Urakoze gusura Kamere.com.Ukoresha verisiyo ya mushakisha hamwe na CSS igarukira.Kuburambe bwiza, turagusaba ko ukoresha mushakisha ivuguruye (cyangwa ugahagarika uburyo bwo guhuza uburyo muri Internet Explorer).Mubyongeyeho, kugirango tumenye inkunga ihoraho, twerekana urubuga rudafite imiterere na JavaScript.
Yerekana karuseli ya sisitemu eshatu icyarimwe.Koresha Utubuto na Ibikurikira kugirango unyuze mumashusho atatu icyarimwe, cyangwa ukoreshe utubuto twa slide kumpera kugirango wimuke unyuze mubice bitatu icyarimwe.
Igishushanyo mbonera hamwe niterambere ryibikorwa byo hejuru byitabiriwe cyane muburyo bwo guhitamo hydrogenation ariko bikomeza kuba ikibazo gikomeye.Hano twatanze raporo ya monatomic RuNi alloy (SAA) aho atome ya Ru ku giti cye ihagarikwa ku buso bwa Ni nanoparticles binyuze mu guhuza Ru-Ni, iherekejwe no guhererekanya electron kuva munsi y'ubutaka Ni i Ru.Ku bumenyi bwacu, umusemburo mwiza 0.4% RuNi SAA icyarimwe yerekanye ibikorwa byinshi (agaciro ka TOF: 4293 h - 1) hamwe na chemoselectivite yo guhitamo hydrogenation ya 4-nitrostyrene kugeza kuri 4-aminostyrene (umusaruro:> 99%), urwego rwo hejuru na ugereranije na catalogène izwi.Mubigeragezo bifatika hamwe no kubara byerekana ko imbuga za interineti ya Ru-Ni, nkimbuga zimbere zikora, ziteza imbere gucamo ibice OYA hamwe na bariyeri yo hasi ya 0.28 eV.Byongeye kandi, isesengura rya Ru-Ni rishyigikira ishyirwaho ryabunzi (C8H7NO * na C8H7NOH *) kandi ryihutisha intambwe igena igipimo (hydrogenation ya C8H7NOH *).
Amine ikora neza, ibyingenzi byubaka imiti myiza, bifite akamaro gakomeye mu nganda mu gukora imiti, imiti y’ubuhinzi, pigment na polymers1,2,3.Hydrogenation ya catalitike ya nitroaromatike iboneka byoroshye hejuru ya catalogène ya heterogeneous yakunze kwitabwaho nkuburyo bwangiza ibidukikije kandi bushobora gukoreshwa muburyo bwo guhuza amine hiyongereyeho 4,5,6,7.Nyamara, kugabanya imiti ya chemoselective ya -NO2 mugihe ugumana andi matsinda agabanuka nka alukene, alkine, halogene, cyangwa ketone ni ikintu cyifuzwa cyane ariko kitoroshye8,9,10,11.Kubwibyo, gukoresha mu buryo bushyize mu gaciro ibintu bigabanya kugabanya -NO2 matsinda bitagize ingaruka ku zindi nguzanyo zigabanywa ni byiza cyane 12,13,14.Hakozwe iperereza ryinshi rya catalizike idafite icyuma-cyuma kugira ngo hydrogène hydrogène ya nitroarene, ariko imiterere ikaze ituma ikoreshwa ryinshi15,16.Nubwo ibyuma byiza byifashishwa (nka Ru17, Pt18, 19, 20 cyangwa Pd21, 22, 23) bikora mubihe byoroheje byitwara neza, mubisanzwe bafite ikibazo cyigiciro cyinshi, guhitamo suboptimal, no gukoresha atome nke.Kubwibyo, kubona catalizike ikora cyane na chemoselective catalizator ukoresheje igishushanyo mbonera no guhuza neza imiterere myiza bikomeje kuba ikibazo gikomeye 24,25,26.
Monatomic Alloy (SAA) catalizator ifite ubushobozi bwiza bwicyuma cyiza, imiterere yihariye ya geometrike na elegitoronike, itanga imbuga zidasanzwe, kandi itanga imikorere idasanzwe ya catalitiki mu guca imyitwarire iranga umurongo 27,28,29,30,31.Gukoporora atome imwe hamwe na atome yicyuma muri SAA irashobora gukora nkibibanza bibiri bikora, byorohereza gukora substrate nyinshi cyangwa kwemerera intambwe zinyuranye zifatika kugaragara kurubuga rutandukanye32,33,34.Byongeye kandi, amashyirahamwe ya heterometallic hagati ya atome yicyuma yanduye hamwe nicyuma cyakira bishobora gutera ingaruka zidasanzwe, nubwo gusobanukirwa ningaruka zoguhuza hagati yibice bibiri byibyuma kurwego rwa atome bikomeje kutavugwaho rumwe 35,36,37,38.Kuri hydrogenation ya nitroarene ikora, ibikoresho bya elegitoroniki na geometrike yibibuga bikora bigomba gutegurwa muburyo bwo kwihutisha imikorere yitsinda rya nitro gusa.Nkuko bisanzwe, amatsinda ya nitro yabuze electron yamamaye cyane mukarere ka nucleophilique yubuso bwa catalizator, mugihe munzira ikurikira hydrogène, inzira ya koperative yibikorwa byabaturanyi bizagira uruhare runini mugucunga reaction na chemoselectivite 4,25.Ibi byaduteye gukora ubushakashatsi kuri catalizike ya SAA nkumukandida utanga ikizere cyo kuzamura imikorere ya hydrogène ya chemoselective ya hydrogène ya nitroaromatike, ndetse no kurushaho gusobanura isano iri hagati yimiterere yikibuga nigikorwa cya catalitiki ikora.
Hano, catalizike ishingiye kuri monatomic RuNi alloys yateguwe hashingiwe ku buryo bubiri bwa sintetike yuburyo bubiri, harimo guhindura imiterere-topologiya ihindura hydroxide ya kabiri (LDH) ikurikirwa no kuvura amashanyarazi.RuNi SAA yerekana imikorere idasanzwe ya catalitiki (> umusaruro wa 99%) kuri hydrogène ya chemoselective ya hydrogène ya 4-nitrostyrene kugeza kuri 4-aminostyrene hamwe ninshuro yo kugurisha (TOF) igera kuri ~ 4300 mol-mol Ru-1 h-1, ikaba ari yo hejuru cyane urwego hagati ya catalogeneous cataliste yanditswe mubihe bisa.Microscopi ya elegitoronike hamwe na spekitroscopique yaranze yerekanaga ko atome ya Ru itandukanijwe ikwirakwizwa hejuru ya Ni nanoparticles (~ 8 nm), igakora ihuzabikorwa rihamye rya Ru-Ni, bikavamo imbuga mbi za Ru (Ruδ-) kubera kohereza electron kuva mubutaka Ni kugeza Ru .Muburyo bwa FT-IR, ubushakashatsi bwa XAFS hamwe nubucucike bwimikorere (DFT) byemeje ko imbuga ziri kuri interineti ya Ru-Ni nkibikorwa byimbere byorohereza nitro.Gukora adsorption (0.46 eV) itandukanye niyi catalizike ya monometallic.(0,74 eV).Byongeye kandi, hydrogène itandukana iboneka mumituranyi Ni, ikurikirwa na hydrogenation yabahuza (C8H7NO * na C8H7NOH *) mumwanya wa Ruδ.Ingaruka ziterwa no gushyigikira doping muri catalizator ya RuNi SAA bivamo ibikorwa bya hydrogène ya nitroarenes idasanzwe no guhitamo, ibyo bikaba bishobora kwaguka no mubindi bikoresho bidasanzwe bya catalizike ikoreshwa muburyo bworoshye.
Dushingiye ku ihindagurika ryimiterere ya topologiya yuburyo bubiri bwa hydroxide (LDH) ibanziriza, twateguye monometallic Ni yashyizwe kuri amorphous Al2O3 substrates.Nyuma yibyo, icyiciro cya RuNi / Al2O3 bimetallic icyitegererezo gifite Ru itandukanye (0.1-2 wt%) yashizwemo neza na electrodisplacement kugirango ishyire atom Ru hejuru ya Ni nanoparticles (NPs) (Ishusho 1a).Ibipimo bya plasma atomic emission sprometrice (ICP-AES) ibipimo byerekana neza ibice bigize Ru na Ni muri izi ngero (Imbonerahamwe yinyongera 1), yegereye imitwaro yo kugaburira amatungo.Amashusho ya SEM (Igicapo c'inyongera 1) hamwe n'ibisubizo BET (Ishusho yinyongera 2-9 hamwe nimbonerahamwe yinyongera 1) yerekana neza ko imiterere ya morfologiya hamwe nubuso bwihariye bwurugero rwa RuNi / Al2O3 bidahinduka mugihe cyo kuvura amashanyarazi.- inzira yo kwimuka.Imiterere ya X-ray (Igishusho 1b) yerekana urukurikirane rwibintu biranga kuri 2θ 44.3 °, 51,6 °, na 76.1 °, byerekana ibyiciro (111), (200), na (220) bya Ni bisanzwe (JCPDS 004–0850 ).Ikigaragara ni uko ingero za RuNi zitagaragaza ibyerekezo bya Ru cyangwa okiside Ru, byerekana ikwirakwizwa ryinshi ryubwoko bwa Ru.Ikwirakwizwa rya electron microscopi (TEM) ibipimo bya monometallic Ni na RuNi (Ishusho 1c1 - c8) byerekana ko nikel nanoparticles ikwirakwijwe neza kandi igahagarikwa ku nkunga ya amorphous Al2O3 ifite ubunini buke (7.7-8.3 nm).Amashusho ya HRTEM (Igishusho 1d1 - d8) yerekana igihe kimwe cya lattice kingana na 0,203 nm mu byitegererezo bya Ni na RuNi, bihuye nindege za Ni (111), ariko, impande za latike za Ru ntizihari.Ibi byerekana ko atome ya Ru ikwirakwijwe cyane hejuru yicyitegererezo kandi ntigire ingaruka kumwanya wa Ni.Hagati aho, 2 wt% Ru / Al2O3 yashizwemo nuburyo bwo kubitsa-kubitsa nkigenzura, aho cluster ya Ru yagabanijwe kimwe hejuru yubutaka bwa Al2O3 (Ishusho yinyongera. 10-12).
Igishushanyo cyinzira ya synthesis ya RuNi / Al2O3, b X-ray itandukanya ya Ni / Al2O3 hamwe na RuNi / Al2O3 zitandukanye.c1 - c8 TEM na d1 - d8 HRTEM yerekana amashusho hamwe nubunini bugabanijwe bwa monometallic Ni, 0.1 wt%, 0.2 wt%, 0.4 wt%, 0,6 wt%, 0, 8% wt., 1 wt.Ishusho.% na 2 wt.% RuNi.“Au” bisobanura ibice uko bishakiye.
Igikorwa cya catalitiki yintangarugero ya RuNi cyakozwe na hydrogenation ya chemoselective hydrogenation ya 4-nitrostyrene (4-NS) kugeza 4-aminostyrene (4-AS).Guhindura 4-NS kuri substrate ya Al2O3 yari 0,6% gusa nyuma yamasaha 3 (Imbonerahamwe yinyongera 2), byerekana ingaruka nke za catalitiki ya Al2O3.Nkuko bigaragara ku gishushanyo.2a, catalizike yumwimerere ya nikel yerekanaga ibikorwa bya catalitiki nkeya cyane hamwe na 4-NS ihinduka 7.1% nyuma yamasaha 3, mugihe 100% ihinduka ryagerwaho imbere ya cataliste ya monometallic Ru mubihe bimwe.Cataliseri zose za RuNi zerekanye ibikorwa bya hydrogenation byiyongereye cyane (guhinduka: ~ 100%, 3 h) ugereranije na monometallic sample, kandi igipimo cyibisubizo cyari gifitanye isano neza nibirimo Ru.Ibi bivuze ko Ru ibice bigira uruhare rukomeye mugikorwa cya hydrogenation.Igishimishije, guhitamo ibicuruzwa (Igishusho 2b) biratandukanye cyane bitewe na catalizator.Kubintu bitagikora neza bya nikel, ibicuruzwa nyamukuru byari 4-nitroethylbenzene (4-NE) (guhitamo: 83,6%) naho guhitamo 4-AC byari 11.3%.Ku bijyanye na monometallic Ru, umurunga wa C = C muri 4-NS ushobora kwibasirwa na hydrogenation kurusha -NO2, bigatuma habaho 4-nitroethylbenzene (4-NE) cyangwa 4-aminoethylbenzene (4-AE);guhitamo 4-AC byari 15.7% gusa.Igitangaje, catalizike ya RuNi ifite ibintu bike ugereranije na Ru (0.1-0.4 wt%) yerekanye guhitamo neza (> 99%) kugeza kuri 4-aminostyrene (4-AS), byerekana ko ari NO2 kandi atari vinyl, idasanzwe ya chemoselective.Iyo ibiri muri Ru byarenze 0,6 wt.%, Guhitamo 4-AS byagabanutse cyane hamwe no kongera imizigo ya Ru, mugihe guhitamo kwa 4-AE byiyongereye aho.Kuri catalizator irimo 2 wt% RuNi, amatsinda ya nitro na vinyl byombi byari hydrogène cyane hamwe no guhitamo cyane kuri 4-AE ya 98%.Kugira ngo hamenyekane ingaruka za dispersion ya Ru kuri reaction ya catalitiki, hateguwe ingero 0.4 wt% Ru / Al2O3 (Ishusho yinyongera 10, 13 na 14) aho uduce twa Ru twakwirakwijwe cyane nka atome kugiti cye hagakurikiraho uduce duto twa Ru.(quasi-atomic Ru).Imikorere ya catalitiki (Imbonerahamwe yinyongera 2) yerekana ko 0.4 wt% Ru / Al2O3 itezimbere 4-AS guhitamo (67.5%) ugereranije na 2 wt% Ru / Al2O3, ariko ibikorwa ni bike (guhinduka: 12.9).%;Amasaha 3).Ukurikije umubare rusange wibibanza byicyuma hejuru byagenwe na CO pulsed chemisorption yapimwe, inshuro yo kugurisha (TOFmetal) ya catalizator ya RuNi yabonetse mugihe gito cya 4-NS (Ishusho yinyongera 15), yerekanaga icyerekezo cyambere cyo kwiyongera hanyuma kugirango ugabanuke hamwe no kwiyongera kwa Ru gupakira (Ishusho yinyongera 16).Ibi birerekana ko imbuga zose zicyuma zitagaragara nkibikorwa gakondo bya catalizike ya RuNi.Byongeye kandi, TOF ya catalizike ya RuNi yabazwe kuva kurubuga rwa Ru kugirango irusheho kwerekana ibikorwa byayo bya catalitiki (Ishusho 2c).Nkuko ibiri muri Ru byiyongera kuva 0.1 wt.% kugeza 0.4 wt.% Catalizator ya RuNi yerekanye indangagaciro za TOF zihoraho (4271–4293 h - 1), ibyo bikaba byerekana aho uduce duto twa Ru dukwirakwiza atome (bishoboka ko hashyizweho RuNi SAA).) kandi ikora nkurubuga nyamukuru rukora.Ariko, hamwe no kwiyongera kwipakurura rya Ru (muri 0,6-2 wt%), agaciro ka TOF kagabanuka cyane, ibyo bikaba byerekana impinduka mumiterere yimbere yikigo gikora (kuva ikwirakwizwa rya atome kugeza kuri Ru nanoclusters).Mubyongeyeho, kubumenyi bwacu, TOF ya 0.4 wt% RuNi (SAA) catalizator iri kurwego rwo hejuru mubikoresho byibyuma byavuzwe mbere mubihe bisa nkibisubizo (Imbonerahamwe yinyongera 3), bikagaragaza kandi ko monoatomic RuNi itanga ibintu byiza bya catalitiki.indorerezi.Igishushanyo cya 17 cyerekana imikorere ya catalitiki ya 0.4 wt% RuNi (SAA) ya catalizator ku muvuduko utandukanye nubushyuhe bwa H2, aho umuvuduko wa H2 wa 1 MPa hamwe nubushyuhe bwa 60 ° C byakoreshejwe nkibipimo bifatika.icyitegererezo kirimo RuNi 0.4 wt.% (Igishusho 2d), kandi nta kugabanuka gukomeye mubikorwa n'umusaruro byagaragaye mugihe cyikurikiranya.X-ray na TEM amashusho ya 0.4 wt% ya catalizator ya RuNi yakoreshejwe nyuma yinzinguzingo 5 (Ishusho yinyongera 18 na 19) yerekanaga ko nta mpinduka nini yagaragaye mumiterere ya kristu, byerekana ihinduka rikomeye ryimikorere ya hydrogenation.Byongeye kandi, 0.4 wt% RuNi (SAA) itanga kandi umusaruro mwiza wa amine kuri hydrogène ya chemoselective hydrogène yandi mavuta ya nitroaromatike arimo halogene, aldehydes, hamwe nitsinda rya hydroxyl (Imbonerahamwe yinyongera 4), byerekana ko ikoreshwa neza.
Guhindura Catalitike no b gukwirakwiza ibicuruzwa bya hydrogène ya nitrostyrene 4-imbere ya monometallic Ni, Ru, na RuNi catalizator ifite ibintu bitandukanye bya Ru (0.1-2 wt%), c murwego rwa catalitiki yingirakamaro, Umuyoboro uhinduka (TOF) kuri RuNi catalizator c bitewe na Ru kuri mole.d Ikizamini gishoboka cyo kongera gukoresha 0.4 wt.% RuNi catalizator ya gatanu yikurikiranya.ln (C0 / C) ishingiye ku gihe cyo kwitwara kwa hydrogenation ya e-nitrobenzene na f-styrene ivanze na nitrobenzene na styrene (1: 1).Imiterere yimyitwarire: reagent ya mmol 1, 8 ml solvent (Ethanol), catalizator 0,02 g, 1 MPa H2, 60 ° C, amasaha 3.Utubari twibeshya dusobanurwa nkibisanzwe gutandukana kwa bitatu byigana.
Kugira ngo hakorwe iperereza ku itandukaniro rikomeye rya chemoselective, hydrogenation yuruvange rwa styrene na nitrobenzene (1: 1) nayo yakozwe imbere ya catalizike monometallic Ni, Ru, 0.4 wt% RuNi, na 2 wt% RuNi, (Isanamu yinyongera 20).Nubwo chemoselectivite ya reaction hydrogenation yitsinda ryimikorere idahwitse, mubyukuri hariho itandukaniro muguhitamo hydrogène yimbere na intermolecular hydrogène kubera ingaruka za molekuline allosteric.Nkuko bigaragara ku gishushanyo.2e, f, umurongo ln (C0 / C) nigihe cyo kwitwara gitanga umurongo ugororotse kuva inkomoko, byerekana ko nitrobenzene na styrene byombi ari pseudo-yambere itondekanya.Monometallic nikel catalizator yerekanaga igipimo cya hydrogène nkeya cyane kuri p-nitrobenzene (0.03 h-1) na styrene (0.05 h-1).Ikigaragara ni uko igikorwa cyiza cya hydrogène styrene (igipimo gihoraho: 0.89 h-1) cyagezweho kuri catalizator ya Ru monometallic, ikaba isumba cyane ibikorwa bya hydrogenation ya nitrobenzene (igipimo gihoraho: 0.18 h-1).Kubijyanye na catalizator irimo RuNi (SAA) 0.4 wt.% hydrogenation ya nitrobenzene ni nziza cyane kuruta hydrogene ya styrene (igipimo gihoraho: 1.90 h-1 na 0.04 h-1), byerekana ko ukunda itsinda -NO2.hejuru ya C hydrogenation = umurunga C. Kuri catalizator hamwe na 2 wt.% RuNi, igipimo gihoraho cya hydrogenation ya nitrobenzene (1,65 h-1) yagabanutse ugereranije na 0.4 wt.% RuNi (ariko iracyari hejuru ya catalizike ya mono-metal), mugihe hydrogenation ya styrene yiyongereye cyane (igipimo gihoraho: 0.68).h - 1).Ibi birerekana kandi ko hamwe ningaruka zo guhuza hagati ya Ni na Ru, ibikorwa bya catalitiki na chemoselectivite kuri -NO2 byiyongereye cyane ugereranije na RuNi SAA.
Kugirango umenye neza imiterere yatatanye ya Ru na Ni, hakozwe uburyo bwo gufata amashusho ukoresheje impeta ndende cyane yijimye ya scanning electron microscopi hamwe no gukosora aberration (AC-HAADF-STEM) hamwe no gushushanya ibintu ukoresheje ingufu zikwirakwiza ingufu za sprosroscopi (EDS).Ikarita yibanze ya EMF yikitegererezo hamwe na 0.4 wt% RuNi (Igishusho 3a, b) yerekana ko Ru ikwirakwizwa cyane kuri nikel nanoparticles, ariko ntabwo iri kuri substrate ya Al2O3, ishusho ihuye na AC-HAADF-STEM (Ishusho. 3c) yerekana, Birashobora kugaragara ko ubuso bwa Ni NP burimo ibibanza byinshi byiza byerekana ubunini bwa atome ya Ru atome (irangwa n imyambi yubururu), mugihe nta cluster cyangwa Ru nanoparticles bigaragara.Igishushanyo 3d), cyerekana ishingwa rya monatomic RuNi.Kuri sample irimo RuNi 0,6 wt.%.Kubijyanye nicyitegererezo kirimo 2 wt% RuNi, classe nini nini za Ru kuri Ni NP zabonetse mumashusho ya HAADF-STEM (Igishusho 3f) hamwe na EDS ikarita yibanze (Ishusho yinyongera 21), byerekana kwirundanya kwinshi kwa Ru .
ishusho ya HAADF-STEM, b ihuye nigishushanyo mbonera cya EDS, c ishusho nini ya AC-HAADF-STEM ishusho, d ishusho ya STEM nini kandi ikwirakwiza ubukana bwa 0.4 wt% RuNi.(e, f) AC - HAADF - STEM amashusho yintangarugero zirimo 0,6 wt.% RuNi na 2 wt.% RuNi.
Ugereranije na Ni / Al2O3 na Ru / Al2O3, icyitegererezo cya DRIFTS ya CO adsorption mu mwanya wacyo (Ishusho 4a) kugirango irusheho kwiga imiterere yimiterere yintangarugero zirimo 0.4 wt.%, 0,6 wt.% na 2 wt.% RuNi.CO adsorption kuri sample ya Ru / Al2O3 itanga impinga nyamukuru kuri cm 2060 cm-1 nindi mpinga yagutse kuri cm 1849 cm-1 biterwa na CO adsorption kumurongo kuri Ru no kurambika kuri atome ebyiri zituranye na Ru, CO39,40.Kuri sample ya monometallic Ni, impinga ikomeye igaragara gusa kuri cm 2057 - 1, ibyo bikaba biterwa n'umurongo wa CO41,42 mukarere ka nikel.Kuri sample ya RuNi, usibye impinga nkuru kuri cm 2056 cm-1, hari igitugu cyihariye gishyizwe kuri ~ 2030 cm-1.Uburyo bwo guhuza impinga ya Gaussiya bwakoreshejwe kugirango habeho gukemura ikibazo cyo gukwirakwiza urugero rwa RuNi mu ntera ya cm 2000-2100 no gukwirakwiza CO mu karere ka Ni (2056 cm-1) no mu karere ka Ru (2031-2039).Impinga ebyiri zashyizwe kumurongo - 1) (Ishusho 4b).Igishimishije, kuva kuri sample ya Ru / Al2O3 (2060 cm - 1) kugeza kuri RuNi (2031–2039 cm - 1), impinga ya CO ifitanye isano n'umurongo wa CO mukarere ka Ru ihura cyane kandi ikiyongera hamwe nibirimo Ru.Ibi byerekana electronegativite yiyongereye ya Ru mu cyitegererezo cya RuNi, ibyo bikaba ibisubizo byo kohereza electroni kuva Ni i Ru, byongera ibitekerezo bya d-π electron kuva Ru kugeza kuri antibonding CO 2π * orbital.Mubyongeyeho, kuburugero rurimo 0.4 mass% RuNi, nta mpinga ya adsorption ikiraro yagaragaye, byerekana ko uduce twa Ru tubaho nka Atome Ni wenyine (SAA).Kubireba ingero zifite 0,6 wt.% RuNi na 2 wt.% RuNi, kuba hari ikiraro CO byemeza ko hariho Ru multimers cyangwa cluster, ibyo bikaba bihuza neza nibisubizo bya AC-HAADF-STEM.
a Muburyo bwa CO-DRIFTS yerekana Ni / Al2O3, Ru / Al2O3 na 0.4 wt.%, 0,6 wt.%, 2 wt.b Ikigereranyo kinini na Gaussiya cyerekanwe na RuNi / Al2O3 icyitegererezo gifite imyanya ihanamye hamwe na FWHM.c Muburyo Ru K-edge XANES yerekanwe na d EXAFS Fourier ihindura ibintu bitandukanye byintangarugero.K2 ifite uburemere bwahinduwe bwa XAFS K-edge Ru ibimenyetso bishingiye kumurongo wa Morlet kuburugero rwa e Ru ruva kuri f Ru, f 0.4 wt% RuNi na g RuO2.“Au” bisobanura ibice uko bishakiye.
Ubusanzwe muburyo bwa X-ray yo kwinjiza imiterere ya X-ray yo kwinjiza (XANES) yerekanwe kugirango bige ibyuma bya elegitoroniki na geometrike byerekana urugero rwa RuNi hamwe na Ru foil hamwe na RuO2.Nkuko bigaragara ku gishushanyo.4c, uko imizigo ya Ru igabanuka, ubukana bwumurongo wera bugabanuka buhoro buhoro kuva kuri Ru / Al2O3 kugeza kuri RuNi.Hagati aho, ubukana bwumurongo wera wa XANES ya spran kuri K-edge ya Ni yerekana kwiyongera gake kuva icyitegererezo cyambere Ni icyitegererezo cya RuNi (Ishusho yinyongera 22).Ibi byerekana impinduka mubucucike bwa electron hamwe no guhuza ibidukikije bya Ru.Nkuko bigaragara kuri X-ray yifoto yerekana amashanyarazi (XPS) (Isanamu yinyongera., byongeye kwerekana ihererekanyabubasha rya electron kuva Ni atom kuri Ru atom muri RuNi SAA.Isesengura rya Bader ryisesengura rya RuNi SAA (111) ryerekana ko atome ya Ru yitaruye itwara amafaranga mabi (Ruδ-) yimuwe avuye munsi y'ubutaka bwa Ni atom (Igishushanyo cya 24), ibyo bikaba bihuye nibisubizo bya DRIFTS hamwe na XPS.Kugira ngo twige uburyo burambuye bwo guhuza ibikorwa bya Ru (Igishusho 4d), twakoze uburyo bwagutse bwo kwinjiza X-ray-nziza ya spekitroscopi (EXAFS) muguhindura Fourier.Icyitegererezo kirimo RuNi 0.4 wt.% ifite impinga ikarishye kuri ~ 2.1 Å, iherereye mukarere kari hagati y’ibisasu bya Ru-O (1.5 Å) na Ru-Ru (2.4 Å), bishobora guterwa no guhuza Ru-Ni44, 45. Amakuru akwiranye n’ibisubizo EXAFS .% RuNi icyitegererezo.Ibi biremeza ko atome nyamukuru ya Ru itatanye kandi ikikijwe na Ni, ikora umusemburo wa monoatomic.Twabibutsa ko ubukana bwimpinga (~ 2,4 Å) bwo guhuza Ru-Ru bugaragara murugero rwa 0,6 wt.% RuNi kandi yazamuwe muri sample na 2 wt.% RuNi.By'umwihariko, umurongo wa EXAFS ukwiye werekanye ko imibare yo guhuza Ru-Ru yiyongereye cyane kuva kuri 0 (0.4 wt.% RuNi) igera kuri 2.2 (0,6 wt.% RuNi) hanyuma ikomeza kwiyongera kuri 6.7 (2 wt. , byerekana ko uko umutwaro wa Ru wiyongera, atome ya Ru igenda yegeranya buhoro buhoro.Impinduka ya K2 ifite uburemere (WT) yerekana ibimenyetso bya Ru K-edge XAFS yongeye gukoreshwa mu kwiga ibidukikije bihuza amoko ya Ru.Nkuko bigaragara ku gishushanyo.4e, Ru foil lobes kuri 2.3 Å, 9.7 Å-1 bivuga umusanzu wa Ru-Ru.Muri sample irimo RuNi 0.4 wt.%.Ru-Ni igaragara kuri 2.1 Å, 7.1 Å-1, ibyo bikaba byerekana ishingwa rya SAA.Byongeye kandi, EXAFS yerekanwe kuri K-edge ya Ni kuburugero rutandukanye yerekanaga ko nta tandukaniro rinini (Ishusho yinyongera 29), byerekana ko imiterere yo guhuza Ni idaterwa cyane na atome ya Ru.Muri make, ibisubizo bya AC-HAADF-STEM, muburyo bwa CO-DRIFTS, no mubushakashatsi bwa XAFS byemeje ko hateguwe neza catalizator ya RuNi SAA hamwe n’ihindagurika ry’ibice bya Ru kuri Ni NP kuva kuri atome imwe kugeza kuri Multimers ya Ru mu kongera Ru umutwaro.Byongeye kandi, amashusho ya HAADF-STEM (Ishusho yinyongera 30) hamwe na EXAFS yerekanwe (Isanamu yinyongera 31) ya catalizator ya RuNi SAA yakoresheje yerekanaga ko imiterere yo gutatanya hamwe nuburyo bwo guhuza imiterere ya atome ya Ru idahindutse cyane nyuma yinzinguzingo 5, byerekana. ko umusemburo uhamye RuNi SAA.
Ibipimo bya H2-TPD byakozwe kugirango bige adsorption ya hydrogène itandukana kuri catalizator zitandukanye kandi ibisubizo byerekanaga ko izo catalizator zose zifite imbaraga zikomeye zo gutandukana H2 zifite impanuka ya desorption kuri ~ 100 ° C (Ishusho yinyongera 32).Ibisubizo by'isesengura ryinshi (Isanamu y'inyongera. 33) ntibyerekanye umurongo ugaragara neza hagati ya reaction na hydrogène desorption.Twongeyeho, twakoze ubushakashatsi hamwe na D2 isotopes hanyuma tubona ingaruka ya kinetic isotope (KIE) agaciro ka 1.31 (TOFH / TOFD) (Ishusho yinyongera. 34), byerekana ko gukora no gutandukana H2 ari ngombwa ariko ntabwo ari intambwe igabanya igipimo.Ibarura rya DFT ryakozwe kugirango hakorwe iperereza ku myitwarire ya adsorption no gutandukana ya hydrogen kuri RuNi SAA na metallic Ni yonyine (Ishusho yinyongera 35).Kuburugero rwa RuNi SAA, molekile ya H2 nibyiza chemisorb hejuru ya atome imwe ya Ru ifite ingufu za adsorption ya -0,76 eV.Nyuma yaho, hydrogène yigabanyamo atome ebyiri zikora H ahantu hatagaragara rwa Ru-Ni RuNi SAA, irenga inzitizi yingufu za 0.02 eV.Usibye imbuga za Ru, molekile ya H2 irashobora kandi guterwa chemisorbed kumwanya wo hejuru wa atome ya Ni yegeranye na Ru (ingufu za adsorption: -0.38 eV) hanyuma igabanywa muri Hs ebyiri kurubuga rwa Ru-Ni na Ni-Ni.Inzitizi ya Atome 0.06 eV.Ibinyuranye na byo, inzitizi zingufu ziterwa na adsorption no gutandukana kwa molekile ya H2 hejuru ya Ni (111) ni -0.40 eV na 0.09 eV.Inzitizi zingufu nkeya cyane kandi itandukaniro ridafite akamaro ryerekana ko H2 itandukana byoroshye hejuru yubuso bwa Ni na RuNi (Ni-site cyangwa Ru-site), ntabwo arikintu cyingenzi kigira ingaruka kubikorwa bya catalitiki.
Gukora adsorption yitsinda runaka ryimikorere ningirakamaro muguhitamo hydrogenation ya substrate.Kubwibyo, twakoze ibarwa rya DFT kugirango dukore iperereza ku miterere ishoboka ya adsorption ya 4-NS hamwe nimbuga zikora ku buso bwa RuNi SAA (111), kandi ibisubizo byiza byerekanwa mu gishushanyo cya 36. Bisa nkibintu bisa (Ishusho 5a hamwe nishusho yinyongera. 36e), aho N atom iherereye ahitwa Ru-Ni ahantu huzuye kandi atom ebyiri O zahujwe na interineti ya Ru-Ni yerekana ingufu nkeya za adsorption (-3.14 eV).Ibi birerekana uburyo bwa termodinamike uburyo bwiza bwa adsorption ugereranije nu buryo buhagaritse nubundi buryo bubangikanye (Ishusho yinyongera. 36a - d).Byongeye kandi, nyuma yo kwiyongera kwa 4-HC kuri RuNi SAA (111), uburebure bwa N-O1 (L (N-O1)) mu itsinda rya nitro bwiyongereye bugera kuri 1.330 Å (Ishusho 5a), ni byinshi muremure kuruta uburebure bwa gaze 4- NS (1.244 Å) (Ishusho yinyongera 37), ndetse irenga L (N-O1) (1.315 Å) kuri Ni (111).Ibi birerekana ko adsorption yimikorere ya N - O1 kumurongo wa RuNi PAA yazamutse cyane ugereranije na Ni (111).
ibishushanyo bya Adsorption ya 4-HC kuri Ni (111) na RuNi SAA (111) (Eads) hejuru (kuruhande no hejuru).Ru - violet, Ni - icyatsi, C - orange, O - umutuku, N - ubururu, H - cyera.b Muburyo bwa FT-IR yerekanwe ya gaze na chemisorbed 4-HC kuri surfactants monometallic Ni, Ru, RuNi (0.4 wt.%) na 2 wt.% RuNi.c Ubusanzwe muri XANES na d-icyiciro-cyakosowe na Fourier EXAFS kuri Ru K-edge ya 0.4 wt% RuNi PAA mugihe cya 4-NS adsorption (RuNi SAA - 4NS) hamwe nintambwe ya hydrogenation (RuNi SAA - 4NS - H2) .Ihinduka ryerekana impinduka. ;“Au” bisobanura ibice uko bishakiye.
Kugirango urusheho kugerageza imyitwarire ya adsorption ya 4-NS, mubipimo bya FT-IR byakorewe kuri Ni monometallic, Ru monometallic, 0.4 wt% RuNi (SAA), na catalizator 2 wt% RuNi (Ishusho 5b).FT-IR ya gaze ya 4-NS yerekanaga impinga eshatu ziranga kuri 1603, 1528, na 1356 cm - 1, zahawe ν (C = C), νas (NO2), na νs (NO2) 46,47, 48.Imbere ya monometallic Ni, hagaragara impinduka zitukura zose uko ari eshatu: v (C = C) (cm 1595 - 1), νas (NO2) (1520 cm - 1), na νs (NO2) (1351 cm - 1) ., byerekana chemisorption ya C = C na -NO2 mumatsinda ya Ni hejuru (birashoboka cyane, muburyo bwa adsorption ibangikanye).Kuri sample ya monometallic Ru, habonetse redshifts yaya matsinda atatu (1591, 1514, na 1348 cm - 1) ugereranije na monometallic Ni yabonetse, ibyo bikaba byerekana ko byongerewe gato adsorption yitsinda rya nitro hamwe na S = С kuri Ru.Kubireba 0.4 wt.% RuNi (SAA), itsinda rya ν (C = C) ryibanze kuri cm 1596 - 1, rikaba ryegereye cyane itsinda rya monometallic Ni (1595 cm - 1), byerekana ko amatsinda ya vinyl akunda adsorb Ni kuri RuNi Imbuga za SAA.Byongeye kandi, bitandukanye na catalizike ya monometallic, ubukana bugereranije bwumurongo wa νs (NO2) (cm 1347 cm-1) buracogora cyane kurenza νas (NO2) bande (1512 cm-1) kuri 0.4 wt.% RuNi (SAA ), ifitanye isano no gutandukanya OYA inkwano kuri -NO2 kugirango ikore intera ya nitroso ukurikije ubushakashatsi bwabanje 49,50.Ikintu gisa nacyo cyagaragaye murugero hamwe na RuNi irimo 2 wt.%.Ibisubizo byavuzwe haruguru byemeza ko ingaruka ziterwa na centre ya bimetallic muri PAA RuNi iteza polarisiyasi no gutandukana kwamatsinda ya nitro, ibyo bikaba bihuza neza nuburyo bwiza bwa adsorption bwabonetse kubarwa bwa DFT.
Muburyo bwa XAFS spectroscopy yakozwe kugirango yige ihindagurika ryimiterere yimiterere ya elegitoronike no guhuza imiterere ya RuNi SAA mugihe cya 4-NS adsorption hamwe na catalitike.Nkuko bigaragara kuri K-edge XANES spektr ya Ru (Igishusho 5c), nyuma ya adsorption ya 4-HC, 0.4 wt.% RuNi PAA, inkombe yo kwinjizwa yimuriwe cyane ku mbaraga zisumba izindi, ibyo bikaba biherekejwe no kwiyongera kwimbaraga zumurongo wera, ibyo bikaba byerekana ko amoko ya Ru Igice cya okiside kibaho bitewe no kohereza electron kuva Ru ikajya kuri 4-NS.Byongeye kandi, icyiciro cyakosowe na Fourier gihindura EXAFS yerekana amatangazo ya 4-NS RuNi SAA (Igishusho 5d) yerekana kuzamura ibimenyetso neza kuri ~ 1.7 Å na ~ 3.2 Å, bifitanye isano no gushiraho Ru-O.XANES na EXAFS yerekanwe kuri 0.4 wt% RuNi SAA yagarutse uko yari imeze nyuma yiminota 30 yatewe gaze ya hydrogen.Ibi bintu byerekana ko amatsinda ya nitro yamamajwe kurubuga rwa Ru akoresheje imiyoboro ya Ru-O ishingiye ku mikoranire ya elegitoroniki.Kubijyanye na XAFS yerekanwe ya Ni-K ku nkombe (Umugereka w'inyongera. 38), nta mpinduka zigaragara zagaragaye, zishobora guterwa n'ingaruka zo kugabanuka kwa atome Ni mu gice kinini ku bice Ni ibice.Ubucucike buteganijwe bwa leta (PDOS) bwa RuNi SAA (Igicapo 5e) bwerekana ko imiterere idahwitse yitsinda rya nitro hejuru yurwego rwa Femi yaguka kandi ikagenda munsi yurwego rwa Femi muri leta yamamajwe, ibyo bikaba byerekana ko electron ziva kuri d- leta ya RuNi SAA inzibacyuho muri leta idatuwe muri −NO2.Itandukaniro ry'ubucucike bw'amafaranga (Isanamu y'inyongera 39) hamwe n'isesengura rya Bader (Isanamu y'inyongera 40) byerekana ko uburinganire bwa elegitoronike bwa 4-NS bwirundanya nyuma yo kwinjizwa hejuru ya RuNi SAA (111).Byongeye kandi, -NO2 yubucucike bwiyongereye cyane ugereranije nitsinda rya vinyl muri 4-NS kubera ihererekanyabubasha rya elegitoronike kuri interineti ya Ru-Ni, byerekana imikorere yihariye ya NO bond mu itsinda rya nitro.
Mu mwanya FT-IR yakozwe kugirango ikurikirane inzira ya catalitiki ya hydrogène ya hydrogène ya 4-NS ku ngero za catalizator (Ishusho 6).Kuri catalizike ya mbere ya nikel (Igishusho 6a), kugabanuka gake gusa mubucucike bwa nitro (1520 na 1351 cm-1) na C = C (1595 cm-1) byagaragaye mugihe cyanyuze H2 kuminota 12, yerekana ko - Gukora NO2 na C = C ahubwo bifite intege nke.Imbere ya monometallic Ru (Igishusho 6b), umurongo wa ν (C = C) (kuri cm 1591 - 1) uragabanuka vuba muminota 0-12, mugihe imirongo ya νs (NO2) na νas (NO2) iragabanuka cyane .Buhoro Ibi byerekana gukora cyane mumatsinda ya vinyl ya hydrogenation, biganisha kumikorere ya 4-nitroethylbenzene (4-NE).Kubireba 0.4 wt.% RuNi (SAA) (Igishusho 6c), umurongo wa νs (NO2) (cm 1347 - 1) uzimira vuba hamwe no kwinjira kwa hydrogène, biherekejwe no kubora buhoro buhoro ν (N = O);itsinda rishya ryibanze kuri cm 1629-1 naryo ryaragaragaye, biterwa no kunama kwa NH.Mubyongeyeho, itsinda rya ν (C = C) (1596 cm - 1) ryerekana kugabanuka gake nyuma yiminota 12.Ihinduka rikomeye ryemeza polarisiyasi na hydrogenation ya -NO2 kugeza -NH2 na 0.4 wt% RuNi (SAA) ishingiye kuri chemoselectivite idasanzwe kuri 4-aminostyrene.Kuri sample ya 2 wt.% RuNi (Igishusho 6d), usibye kugaragara kw'itsinda rishya kuri cm 1628 - 1 ryitiriwe δ (NH), itsinda rya ν (C = C) rigabanuka cyane kandi rikabura hamwe no kwiyongera kwitsinda rya nitro (1514) na cm 1348 - 1).Ibi byerekana ko C = C na -NO2 zikora neza bitewe nuko hariho Ru-Ru na Ru-Ni hagati y’imikoranire, ibyo bikaba bihuye n’ishyirwaho rya 4-NE na 4-AE kuri 2 wt.% RuNi.
Muburyo bwa FT-IR ya hydrogenation ya 4-NS imbere ya monometallic Ni, b monometallic Ru, c 0.4 wt% RuNi SAA, na d 2 wt% RuNi muri H2 itemba kuri cm 1700–1240– Urutonde 1 rwanditswe nka gaze ya reaction nyuma yiminota 0, 3, 6, 9 na 12.“Au” bisobanura ibice uko bishakiye.Ikwirakwizwa ryingufu hamwe nuburyo bujyanye nuburyo bwiza bwa hydrogène ya C = C kandi NTA gusohora muri 4-NS kuri e Ni (111) na f RuNi SAA (111).Ru - violet, Ni - icyatsi, C - orange, O - umutuku, N - ubururu, H - cyera."Amatangazo", "IS", "TS", na "FS" byerekana leta ya adsorption, leta yambere, leta yinzibacyuho, na leta yanyuma.
Inzira zishoboka zo guhindura 4-NS kuri Ni (111) na RuNi SAA (111), harimo hydrogenation ya C = C na NO kuvanaho inkwano, byakorewe iperereza kubara DFT kugirango irusheho gusobanura uruhare rukomeye rwa 4-NS.Ibice bya interineti ya Ru-Ni yo gukora intego za 4-AS.Ku buso bwa Ni (111) (Igishusho 6e), inzitizi z’ingufu zo Kutagira isukari hamwe na hydrogenation y’amatsinda ya vinyl mu cyiciro cya mbere ni 0,74 na 0,72 eV, ibyo bikaba byerekana ko hydrogène ya chemoselective hydrogène ya nitro muri 4-HC ari nabi.kuri monometallic nikel igaragara.Ibinyuranye na byo, inzitizi y’ingufu zo Kutitandukanya ni 0.46 eV gusa hejuru ya RuNi SAA (111), iri munsi cyane ugereranije na C = C ihuza hydrogenation (0,76 eV) (Ishusho 6f).Ibi birashimangira bidasubirwaho ko ibigo bya Ru - Ni bigabanya neza inzitizi yingufu zidafite NO mu gusohora mu matsinda ya nitro, biganisha ku kugabanya amashyuza ya nitro ugereranije na C = C ku matsinda ya C = C ku buso bwa RuNi, ibyo bikaba byemeranya n’ibisubizo by’ubushakashatsi.
Uburyo bwo kubyitwaramo no kubara umurongo w'ingufu za hydrogène ya 4-NS kuri RuNi SAA byakorewe iperereza hashingiwe ku mibare ya DFT (Ishusho 7), kandi ibisobanuro birambuye bya adsorption y'intambwe nyamukuru byerekanwe ku gishushanyo cya 41. Kugira ngo gahunda yo kubara, inzitizi zitanga ingufu kuri molekile zamazi zashyizwe mubibare.icyitegererezo cy'isahani 9.17.Nkuko bigaragara ku gishushanyo.7, molekile ya 4-NS yabanje kwinjizwa mu buryo bubangikanye na surfactant ya RuNi, na atome ebyiri O zo mu itsinda rya nitro zihuzwa na santere ya Ru-Ni (S0; intambwe ya I).Ibikurikiraho, NTA nkunga ifatanye kurubuga rwa Ru yaracitse, iherekejwe no gushiraho intera ya nitroso (C8H7NO *) kurubuga rwa Ru-Ni na O * kurubuga rwa Ni ubusa (S0 → S1 ukoresheje TS1; bariyeri: 0.46 eV, intambwe ya kabiri).O * radicals ihindurwa na atome ikora H ikora molekile ya H2O hamwe na exotherm ya 0,99 eV (S1 → S2).Inzitizi zingufu za hydrogène ya C8H7NO * hagati (Ishusho yinyongera 42 na 43) yerekana ko atome H ituruka kumyanya ya Ru-Ni yibasiye cyane cyane atome O hejuru ya N atom, bikavamo C8H7NOH * (S2 → S4; inzitizi yingufu TS2: 0.84 eV, intambwe ya III).Atome ya N muri C8H7NOH * noneho yashizwemo hydrogène kugirango ibe C8H7NHOH * nyuma yo kurenga bariyeri 1.03 eV (S4 → S6; intambwe ya IV), iyo ikaba ari intambwe isobanura ibyakozwe byose.Ibikurikira, umurunga wa N - OH muri C8H7NHOH * wacitse kuri interineti ya Ru - Ni (S6 → S7; inzitizi yingufu: 0.59 eV; icyiciro V), nyuma OH * ihindurwamo hydrogene kuri HO (S7 → S8; exotherm: 0.31 eV ) Nyuma yibyo, N atom za site ya Ru-Ni ya C8H7NH * yongeyeho hydrogène kugirango ibe C8H7NH2 * (4-AS) ifite inzitizi yingufu za 0,69 eV (S8 → S10; intambwe ya VI).Hanyuma, molekile ya 4-AS na HO yambuwe hejuru ya RuNi-PAA, maze catalizator isubira uko yari imeze (intambwe ya VII).Iyi miterere idasanzwe hagati ya atome imwe ya Ru na Ni substrates, iherekejwe ningaruka zo guhuza abashyitsi doping muri RuNi SAA, bivamo ibikorwa bidasanzwe hamwe na chemoselectivite ya hydrogenation ya 4-NS.
Umuceri.4. Igishushanyo mbonera cyuburyo bwa hydrogenation reaction ya NS kuri 4-AS hejuru ya RuNi PAA.Ru - violet, Ni - icyatsi, C - orange, O - umutuku, N - ubururu, H - cyera.Inet yerekana ikwirakwizwa ryingufu zishobora kuba 4-NS hydrogenation hejuru ya RuNi SAA (111), ubarwa hashingiwe kuri DFT."S0 ″ byerekana leta yambere, naho" S1-S10 ″ igereranya urukurikirane rwa adsorption.“TS” bisobanura leta yinzibacyuho.Imibare iri mumutwe yerekana inzitizi zingufu zintambwe zingenzi, naho imibare isigaye igereranya ingufu za adsorption zabahuza.
Gutyo, catalizator ya RuNi SAA yabonetse hakoreshejwe reaction ya electrosubstitution hagati ya RuCl3 na Ni NPs zabonetse kubabanjirije LDH.Ugereranije na monometallic Ru, Ni hamwe na catalizeri itavanze, RuNi SAA yavuyemo yerekanye imikorere myiza ya catalitiki ya hydrogenation ya 4-NS (umusaruro wa 4-AS:> 99%; agaciro ka TOF: 4293 h-1).Ibiranga byose hamwe birimo AC-HAADF-STEM, muri CO-DRIFTS, na XAFS byemeje ko atome ya Ru yimuwe kuri Ni NPs kurwego rumwe rwa atome binyuze kuri bonds ya Ru-Ni, iherekejwe no kohereza electroni i Ni i Ru.Muburyo bwa XAFS, ubushakashatsi bwa FT-IR, hamwe na DFT kubara byerekanaga ko urubuga rwa Ru-Ni rukora nk'urubuga rukora imbere kugirango rukoreshe neza OYA inkwano mu itsinda rya nitro;Gukomatanya hagati ya Ru hamwe n’abaturanyi Ni byorohereza gukora hagati na hydrogenation hagati, bityo bikazamura cyane imikorere ya catalitiki.Aka kazi gatanga ubushishozi ku isano iri hagati yimikorere ikora hamwe nimyitwarire ya catalitiki ya SAA kurwego rwa atome, itanga inzira yo gushushanya neza kubindi bice bibiri byifashishwa muburyo bwo guhitamo.
Isesengura ryisesengura ryakoreshejwe mubushakashatsi ryaguzwe muri Sigma Aldrich: Al2 (SO4) 3 18H2O, sodium tartrate, CO (NH2) 2, NH4NO3, Ni (NO3) 2 6H2O, RuCl3, Ethanol, 4-nitrostyrene (4- NS) , 4-aminostyrene, 4-nitroethylbenzene, 4-aminoethylbenzene na nitrostyrene.Amazi meza yakoreshejwe mubushakashatsi bwose.
Inzego za NiAl LDHs zashizwe hamwe nkibibanziriza gukura kwimiterere.Ubwa mbere, urea (3,36 g), Al2 (SO4) 3 · 18H2O (9.33 g) na sodium tartrate (0,32 g) byashongeshejwe mumazi ya deioni (140 ml).Igisubizo cyavuyemo cyimuriwe muri autoclave isize Teflon hanyuma gishyuha kugeza kuri 170 ° C kuri 3 h.Imvura yavuyemo yogejwe namazi yatoboye hanyuma yumishwa neza, nyuma ibarwa kuri 500 ° C (2 ° C min - 1; 4 h) kugirango ibone amorphous Al2O3.Noneho Al2O3 (0.2 g), Ni (NO3) 2 6H2O (5.8 g) na NH4NO3 (9,6 g) bakwirakwijwe mumazi asukuye (200 ml) hanyuma pH ihinduka kuri ~ 6.5 hongerwamo amazi 1 mol l -1 amoniya..Ihagarikwa ryimuriwe muri flask kandi rigumishwa kuri 90 ° C kuri 48 h kugirango ubone NiAl-LDH.Ifu ya NiAl-LDH (0,3 g) yagabanutse mumugezi wa H2 / N2 (10/90, v / v; 35 ml min - 1) kuri 500 ° C kuri 4 h (igipimo cyo gushyushya: 2 ° C min -1 ).Gutegura ingero za nikel monometallic (Ni / Al2O3) yashyizwe kuri amorphous Al2O3.Ingero za bimetallic zabitswe za RuNi zahujwe nuburyo bwa electrodisplacement.Ubusanzwe, icyitegererezo gishya cya Ni / Al2O3 (0,2 g) cyakwirakwijwe muri ml 30 y’amazi meza, hanyuma igisubizo cya RuCl3 (0.07 mmol l-1) kongerwaho buhoro buhoro hanyuma kibyutsa ingufu mu minota 60 mu rwego rwo kurinda ikirere cya N2 .Imvura yavuyemo yashizwemo, yozwa n'amazi meza, hanyuma yumishwa mu ziko rya vacu kuri 50 ° C kuri 24 h, ibona icyitegererezo kirimo 0.1% RuNi.Mbere yisuzuma rya catalitiki, ingero nshya yashizwemo yagabanutse mbere yumugezi wa H2 / N2 (10/90, v / v) kuri 300 ° C (igipimo cyo gushyushya: 2 ° C min - 1) kuri 1 h, hanyuma ushushe N2 Ubukonje kubushyuhe bwicyumba.Kubisobanura: ingero zifite Ru / Al2O3 zingana na 0.4% na 2% kubwinshi, hamwe na Ru nyayo ya 0.36% kubwinshi na 2,3% kubwinshi, byateguwe nubushyuhe bwimvura kandi bishyuha kuri 300 ° C (gukoresha H2 / N2: 10/90, v / v, igipimo cyo gushyushya: 2 ° C min - 1) kumasaha 3.
Ubushakashatsi bwa X-ray (XRD) bwakorewe kuri Bruker DAVINCI D8 ADVANCE diffractometero ifite isoko ya Cu Kα (40 kV na 40 mA).Shimadzu ICPS-7500 Yashizwe hamwe na Plasma Atomic Emission Spectrometer (ICP-AES) yakoreshejwe kugirango hamenyekane ubwinshi bwibintu mubitegererezo bitandukanye.Gusikana amashusho ya microscopi ya electron (SEM) yafashwe amashusho akoresheje microscope ya Zeiss Supra 55.Ubushakashatsi bwa N2 adsorption-desorption bwakorewe ku gikoresho cya Micromeritike ASAP 2020 kandi ubuso bwihariye bwabazwe hakoreshejwe uburyo bwa Brunauer-Emmett-Teller (BET).Ikwirakwizwa rya electron microscopi (TEM) ibiranga byakorewe kuri JEOL JEM-2010 mikorosikopi ikwirakwiza cyane.High Angle Aberration Yakosowe Gusikana Ikwirakwizwa rya Electron Microscope Yijimye (AC-HAADF) - STEM hamwe na FEI Titan Cube Themis G2 300 hamwe na sisitemu ya aberration ikosora hamwe na sisitemu yo gukwirakwiza ingufu za X-ray Spectroscopy (EDS) hamwe nibikoresho bya JEOL JEM-ARM200F) .Imiterere myiza ya X-ray yakira spekitroscopi (XAFS) mumwanya K-edge wa Ru na Ni K-edge yapimwe kumuyoboro 1W1B na 1W2B yikigo cya Beijing Synchrotron Imirasire (BSRF) yikigo cya fiziki yingufu zikomeye (IHEP), mubushinwa .Ishuri Rikuru ry'Ubumenyi (KAN).Ubushakashatsi bwa CO chemisorption hamwe nubushyuhe bwateguwe na hydrogen desorption (H2-TPD) byakorewe ku gikoresho cya Micromeritics Autochem II 2920 hakoreshejwe icyuma gipima ubushyuhe (TCD).Ubushakashatsi bwa DRIFTS hamwe na FT-IR bwakorewe kuri Bruker TENSOR II ya infragre ya spekrometrike ifite ibikoresho byahinduwe muri selile reaction hamwe na MCT yunvikana cyane.Uburyo burambuye bwo kuranga bwasobanuwe mumakuru yinyongera.
Ubwa mbere, substrate (4-NS, 1 mmol), solvent (Ethanol, ml 8) na catalizator (0,02 g) byongeweho neza kuri ml 25 autoclave idafite ibyuma.Imashini yahise isukurwa burundu hamwe na 2.0 MPa (> 99,999%) hydrogène inshuro 5, hanyuma ikanda hanyuma igashyirwa kuri 1.0 MPa hamwe na H2.Igisubizo cyakozwe kuri 60 ° C kumuvuduko uhoraho wa 700 rpm.Nyuma yo kubyitwaramo, ibicuruzwa byavuyemo byamenyekanye na GC-MS hanyuma bisesengurwa mu buryo bwuzuye hifashishijwe sisitemu ya chromatografiya ya Shimadzu GC-2014C ifite inkingi ya capillary ya GSBP-INOWAX (30 m × 0,25 mm × 0,25 mm) hamwe na deteri ya FID.Guhindura 4-nitrostyrene no guhitamo ibicuruzwa byagenwe kuburyo bukurikira:
Inshuro zingana (TOF) agaciro kabaruwe nka mol 4-NS yahinduwe kumwanya wibyuma bya mol kumasaha (mol4-NS mol-1 h-1) hashingiwe kuri 4-NS ihinduka (~ 15%).Kubijyanye numubare wa Ru node, Ru-Ni Imigaragarire yumubare numubare wuzuye wa metero zubutaka.Kubizamini bisubirwamo, catalizator yakusanyirijwe hamwe na centrifugation nyuma yo kubyitwaramo, yoza inshuro eshatu hamwe na Ethanol, hanyuma yongera kwinjizwa muri autoclave kugirango ikurikirane.
Ibarura ryimikorere yose (DFT) ibarwa ryakozwe hifashishijwe porogaramu yo kwigana ya Vienne ab initio (VASP 5.4.1).Imikorere rusange ya Gradient Yegeranye (GGA) imikorere ya PBE ikoreshwa mugusobanura uburyo bwo guhanahana ibikoresho bya elegitoronike.Uburyo bwa Projector Augmented Wave (PAW) bukoreshwa mugusobanura imikoranire hagati ya nuclei ya atome na electron.Uburyo bwa Grimm DFT-D3 busobanura ingaruka zimikoranire ya van der Waals hagati ya substrate ninteruro.Kubara Inzitizi Zingufu Zamuka Kuzamuka Amatsinda ya Elastike hamwe na Boost (CI-NEB) hamwe nuburyo bwa Dimer.Isesengura ryinshuro zinyeganyeza ryakozwe, ryemeza ko muri leta yinzibacyuho hariho inshuro imwe gusa yibitekerezo (Ishusho yinyongera 44-51).Ibiharuro birambuye bisobanuwe mumakuru yinyongera.
Amakuru yingenzi ashyigikira ibibanza muriyi ngingo yatanzwe mumasoko yamakuru yatanzwe.Andi makuru ajyanye nubu bushakashatsi araboneka kubanditsi babisabwe babisabye.Iyi ngingo itanga amakuru yumwimerere.
Korma A. na Serna P. Hydrogene ya chemoselective ya hydrogène ya nitro hamwe na catalizaires ya zahabu.Ubumenyi 313, 332–334 (2006).
Formenti D., Ferretti F., Sharnagle FK na Beller M. Kugabanya ibice bya nitro ukoresheje 3d base catalizator.Imiti.119, 2611-22680 (2019).
Tan, Y. n'abandi.Au25 nanoclusters ishyigikiwe na ZnAl hydrotalcite nkibisubizo bya hydrogène ya chemoselective ya 3-nitrostyrene.Angie.Imiti.imbere Ed.56, 1-6 (2017).
Zhang L, Zhou M, Wang A, na Zhang T. Guhitamo hydrogenation kuri catalizator zishyigikiwe: kuva nanoparticles kugeza kuri atome kugiti cye.Imiti.120, 683–733 (2020).
Izuba, K. n'abandi.Monoatomic rhodium catalizator ikubiye muri zeolite: Umusemburo mwiza wa hydrogène hamwe na hydrogenation ya casade yatoranijwe ya nitroaromatike.Angie.Imiti.imbere Ed.58. 18570–18576 (2019).
Tian, ​​S.n'abandi.Diatomic Pt itera imbaraga hamwe nibikorwa byiza bya catalitiki yo guhitamo hydrogenation na epoxidation.Komini y'igihugu.12, 3181 (2021).
Wang, Yu.n'abandi.Hydrogenation ya chemoselective ya nitroarenes kuri nanosize fer (III) –OH - platine.Angie.Imiti.imbere Ed.59, 12736–12740 (2020).
Wei, H. n'abandi.FeOx yashyigikiye platine monatomic na pseudomonoatomic catalizator ya chemoselective hydrogenation ya nitroaromatike ikora.Komini y'igihugu.5, 5634 (2014).
Khan, A. n'abandi.Gutandukanya atom ya Pt ikurikiranye no gushiraho Pt-Zn intermetallic nanoparticles kugirango ihuze guhitamo hydrogène ya nitrophenylacetylene 4.Komini y'igihugu.10, 3787 (2019).
Wang, K. n'abandi.Kureba ubunini budasanzwe bushingiye kuri monatomic Pt catalizaires ishyigikiwe na CeO2.Chimie 6, 752–765 (2020).
Feng Yu n'abandi.Kubisabwa ultra-selitifike ya hydrogenation sisitemu ukoresheje neza Pd-Cd nanocubes.Jam.Imiti.sosiyete.142, 962–972 (2020).
Fu, J. n'abandi.Ingaruka zo guhuza imbaraga zongerewe muri catalizike ebyiri.SAU.11, 1952–1961 (2021).
Liu, L. n'abandi.Kumenya ubwihindurize bwa atome itandukanye ya metero imwe na nanoclusters mubihe byitwara: ni izihe mbuga za catalitiki zikora?SAU.9, 10626–10639 (2019).
Yang, N. n'abandi.Amorphous / crystalline heterogeneous palladium nanosheets: synthesis yinkono imwe hamwe na hydrogenation ihitamo cyane.Amashuri yisumbuye.30, 1803234 (2018).
Gao, R. n'abandi.Guhagarika ubucuruzi hagati yo guhitamo nigikorwa cya catisale ya hydrogenation ishingiye kuri nikel muguhuza ingaruka zidasanzwe hamwe na d-band center.Ubumenyi buhanitse.6, 1900054 (2019).
Lee, M. n'abandi.Inkomoko ifatika ya Co-NC itanga hydrogène hydrogène ya nitroaromatike.SAU.11, 3026–3039 (2021).