Muri ubu bushakashatsi, twakoze ubushakashatsi kuri Cu / Ni nanoparticles ikomatanyirizwa mu masoko ya microcarubone mugihe cyo gufatanya na RF sputtering na RF-PECVD, hamwe na plasmon resonance yo hejuru kugirango tumenye gaze ya CO dukoresheje Cu / Ni nanoparticles.Morphologiya yibice.Ubuso bwa morfologiya bwakozweho isesengura mikorobe ya 3D atomike ikoresheje gutunganya amashusho hamwe nubuhanga bwo gusesengura ibice / byinshi.Isesengura mibare ryakozwe hifashishijwe porogaramu ya MountainsMap® Premium hamwe nisesengura ryibice bibiri bitandukanye (ANOVA) kandi ikizamini cyo gutandukanya byibuze.Ubuso bwa nanostructures bufite aho bugarukira no kwisi yose.Ubushakashatsi kandi bwigana Rutherford inyuma yinyuma yerekana ubuziranenge bwa nanoparticles.Ingero zateguwe vuba zahise zerekanwa na chimney ya dioxyde de carbone hanyuma ikoreshwa ryayo nka sensor ya gaze ryakozwe hakoreshejwe uburyo bwa plasmon resonance yaho.Kwiyongera kwa nikel hejuru yumuringa werekanye ibisubizo bishimishije haba mubijyanye na morphologie no kumenya gaze.Ihuriro rya stereo yambere yisesengura rya firime yoroheje yubutaka hamwe na Rutherford inyuma yinyuma ya sprosroscopi hamwe nisesengura rya spekitroscopique irihariye muriki gice.
Ihumana ry’ikirere ryihuse mu myaka mike ishize, cyane cyane kubera inganda zihuse, byatumye abashakashatsi bamenya byinshi ku kamaro ko kumenya imyuka.Ibyuma bya nanoparticles (NPs) byagaragaye ko ari ibikoresho bitanga ibyuma bifata ibyuma bikoresha ibyuma bya gaze 1,2,3,4 kabone niyo ugereranije na firime yoroheje ifite ubushobozi buke bwa plasmon resonance (LSPR), ni ibintu byumvikanisha imbaraga za electronique nini cyane. imirima 5,6,7,8.Nkicyuma kidahenze, gifite ubumara buke, kandi butandukanye, icyuma gifatwa nkikintu cyingenzi nabahanga ninganda, cyane cyane abakora sensor9.Kurundi ruhande, nikel yinzibacyuho yicyuma ikora neza kurusha izindi catalizator10.Porogaramu izwi cyane ya Cu / Ni kuri nanoscale ituma barushaho kuba ingenzi, cyane cyane ko imiterere yimiterere yabo idahinduka nyuma yo guhuza11,12.
Mugihe ibyuma bya nanoparticles hamwe nintera yabyo hamwe na dielectric medium byerekana impinduka zikomeye mumiterere ya plasmon resonance yaho, byakoreshejwe nkibice byo kubaka gaze13.Iyo kwinjiza ibintu byahindutse, ibi bivuze ko ibintu bitatu byuburebure bwumurambararo hamwe na / cyangwa kwinjirira kwinshi kwinshi hamwe na / cyangwa FWHM bishobora guhinduka kuri 1, 2, 3, 4. Ku buso bwa nanostructures, bufitanye isano nubunini buke, ubuso bwaho plasmon resonance muri nanoparticles, aho kuba muri firime yoroheje, ni ikintu cyiza cyo kumenya kwinjiza molekile14, nkuko byagaragajwe na Ruiz n'abandi.yerekanye isano iri hagati yuduce twiza no kumenya neza15.
Kubijyanye no kumenya neza gaze ya CO, ibikoresho bimwe na bimwe nka AuCo3O416, Au-CuO17 na Au-YSZ18 byavuzwe mubitabo.Turashobora gutekereza kuri zahabu nkicyuma cyiza cyegeranijwe hamwe na okiside yicyuma kugirango tumenye molekile ya gaze ya chimique yandujwe hejuru yububiko, ariko ikibazo nyamukuru hamwe na sensor ni uko bitwara mubushyuhe bwicyumba, bigatuma bidashoboka.
Mu myaka mike ishize, microscopi yingufu za atome (AFM) yakoreshejwe nkubuhanga buhanitse bwo kuranga micromorphologie yubuso butatu kuri reaction ya nanoscale ndende 19,20,21,22.Mubyongeyeho, stereo, gusesengura / gusesengura byinshi 23,24,25,26, ubucucike bwimbaraga (PSD) 27 hamwe na Minkowski28 imikorere nibikoresho bigezweho byo kuranga imiterere yubutaka bwa firime zoroshye.
Muri ubu bushakashatsi, bushingiye ku kwinjirira hejuru ya plasmon resonance (LSPR) kwinjizwa, ibimenyetso bya acetylene (C2H2) Cu / Ni NP byashyizwe mubushyuhe bwicyumba kugirango bikoreshwe nka sensor ya gaze ya CO.Rutherford backscatter spectroscopy (RBS) yakoreshejwe mu gusesengura ibihimbano na morphologie bivuye ku mashusho ya AFM, kandi amakarita ya topografiya ya 3D yatunganijwe hifashishijwe porogaramu ya MountainsMap® Premium yiga isotropy yo hejuru hamwe nibindi bipimo bya micromorphologique byose bya microtextures.Ku rundi ruhande, ibisubizo bishya bya siyansi byerekanwe bishobora gukoreshwa mu nganda kandi bifite inyungu nyinshi mu gusaba gaze gaze (CO).Ubuvanganzo butanga raporo kunshuro yambere synthesis, kuranga no gushyira mubikorwa iyi nanoparticle.
Filime yoroheje ya Cu / Ni nanoparticles yateguwe na RF sputtering hamwe na RF-PECVD ifatanije hamwe na 13.56 MHz itanga amashanyarazi.Uburyo bushingiye kuri reaktor ifite electrode ebyiri yibikoresho bitandukanye.Gitoya ni icyuma nka electrode ifite ingufu, nini nini igashyirwa mucyumba cyuma kitagira ingese ku ntera ya cm 5 uvuye hamwe.Shira substrate ya SiO 2 hamwe na Cu intego mucyumba, hanyuma wimure icyumba kuri 103 N / m 2 nkumuvuduko wibanze mubushyuhe bwicyumba, winjize gaze ya acetylene mubyumba, hanyuma ukande kotsa igitutu cyibidukikije.Hariho impamvu ebyiri nyamukuru zo gukoresha gaze ya acetylene muriyi ntambwe: icya mbere, ikora nka gaze itwara umusaruro wa plasma, icya kabiri, mugutegura nanoparticles mukigereranyo cya karubone.Igikorwa cyo kubitsa cyakozwe mu minota 30 ku gipimo cya gaze ya mbere na ingufu za RF zingana na 3.5 N / m2 na 80 W.Noneho gabanya icyuho hanyuma uhindure intego kuri Ni.Igikorwa cyo kubitsa cyagarutsweho ku gitutu cya gaze ya mbere na ingufu za RF zingana na 2.5 N / m2 na 150 W, kimwe.Hanyuma, umuringa na nikel nanoparticles yashyizwe mu kirere cya acetylene ikora umuringa / nikel nanostructures.Reba Imbonerahamwe 1 yo gutegura icyitegererezo no kubiranga.
Amashusho ya 3D yintangarugero yateguwe yanditswe mumwanya wa 1 μm × 1 μ m kare ya scan kare ukoresheje nanometero ya multimode ya atome yingufu za microscope (Digital Instruments, Santa Barbara, CA) muburyo bwo kudahuza kumuvuduko wa 10-20 μm / min .Hamwe na.Porogaramu ya MountainsMap® Premium yakoreshejwe mugutunganya ikarita ya 3D AFM.Ukurikije ISO 25178-2: 2012 29,30,31, ibipimo byinshi bya morphologie byanditswe kandi biraganirwaho, uburebure, intangiriro, ingano, imiterere, imikorere, umwanya hamwe no guhuza.
Ubunini hamwe nibigize ingero zateguwe bishya byagereranijwe kuri gahunda ya MeV ukoresheje ingufu nyinshi za Rutherford backscattering spectroscopy (RBS).Ku bijyanye no gupima gaze, LSPR spectroscopy yakoreshejwe hifashishijwe UV-Vis yerekanwe mu burebure bw’umuraba uri hagati ya 350 na 850 nm, mu gihe icyitegererezo cyabahagarariye cyari muri cuvette y’icyuma ifunze idafite umurambararo wa cm 5.2 n'uburebure bwa cm 13.8. ku gipimo cya 99.9% ya gazi ya gazi (ukurikije igipimo cya Arian Gas Co IRSQ, 1,6 kugeza 16 l / h kumasegonda 180 namasegonda 600).Iyi ntambwe yakozwe mubushyuhe bwicyumba, ubuhehere bwibidukikije 19% na fume hood.
Rutherford backscattering spectroscopy nka tekinike yo gukwirakwiza ion izakoreshwa mu gusesengura ibice bya firime zoroshye.Ubu buryo budasanzwe butuma umubare udakoreshwa hifashishijwe ibipimo ngenderwaho.Isesengura rya RBS ripima ingufu nyinshi (He2 + ion, ni ukuvuga uduce twa alpha) ku rutonde rwa MeV kuri sample na He2 + ion zasubiye inyuma ku mpande runaka.Kode ya SIMNRA ni ingirakamaro mu kwerekana imirongo igororotse n'imirongo, kandi ibyo yandikiranye na RBS igerageza yerekana ubwiza bw'icyitegererezo cyateguwe.Ikirangantego cya RBS cyerekana icyitegererezo cya Cu / Ni NP cyerekanwe ku gishushanyo cya 1, aho umurongo utukura ari igeragezwa rya RBS, naho umurongo w'ubururu ukaba wigana gahunda ya SIMNRA, urashobora kubona ko imirongo ibiri yerekanwe ari nziza amasezerano.Ikintu cyabaye gifite ingufu za 1985 keV cyakoreshejwe kugirango hamenyekane ibintu biri murugero.Ubunini bwurwego rwo hejuru ni nka 40 1E15Atom / cm2 irimo 86% Ni, 0,10% O2, 0.02% C na 0.02% Fe.Fe ifitanye isano numwanda muri Ni intego mugihe cyo gusohora.Impinga ya Cu na Ni igaragara munsi ya 1500 keV, hamwe nimpinga ya C na O2 kuri 426 keV na 582 keV.Intambwe ya Na, Si, na Fe ni 870 keV, 983 keV, 1340 keV, na 1823 keV.
Square ya 3D topografiya AFM amashusho ya Cu na Cu / Ni NP hejuru ya firime irerekanwa mumashusho.2. Byongeye kandi, 2D topografiya yerekanwe kuri buri shusho yerekana ko NPs yagaragaye hejuru ya firime ihurira hamwe muburyo butandukanye, kandi iyi morphologie isa niyasobanuwe na Godselahi na Armand32 na Armand et.33.Nyamara, Cu NP yacu ntabwo yari yegeranijwe, kandi icyitegererezo kirimo Cu gusa cyerekanaga ubuso bworoshye cyane hamwe nimpinga nziza kuruta izikomeye (Ishusho 2a).Ibinyuranye na byo, impinga zifunguye ku ngero za CuNi15 na CuNi20 zifite imiterere igaragara kandi ifite ubukana bwinshi, nkuko bigaragazwa n'uburebure bw'uburebure ku gishushanyo cya 2a na b.Impinduka zigaragara muri morphologie ya firime yerekana ko ubuso bufite imiterere yimiterere yimiterere ya topografiya, bigira ingaruka kumwanya wo kubika nikel.
AFM amashusho ya Cu (a), CuNi15 (b), na CuNi20 (c) firime yoroheje.Ikarita ikwiye ya 2D, gukwirakwiza hejuru hamwe na Abbott Firestone imirongo yashyizwe muri buri shusho.
Impuzandengo y'ibinyampeke bya nanoparticles yagereranijwe uhereye kuri diametre yo gukwirakwiza diameter yabonetse mugupima nanoparticles 100 ukoresheje Gaussian nkuko bigaragara muri FIG.Birashobora kugaragara ko Cu na CuNi15 bifite ingano zingana zingana (27.7 na 28.8 nm), mugihe CuNi20 ifite ibinyampeke bito (23.2 nm), bikaba hafi yagaciro kavuzwe na Godselahi nabandi.34 (hafi 24 nm).Muri sisitemu ya bimetallic, impinga yubutaka bwa plasmon resonance irashobora guhinduka hamwe nimpinduka mubunini bwingano35.Ni muri urwo rwego, dushobora gufata umwanzuro ko igihe kirekire cyo kubitsa kigira ingaruka ku buso bwa plasmonic ya firime ya Cu / Ni yoroheje ya sisitemu yacu.
Ingano nini yo gukwirakwiza (a) Cu, (b) CuNi15, na (c) CuNi20 ya firime yoroheje yakuwe mubutaka bwa AFM.
Ubwinshi bwimiterere nabwo bugira uruhare runini muburyo bwimiterere yimiterere yimiterere yimiterere ya firime.Imbonerahamwe 2 irerekana uburebure bushingiye ku burebure bwa topografiya bujyanye n'ikarita ya AFM, bushobora gusobanurwa nigihe cyagaciro cyo kugereranya (Sa), skewness (Ssk), na kurtose (Sku).Indangagaciro za Sa ni 1.12 (Cu), 3.17 (CuNi15) na 5.34 nm (CuNi20), zemeza ko film zigenda zikomera hamwe no kongera igihe cyo kubitsa.Indangagaciro ziragereranywa nizo zavuzwe mbere na Arman et al.33 (1-4 nm), Godselahi et al.34 (1-1.05 nm) na Zelu et.36 (1.91–6.32 nm), aho bisa gusohora byakozwe hakoreshejwe ubu buryo bwo kubitsa firime za Cu / Ni NPs.Nyamara, Ghosh et al.37 yashyize Cu / Ni multilayers kuri electrodeposition kandi itangaza agaciro gakomeye, bigaragara ko kari hagati ya 13.8 na 36 nm.Twabibutsa ko itandukaniro mubikorwa byuburyo bwuburyo butandukanye bishobora kuganisha kumiterere yimiterere hamwe nuburyo butandukanye.Nubwo bimeze bityo ariko, birashobora kugaragara ko uburyo bwa RF-PECVD bugira akamaro mukubona firime za Cu / Ni NPs zifite ubukana butarenze 6.32 nm.
Kubijyanye nuburebure bwuburebure, urwego-rwohejuru rwibarurishamibare ibihe Ssk na Sku bifitanye isano na asimmetrie nibisanzwe byo gukwirakwiza uburebure, kimwe.Indangagaciro zose za Ssk ninziza (Ssk> 0), byerekana umurizo muremure wiburyo38, ushobora kwemezwa numwanya wo gukwirakwiza uburebure muri inset 2. Byongeye kandi, imyirondoro yose yuburebure yari yiganjemo impinga ikarishye 39 (Sku> 3) , kwerekana ko umurongo Uburebure bwo gukwirakwiza butaringaniye kurenza inzogera ya Gaussian.Umurongo utukura muburebure bwo gukwirakwiza ni Abbott-Firestone 40 umurongo, uburyo bukwiye bwibarurishamibare bwo gusuzuma ikwirakwizwa risanzwe ryamakuru.Uyu murongo uboneka mubiteranyo byuzuye hejuru yuburebure bwa histogramu, aho impinga ndende ninkono ndende ijyanye nibiciro byabo (0%) nibiciro ntarengwa (100%).Iyi mirongo ya Abbott-Firestone ifite S-shusho nziza kuri y-axis kandi mubihe byose byerekana kwiyongera gahoro gahoro kwijanisha ryibintu byambukiranya agace kegeranye, guhera kumasonga akomeye kandi akomeye.Ibi biremeza imiterere yimiterere yubuso, byibasiwe cyane nigihe cyo kubika nikel.
Imbonerahamwe 3 irerekana ibipimo bya ISO byihariye bijyanye na buri buso bwabonetse mumashusho ya AFM.Birazwi neza ko agace kagereranijwe kubintu (Smr) hamwe na konte yo kugereranya ibintu (Smc) nibipimo byimikorere 29.Kurugero, ibisubizo byacu byerekana ko akarere kari hejuru yindege ya median yubuso bwuzuye hejuru muri firime zose (Smr = 100%).Nyamara, indangagaciro za Smr ziboneka muburebure butandukanye bwuburinganire bwa coefficient ya terrain41, kuva ibipimo Smc bizwi.Imyitwarire ya Smc isobanurwa nubwiyongere bwuburakari buva kuri Cu → CuNi20, aho dushobora kubona ko agaciro gakabije kabonetse kuri CuNi20 gatanga Smc ~ 13 nm, mugihe agaciro ka Cu kangana na 8 nm.
Guhuza ibipimo bya RMS gradient (Sdq) hamwe niterambere ryahantu hagereranijwe (Sdr) ni ibipimo bijyanye nuburinganire bwimiterere kandi bigoye.Kuva kuri Cu → CuNi20, indangagaciro za Sdq ziri hagati ya 7 na 21, byerekana ko amakosa ya topografiya muri firime yiyongera mugihe Ni layer yashyizwe kuminota 20.Twabibutsa ko ubuso bwa CuNi20 butameze neza nkubwa Cu.Mubyongeyeho, byagaragaye ko agaciro ka parameter Sdr, kajyanye nuburemere bwa microtexture yo hejuru, yiyongera kuva Cu → CuNi20.Nk’uko ubushakashatsi bwakozwe na Kamble et al.42 bubivuga, ubunini bwa microtexture yo hejuru bwiyongera hamwe no kwiyongera kwa Sdr, byerekana ko CuNi20 (Sdr = 945%) ifite microstructure igoye cyane ugereranije na firime Cu (Sdr = 229%)..Mubyukuri, ihinduka rya microscopique igoye yimiterere igira uruhare runini mugukwirakwiza no kumiterere yimisozi miremire, ishobora kugaragara uhereye kumiterere yibiranga uburinganire bwimisozi (Spd) hamwe nimibare isobanura impinduramatwara (Spc).Ni muri urwo rwego, Spd yiyongera kuri Cu → CuNi20, byerekana ko impinga zitunganijwe neza hamwe no kwiyongera kwa Ni layer.Mubyongeyeho, Spc nayo yiyongera kuva Cu → CuNi20, byerekana ko imiterere yimpinga yubuso bwikitegererezo cya Cu iringaniye cyane (Spc = 612), mugihe iya CuNi20 ikarishye (Spc = 925).
Umwirondoro utoroshye wa buri firime urerekana kandi uburyo butandukanye butandukanye muburyo bwo hejuru, hejuru, hamwe nuduce twubuso bwubuso.Uburebure bwimbere (Sk), kugabanuka hejuru (Spk) (hejuru yinturusu), hamwe ninkono (Svk) (munsi yintangiriro) 31,43 ni ibipimo bipimwa perpendikulari hejuru yindege yo hejuru30 kandi byiyongera kuva Cu → CuNi20 bitewe na Ubuso bukabije Ubunini bugaragara.Mu buryo nk'ubwo, ibikoresho byo hejuru (Vmp), ibikoresho byingenzi (Vmc), icyuho cyuzuye (Vvv), hamwe nubunini bwibanze (Vvc) 31 byerekana icyerekezo kimwe nkuko indangagaciro zose ziyongera kuva Cu → CuNi20.Iyi myitwarire yerekana ko ubuso bwa CuNi20 bushobora gufata amazi menshi kurenza izindi ngero, nibyiza, byerekana ko ubu buso bworoshye gusiga44.Kubwibyo, twakagombye kumenya ko uko ubunini bwurwego rwa nikel bwiyongera kuva CuNi15 → CuNi20, impinduka mumiterere yimiterere yimiterere yimiterere yimiterere yimiterere yimiterere yimiterere ya morfologiya, bigira ingaruka kuri microtexture yo hejuru hamwe nuburyo bwa firime.
Isuzuma ryujuje ubuziranenge bwa microscopique yubuso bwa firime ryabonetse mukubaka ikarita ya topografiya ya AFM ukoresheje software yubucuruzi ya MountainsMap45.Guhindura byerekanwe ku gishushanyo cya 4, cyerekana umusego uhagarariye hamwe na polar ikibanza cyerekeranye n'ubuso.Imbonerahamwe 4 irerekana umwanya hamwe nuburyo bwo guhitamo.Amashusho ya shobuja yerekana ko icyitegererezo cyiganjemo sisitemu isa na ya miyoboro hamwe na homogeneity ya ruhago.Nyamara, ibipimo byuburebure bwimbitse (MDF) hamwe nuburinganire bwimbitse (MDEF) byiyongera kuva Cu kugera kuri CuNi20, byemeza ubushakashatsi bwibanze kubyerekeranye nubushobozi bwa CuNi20.Twabibutsa ko ingero za Cu (Igishusho 4a) na CuNi15 (Igishusho 4b) zifite umunzani umwe wamabara, ibyo bikaba byerekana ko microtexture yubuso bwa Cu itigeze ihinduka cyane nyuma yuko film ya Ni ishyizwe kuri 15 min.Ibinyuranye, icyitegererezo cya CuNi20 (Igishusho 4c) cyerekana iminkanyari ifite umunzani wamabara atandukanye, ifitanye isano nagaciro kayo ka MDF na MDEF.
Grooves hamwe nubuso bwa isotropy ya microtextures ya Cu (a), CuNi15 (b), na CuNi20 (c).
Igishushanyo cya polar.4 irerekana kandi ko microtexture yo hejuru itandukanye.Biragaragara ko gushira kwa Ni layer bihindura cyane imiterere yimiterere.Microtextural isotropy yabazwe yintangarugero yari 48% (Cu), 80% (CuNi15), na 81% (CuNi20).Birashobora kugaragara ko gushira kwa Ni layer bigira uruhare mu gushiraho microtexture nyinshi ya isotropic, mugihe firime imwe ya Cu ifite microtexture ya anisotropique.Mubyongeyeho, umwanya wiganje wa CuNi15 na CuNi20 uri hasi kubera uburebure bwa autocorrelation ndende (Sal) 44 ugereranije na Cu.Ibi kandi byahujwe nicyerekezo gisa nicyerekezo cyerekanwe nizi ngero (Std = 2,5 ° na Std = 3.5 °), mugihe agaciro kanini cyane kanditswe kuri sample ya Cu (Std = 121 °).Ukurikije ibisubizo, firime zose zerekana intera ndende itandukanye bitewe na morphologie zitandukanye, imyirondoro yabantu, hamwe nubusambo.Rero, ibisubizo byerekana ko igihe cyo kubika Ni layer kigira uruhare runini mugushinga CuNi bimetallic sputtered surface.
Kugira ngo wige imyitwarire ya LSPR ya Cu / Ni NPs mu kirere ku bushyuhe bw’icyumba no mu masoko atandukanye ya gaze ya CO, spekiteri yo kwinjiza UV-Vis yashyizwe mu burebure bwa 350-800 nm, nkuko bigaragara ku gishushanyo cya 5 kuri CuNi15 na CuNi20.Mugutangiza ubucucike butandukanye bwa gazi ya CO, impinga nziza ya LSPR CuNi15 izaguka, iyinjizwa rizakomera, kandi impinga izahinduka (redshift) ijya kumurongo muremure, kuva kuri 597.5 nm mumyuka uva kuri 16 L / h 606.0 nm.CO itemba amasegonda 180, 606.5 nm, CO itemba 16 l / h kumasegonda 600.Ku rundi ruhande, CuNi20 igaragaza imyitwarire itandukanye, bityo kwiyongera kwa gazi ya CO bituma igabanuka ryumwanya wa LSPR w’umurambararo (blueshift) uva kuri 600.0 nm mu kirere ugera kuri 589.5 nm kuri 16 l / h CO itemba kuri 180 s .16 l / h CO itemba amasegonda 600 kuri 589.1 nm.Kimwe na CuNi15, turashobora kubona impinga nini kandi byongera ubukana bwa CuNi20.Turashobora kugereranya ko hamwe no kwiyongera kwubugari bwurwego rwa Ni kuri Cu, kimwe no kwiyongera k'ubunini n'umubare wa nanoparticles ya CuNi20 aho kuba CuNi15, Cu na Ni byegerana, amplitude yo guhindagurika kwa elegitoronike ariyongera , kandi, kubwibyo, inshuro ziriyongera.bivuze: uburebure bwumurongo bugabanuka, ihinduka ryubururu ribaho.
Igihe cyo kohereza: Kanama-16-2023