthencheunak cu RDS tiah theih a si. Theory tuaktannak nih a langhter ning ahcun Co NP doping nih pehtlaihnak thawngin Co atom pakhat cio i d-band center kha 0.13 eV in a karhter, HCOOH* le HCOO* karlak thilri hna i an i laknak kha a ṭhanchoter, cucaah Co SA caah 1.20 eV in 0 .86 eV tiang a zorter. Amah cu a ttha tukmi riantuannak caah ttuanvo a lak.
A kau deuh in, hi hlathlainak nih hin atom pakhat lawng a ngeimi thir catalysts thar suaisamnak caah ruahnak a pek i a ngan le a hme aa dangmi thir center hna i riantuan ttinak thawngin zeitindah catalytic riantuan ning tthanchoter khawh a si timi theihthiamnak a thanchoter. Hi lam hi a dang catalytic system tampi ah fawi tein karhter khawh a si lai tiah kan zumh.
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%) cu McLean, China in cawk a si. Formic acid (HCOOH, 98%) cu Tuluk ram Rhawn in cawkmi a si. Reagents vialte cu thianhnak chap loin direct in hman an si, cun ultrapure ti cu ultrapure thianhnak system hmangin timhtuah a si. Pt/C (5% mass loading) le Pd/C (5% mass loading) cu Sigma-Aldrich in cawkmi an si.
CoZn-ZIF nanocrystals sernak cu a hlan i hmanmi lam hna cung ah hram bunh in remhnak cheukhat he tuah a si23,64. Pakhatnak ah, 30 mmol Zn(NO3)2·6H2O (8.925 g) le 3.5 mmol Co(NO3)2·6H2O (1.014 g) cu cawh in 300 ml methanol ah cawh an si. Cun, 2-methylimidazole (9.853 g) 120 mmol cu ​​methanol 100 ml ah cawh in a cunglei cawhmi ah cawh. Cawhmi cu innchung lumnak ah suimilam 24 chung cawh a si. A donghnak ah, thilchuak cu 6429 g ah 10 min chung centrifugation in tthen a si i methanol in voithum ttha tein tawl a si. A chuakmi vutcam cu hman hlan ah 60°C ah zankhuadei vacuum ah an roter.
Co-SAs/NPs@NC-950 ser khawhnak ding caah, a ro cangmi CoZn-ZIF buh cu 950 °C ah 1 h chung 6% H2 + 94% Ar gas luannak ah 5 °C/min lumternak he pyrolyze a si. Co-SA/NPs@NC-950 hmuh khawhnak dingah zohchunhmi cu khaan lum tiang lumter a si. Co-SAs/NPs@NC-850 asiloah Co-SAs/NPs@NC-750 caah, pyrolysis lumnak cu 850 le 750 °C tiang thlen a si. Timhcia mi zohchunhmi hna cu acid etching tibantuk thil dang tuah hau loin hman khawh an si.
TEM (transmission electron microscopy) tahnak cu Thermo Fisher Titan Themis 60-300 “cube” microscope ah hmanthlak thlennak remhnak le 300 kV probe sertu lens he an tuah. HAADF-STEM hneksaknak hna cu FEI Titan G2 le FEI Titan Themis Z microscope hmangin hlathlainak le hmanthlak remhnak thilri hna he an tuah, cun DF4 tthen li hmuh khawhnak thilri hna he an tuah. EDS elemental mapping hmanthlak pawl zong FEI Titan Themis Z microscope in hmuh an si. XPS hlathlainak cu X-ray photoelectron spectrometer (Thermo Fisher model ESCALAB 250Xi) ah tuah a si. XANES le EXAFS Co K-edge spectra cu XAFS-500 cabuai (China Spectral Instruments Co., Ltd.) hmangin an lak hna. Co a tlawmtam cu atomic absorption spectroscopy (AAS) (PinAAcle900T) in tuak a si. X-ray thlennak (XRD) spectra cu X-ray thlennak tahnak (Bruker, Bruker D8 Advance, Germany) ah an khumh. Nitrogen laknak isotherms cu taksa laknak thilri (Micromeritics, ASAP2020, USA) hmangin hmuh an si.
Dehydrogenation reaction cu argon thli lakah thli chuah in Schlenk phunglam ningin tuah a si. Reaction vessel cu an chuah i argon in voi 6 an khahter tthan. Condenser ti peknak kha on law catalyst (30 mg) le solvent (6 ml) kha cawh. Thermostat hmangin thilri kha na duhmi lumnak tiang lumter law minutes 30 chung aa tluk tein umter. Formic acid (10 mmol, 377 μL) cu argon tang i thlennak um chungah an cawh. Reactor kha a tlawmter awkah lam thum in a ummi burette valve kha mer law, khar ṭhan law, kut in tuahmi burette hmangin a chuakmi gas zat kha tah hram thawk (Figure S16). Reaction a dih khawhnak ding caah a herhmi caan hnu ah, argon in thianhmi gas-tight syringe hmangin GC hlathlainak caah gas sample pakhat an lak.
In situ DRIFT hneksaknak hna cu Fourier transform infrared (FTIR) spectrometer (Thermo Fisher Scientific, Nicolet iS50) ah mercury cadmium telluride (MCT) hmuh khawhnak thilri he an tuah. Catalyst powder cu reaction cell (Harrick Scientific Products, Praying Mantis) ah chiah a si. Catalyst cu innchung lumnak ah Ar (50 ml/min) in thlop hnu ah, sample cu pekmi lumnak tiang lumter a si, cun HCOOH cawhmi ah Ar (50 ml/min) he cawh i in-situ reaction cell chungah thlet a si. lehrulhnak caah. Aa dangmi thlennak kalning hna kha zohchunh. Infrared spectra cu second 3.0 in suimilam 1 karlak ah an khumh.
HCOOH, DCOOH, HCOOD le DCOOD cu propylene carbonate ah a tanglei ah hman an si. A tangmi thil sining hna cu HCOOH ti tlawmternak phunglam he aa tlak.
A hmasa bik phunglam tuaktannak hna cu Vienna Ab initio modeling package (VASP 5.4.4) 65,66 chung i density functional theory framework hmangin tuah a si. CoN2C2 le CoN2C2-Co6 caah a tanglei ah 12.5 Å hrawng a kau mi graphene cunglei (5 × 5) a ngeimi superunit cell cu hman a si. A pawng i a ummi substrate tthen hna karlak pehtlaihnak hrial khawhnak ding caah 15 Å nak tam deuh a ummi vacuum hlatnak kha an chap. Ion le electron karlak pehtlaihnak cu projected amplified wave (PAW) method65,67 in a langhter. Grimm68,69 nih a chuahpimi van der Waals remhnak he Perdue-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) function kha hman a si. Thazaang le thazaang dihlak caah i tonnak tahfung cu 10−6 eV/atom le 0.01 eV/Å an si. Monkhorst-Pack 2 × 2 × 1 K-point grid hmangin thazaang tthennak cu 600 eV ah chiah a si. Hi model ah hmanmi pseudopotential cu electronic dirhmun in C 2s22p2 dirhmun, N 2s22p3 dirhmun, Co 3d74s2 dirhmun, H 1 s1 dirhmun, le O 2s22p4 dirhmun ah sermi a si. Adsorption thazaang le electron density i dannak cu adsorption asiloah interface models70,71,72,73,74 ningin adsorpted system thazaang chungin gas phase le surface species thazaang kha tlawmter in tuak a si. Gibbs zalongmi thazaang remhnak cu DFT thazaang kha Gibbs zalongmi thazaang ah thlennak caah hman a si i entropy le zero point thazaang75 ah hninhnonak bawmhnak kha a lak. A kai cuahmahmi hmanthlak-nudging elastic band (CI-NEB) phunglam cu thlennak dirhmun kawlnak caah hman a si76.
Hi hlathlainak chung ah hmuhmi le hlathlainak tuahmi data vialte cu capar le bawmchantu thilri ah aa telmi an si asiloah aa tlakmi halnak ah aa pehtlaimi catialtu sin in hmuh khawh an si. Hi capar caah hrampi data pek a si.
Hi capar he aa pehtlaimi zohchunhnak ah hmanmi code vialte cu aa pehtlaimi catialtu hna sin in halnak tuah tikah hmuh khawh a si.
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Wei, D. le a dangdang. Hydrogen sipuazi lei ah: hydrogen chiahnak le chuahnak chemistry caah aa khat lomi thilri sernak. ACS Thazaang Cakuat. 7, 3734–3752 (2022).
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