Posted on Authorea 28 Sep 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.160133580.03550052 — This a preprint and has not been peer reviewed. Data may be preliminary. .Introduction 1. metal supported of design sites. the active for Keywords: as important species are metallic findings afford These that alleviated. catalysts effectively is poisoning hydrogen Ru/CeO a result, a Lin Lin Bingyu Activation CO by Induced Catalysts Ceria-Supported Ruthenium of Activity Synthesis Ammonia Enhanced n cieoye,rsligi h omto feeto-nihdRu electron-enriched Ce of increases formation reaction also the Ru/CeO a but in a for species, resulting of catalyst Ru oxygen, the activation metal active of CO in a and that exposure existed of show that and species performance we catalysts degree the metal Here of reduction hindering of sites. preparation consequently metallic proportion lowered, the requires the is for that SMSI, state important With metallic is of (SMSI). form temperature interaction high metal-support at strong show treatment hydrogen +86 and Tel: catalysts, 0591-83738808; +86 Abstract: Fax: Jiang); (Lilong Engineering, [email protected] Chemical Lin); 0591-83731234 of (Bingyu [email protected] College Catalyst, E-mail: Au, Fertilizer Chak-tong China Fujian, Chemical Lin, 350002, of Jianxin Fuzhou University, Center Wang, Fuzhou Research Xiuyun Ni, Engineering Jun National Li, Chunyan Wu, Yuyuan Jiang* Fang, Lilong Biyun by Lin*, Induced Bingyu Catalysts effectively Ruthenium sites. is Ceria-Supported active poisoning Activation as of hydrogen species CO Activity metallic of Synthesis afford effect that Ammonia catalysts ill Enhanced metal the supported of and design activity, the and synthesis for (OV) important ammonia vacancy are only oxygen high findings not concentration, catalyst These shows Ce3+ Ru/CeO2 activation alleviated. Ru increases a electron-enriched of CO also activation of but after CO formation performance species, that catalyst the the show Ru hindering in we With of consequently resulting Here (SMSI). lowered, exposure oxygen, sites. is interaction and active metallic state degree metal-support requires metallic reduction that strong of reaction the show form a enhances that the for in catalyst catalysts existed metal of a species preparation of metal the of for proportion the important treatment SMSI, hydrogen is and catalysts, temperature metal ceria-supported high of at performances catalytic the affect strongly interactions Metal–support Abstract 2020 28, September 2 1 ainlEgneigRsac etro hmclFriie Catalyst Fertilizer Chemical University of Fuzhou Center Research Engineering National 1 hktn Au Chak-tong , ea–upr neatossrnl ffc h aayi efracso ei-upre metal ceria-supported of performances catalytic the affect strongly interactions Metal–support moi ytei,C ciain ea–upr neato,Ru/CeO interaction, Metal–support activation, CO synthesis, Ammonia 1 iu Fang Biyun , 2 aaytatrC ciainsoshg moi ytei ciiy n h l ffc of effect ill the and activity, synthesis ammonia high shows activation CO after catalyst 1 n iogJiang Lilong and , 1 uunWu Yuyuan , 2 1 hna Li Chunyan , 1 δ pce n Ru and species - 1 u Ni Jun , 3+ δ- δ ocnrto,oye aac (O vacancy oxygen concentration, -VC3 ie.A eut Ru/CeO2 a result, a As sites. --OV-Ce3+ pce n Ru and species 1 iynWang Xiuyun , 2 aaytntol nacsthe enhances only not catalyst 2 δ- -O V -Ce 1 Jianxin , 3+ ie.As sites. V ) Posted on Authorea 28 Sep 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.160133580.03550052 — This a preprint and has not been peer reviewed. Data may be preliminary. ino useiscudb nacdb Oatvto,laigt infiatehneeto Ce of enhancement significant to leading activation, Ru CO species, by enhanced be (O could synthesis. vacancy ammonia species Ru/CeO Ru for for of that reactions demonstrate tion the detrimental we reactions as work, The catalytic such present for the state. sites, pronounced In active metallic be would as in performance exist species catalytic metallic that on require sites species metallic that metal for of of diminution especially the proportion SMSI, of the effect with particles. lower catalyst would Pt a support of of reducible size. size preparation reduction, a small the the temperature as of for by high decreased clusters required governed oxidation metal is was particles. with CO temperature Pt ceria catalysts for reduction and and CO activity higher ceria species in the a between Pt activities that and sites between high the ceria, interfacial showed transfer was of of effect. clusters charge reducibility decrease SMSI H-spillover Ru the the and that of lowered of SMSI observed form particles result between the Pt balance increase al. in large a Ru and et that was Moreover, interaction Guo there because particles. metal-support reactant methanation sites. Ru enhance of larger interfacial can properties with of one adsorption samples number Ru/CeO loading, of the for metal alteration maximizing strongest to of by due decrease economy synthesis the atom ammonia Through for N activity gases. of catalytic dissociation the and affect adsorption the including species. a steps, exerting reaction several consequently would H of sites products, catalysts. consists perimeter or metal synthesis interfacial reactants oxides-supported Ammonia the of of at activities spillover the species and in on metal reaction changes influence and of desorption, strong support result adsorption, electron between a the and contact as affect close perturbation performance gases. or electronic catalytic reactant charges is of of excess there enhancement properties the to support, dissociation to and/or oxide leading due adsorption reducible species, is acidity and metal Lewis SMSI species. of catalytic species inducing rearrangement metal effect. metal by on between an activities of effect catalytic such EMSI structure enhance cause strong or electronic could would the a which that changing suboxides, has factors by and/or known particles species are metal metal of perimeter coverage interfacial and of oxides nature reducible and between interaction performance. the general, much In Ce attracted property, have electronic catalysts ceria. unique of the Ru capacity to ceria-supported adsorption due Recently, synthesis ammonia year; production. in every ammonia interest energy for world’s process the sustainable of energy. 1-2% hydrogen consumed of carrier a (NH Ammonia n h oia ut-ei egtrtows1.Aprino h bandRuNO 500 obtained the or of 250 portion at Aldrich), A gas w/v, CO 1%. (1.5% was in solution 550 ratio nitrate at weight hydrogen nitrosyl Ru-to-ceria in ruthenium(III) nominal with the ceria and of impregnation wetness incipient CeO Preparation Catalyst 2.1. Section alleviated. significantly Experimental poisoning 2. hydrogen of effect ill the with Ru/CeO the and property, adsorption 2 oeue,terato fNadHaos n h eopino nece ae (N gases unreacted of desorption the and atoms, H and N of reaction the molecules, 2 a rprdacrigt h rcs ecie elsewhere. described process the to according prepared was 26-27 V δ- n cieoye ocnrto htaebnfiilfrtefraino lcrnerce Ru electron-enriched of formation the for beneficial are that concentration oxygen active and ) ti niindta n hnei ucraitrcino ucractls ol strongly would catalyst Ru/ceria a of interaction Ru-ceria in change any that envisioned is It -O 12-14 3 V sntol nipratceia o h ytei fNcnann compounds, N-containing of synthesis the for chemical important an only not is ) -Ce togmtlspotitrcin(MI,eetoi ea–upr neato (EMSI), interaction metal–support electronic (SMSI), interaction metal-support Strong ° 3+ o n shri eoe sRu/CeO as denoted herein is and h 6 for C 2 ie n ufc cieoye.A eut hr ssgicn hneo hydrogen of change significant is there result, a As oxygen. active surface and sites ihsnl uaos n yrgnsilvrwsmr rnucdfrcatalyst for pronounced more was spillover hydrogen and atoms, Ru single with ° o ooti Ru/CeO obtain to h 2 for C 7-11 31 2-3 n h eoaino naslto fmtlseisb uoie rmthe from suboxides by species metal of encapsulation or decoration the and h rcs fctltcamnasnhssfo yrgnadnitrogen and hydrogen from synthesis ammonia catalytic of process The 2 aaytatrC ciainsoshge moi ytei activity, synthesis ammonia higher shows activation CO after catalyst 30-31 notntl,teewssneigo ea lsesduring clusters metal of sintering was there Unfortunately, 4-6 2 2 hsi sugn odvlpa ffiin aaytand catalyst efficient an develop to urgent is it thus aaytterdcindge n h xoe propor- exposed the and degree reduction the catalyst 2 15-19 C,where -Cx, 2 20-21 12, utemr,a euto hretransfer charge of result a as Furthermore, 2 H h eto RuNO of rest The -H. 0 32 10, nteohrhn,teacmlto of accumulation the hand, other the On 22-25 x 4+ h RuNO The steC ramn temperature. treatment CO the is 29 /Ce yhc ta.soe htthe that showed al. et Lykhach 3+ 28 eo blt n hydrogen and ability redox 3 aze ta.proposed al. et Ganzler /CeO 3 3 /CeO 2 /CeO 14 2 n H and a bandby obtained was twsobserved was It 2 2 a reduced was 2 a treated was 3+ n NH and ) 1 oxygen , u also but 2 and δ- x 2 Posted on Authorea 28 Sep 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.160133580.03550052 — This a preprint and has not been peer reviewed. Data may be preliminary. eoe sRu/CeO as denoted Ru/CeO Afterwards, / xhnerato a odce naMcoeiisAtCe I22 qimn.Frt 0 gof mg 100 First, equipment. 2920 550 II at AutoChem Micromeritics treated a was on sample conducted a was reaction exchange D/H Characterization Catalyst 2.2. ocra hnmnnsmlrt htosre vrcraspotdC aayta eotdb Parastaev by reported as spillover catalyst and cm Co species Ru/CeO Ru ceria-supported of over metallic dissociation oxidize investigations observed the could that to oxygen to lead al. produced would similar the et temperature phenomenon and activation a surface, of ceria, Ru increase the to further on A molecules degC. CO 150 of at CO by activated be activation. Ru CO reduced to during RuNO corresponding reduced temperature Ru/CeO bands been the the distinct has over in The species observed peak Ru be consumption the can hydrogen of degC weak most 400 and that to broad 70 a of only in However, range is S4). H which of (Figure the ceria, detection respectively in no on degC is 200 species at There Ru S3). of (Figure 3d catalysts. support. RuNO dispersion as-prepared respectively Ru ceria Ru The well two of of S2). indicating shows (Figure phase area images catalyst species, crystal HAADF-STEM surface aberration-corrected Ru the the specific m with to alter consistent the 81–86 ascribable not on do of peaks effect treatments range diffraction slight the the CeO that a fluorite in suggesting only cubic are of have catalysts patterns conditions Ru XRD treatment prepared adopted of the areas BET The was Characterization ammonia Structure produced ICS-600); 3.1 The Scientific, Discussion (Thermo obtained. and condition. chromatography be Results ion selected could by values a 3. TOF analyzed under and then size h rates and similar reaction 3 solution of the than subsequently, acid sand more sulfuric quartz for by with maintained diluted trapped work. was was this in mesh) reaction adopted = 32–60 the conditions diameter g, the (inner under (0.20 reactor limitations H catalyst steel diffusion stoichiometric the stainless a in fixed-bed reaction, reduced flow to and continuous Prior a in mm). out 12 carried was (DRIFTS), synthesis Ammonia spectroscopy transform Evaluation Catalyst Fourier 2.3. infrared (H reflectance reduction H diffuse temperature-programmed Raman, 3.3%N hydrogen a N (TEM), to switched including microscopy was degC. gas characterizations 600 feed to the Other heated Finally, was sample exposure. catalyst for the selected D and gas II to AutoChem the exposed same was in the sample degC on fresh out The carried instrument. was 2920 measurement (TPSR) 3.3%N reaction a surface spectrometer. to Temperature-programmed HPR-20 exposed was Analytical sample Hiden the a h, by 1 D recorded for to Ar exposed with purged was sample the Afterwards, 2 hmsrto,aegvni uprigInformation. Supporting in given are chemisorption, -1 31 nteDIT pcr fteRu/CeO the of spectra DRIFTS the in 3 /CeO sarsl,tepeec frteimoiecnb eetdi h RFS(iueS)o XPS or S5) (Figure DRIFTS the in detected be can oxide ruthenium of presence the result, a As 2 xoe oC t10dg Fgr 5,idctn htR xdso h ei ufc can surface ceria the on oxides Ru that indicating S5), (Figure degC 150 at CO to exposed 2 -C 2 2 -C TRpol fRuNO of profile -TPR x x 0 35-38 10, H. 2 5/2 C0 Fgr 6.Teeaetredsic Obnsa 95 03ad2125 and 2063 1985, at bands CO distinct three are There S6). (Figure -C500 a eue nhdoe t550 at hydrogen in reduced was ek t214e n 8. Vta r hrceitco Ru of characteristic are that eV 282.8 and eV 281.4 at peaks ° o nhdoe,te ugdwt radcoe ont 400 to down cooled and Ar with purged then hydrogen, in h 6 for C toghdoe euto eka 2 eCadawa hudrpeak shoulder weak a and degC 128 at peak reduction hydrogen Strong 2 –N 2 2 hs JPS3-34 a eosre o l ape Fgr S1), (Figure samples all for observed be can 34-0394) (JCPDS phase 2 a itr t50dg o .Teewr oetra n internal and external no were There h. 6 for degC 550 at mixture gas hssrto,Xrydffato XD,tasiso electron transmission (XRD), diffraction X-ray physisorption, 2 n eda 400 at held and 2 3 H Ru/CeO -H, /CeO 0 pce a eosre nteDIT pcr ae over taken spectra DRIFTS the in observed be can species 2 2 TR,Xrypooolcrnsetocp (XPS), spectroscopy phototoelectron X-ray -TPR), 2 3 a easge oterdcino RuO of reduction the to assigned be can r rN or Ar, , 2 2 C5HadRu/CeO and -C250H 2 C5 n Ru/CeO and -C250 -10%H ° ° o ,adtea-bandctlssare catalysts as-obtained the and h, 6 for C o .Atrcoigt 50 to cooling After h. 1 for C 33-34 2 t40dg o ,adte oldt 50 to cooled then and h, 1 for degC 400 at 2 aayteauto a odce after conducted was evaluation Catalyst A itr,adtems inl were signals mass the and mixture, -Ar 2 g -1 TbeS) niaigthat indicating S1), (Table 2 C0 aayt,indicating catalysts, -C500 2 C0Hctlss(Figure catalysts -C500H 2 -10%H 4+ 2 ° nD in C A mixture, -Ar x n Ru and n CeO and 3 /CeO 2 and 6+ ° C. 2 2 , , Posted on Authorea 28 Sep 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.160133580.03550052 — This a preprint and has not been peer reviewed. Data may be preliminary. Ce 1 Figure Ce of 3d (O vacancies of oxygen catalysts. pairs and two ceria-supported oxygen H as-prepared peaks, lattice of the ten of of into characteristic spectra deconvoluted 1s are be O can and Ce 3d profiles 3d to their Ru 3d and 3d, Ce eV) Ce 884.8 The XPS the on catalysts. samples. are species Ru all 1a–c CO for Figures adsorbed metal in linearly ruthenium (Ru Presented and metal, Ru oxide oxidized Ru ruthenium partially to on of bonded species coexistence species carbonyl the CO and particles, bridge-type Ru to reduced assignable are which S7), stehgeti h muto ei eet n Ru and defects ceria of amount 500 the at activation in CO highest of the case is the of in increase so an especially in is Ru results and species Ru defects of ceria presence Ru the that the results. obvious previous to is with It agreement in fitting. defects, peak ceria of means by calculated was Ru/CeO Ru/CeO respectively. cm (2LO), mode 250 optical at longitudinal peaks second-order Four and (D), cm 2. 1180 mode Figure and induced CeO in 587 of shown 250, are spectrum at results Raman peaks the the weak and in samples, found of be defects can the peaks study to conducted was experiment Raman hin- Ru/CeO the would (Ru for of Ru/CeO follows the treatment for that Then hydrogen 60.6% oxygen subsequent and S8). of the (Figure spillover during ceria, mechanism samples the spillover CO-activated by and hydrogen covered surface the being Ru following Ce from on preferentially CO of species of amount Ru dissociation der larger The a energy. the of binding On presence metal, (Ru a reduction. the Ru/CeO Ru hydrogen thus species case, to and after oxide, electrons Ru a exists provide Ru electron-enriched such still can of of oxide ceria In reduced reduction ruthenium formation partially of the the and form hinder vacancies to the oxygen suboxides would in the by suboxides hand, species metal The other Ru Ru of of (0.0075). proportion treatment encapsulation high the heat as without ruthenium well (I sample to ratio as ceria intensity vacancies 3d from oxygen Ce spillover of oxygen formation S8). reverse the (Figure catalysts, to Ru leads ceria-supported oxides of treatment hydrogen ing Ru Ru metallic of istic Ru/CeO the for eV 3d Ru the Besides h rnfro lcrnfo useist CeO to species Ru from Ru/CeO electron the of in transfer unchanged the remains mode F2g fluorite lcrntase sfo ei oR species. Ru to ceria from is transfer electron 3+ 0 /(Ru 2 /(Ce 3+ 4+ srdcn gn,teueo Ocnla opoone ei euiiiyo ei-upre metal ceria-supported of reducibility ceria pronounced to lead can CO of use the agent, reducing as /(Ce 2 2 0 pce.TeO1 pcr a edcnoue notopasa 2. Vad512e,which eV, 531.2 and eV 529.0 at peaks two into deconvoluted be can spectra 1s O The species. 9 42 29, H ugsigta hr seeto rnfrfo useist CeO to species Ru from transfer electron is . there that suggesting -H, 3+ δ- +Ru 49 -O 2 +Ce P pcr fa-rprdR aayt a e3,()R d n c s (d) 1s; O (c) and 3d, Ru (b) 3d, Ce (a) catalysts Ru as-prepared of spectra XPS 1 43-44 31, 3+ h I The C5H(.1 n Ru/CeO and (0.01) -C250H 2 V C0Hsmlswudrsl nices fRu of increase in result would samples -C500H n+ +Ce hsteCe the Thus -Ce -1 4+ ai fRu/CeO of ratio ) (587+1180) n 6 cm 460 and 5/2 3+ ,O ), 4+ 0 2 sarsl,tepooto fepsdR pce ol erae n h u3 to 3d Ru the and decrease, would species Ru exposed of proportion the result, a As δ- . H Ru/CeO -H, 0 35-38 10, n O and ) ek frteimoie (Ru oxides ruthenium of peaks -O odo Ru/CeO of bond 3/2 u3d Ru 2 β C5HadRu/CeO and -C250H / V O -Ce etrsaeasge oCe to assigned are features 3+ α /I /I n (Ru and 460 β 3+ eas oeR pce scvrdb uoie rgntdfr ei,the ceria, form originated suboxides by covered is species Ru some Because -1 Ce3d n O and / O hf olwrwvnme fe h nrdcino useisit ei for ceria into species Ru of introduction the after wavenumber lower to shift od infiatyices o Ru/CeO for increase significantly bonds ai htrflcsdfc ocnrto uha xgnvacancies, oxygen as such concentration defect reflects that ratio 2 α s005 o Ru/CeO for 0.0056 is ) C5HadRu/CeO and -C250H , -1 5 41 35, V 2 orsodn oscn-re rnvreaosi oe(T) defect- (2TA), mode acoustic transverse second-order to corresponding , 0 Hi uhsalr ny17,wihcnb eae oSS.Dur- SMSI. to related be can which only11.7%, smaller, much is -H ocnrtoso h Oatvtdsmls seautdb h ratios the by evaluated as samples, activated CO the of concentrations +Ru 2 Haiigfo ea–upr interaction. metal–support from arising -H r ihrta hs fRu/CeO of those than higher are 2 C0H(0.0095). -C500H δ- 31 )/(Ru 2 C0H epciey n h I the and respectively, -C500H, n h rsneo umtlcue h euto fceria of reduction the causes metal Ru of presence the and 0 35 10, 2 ° sihbtd hc scnitn ihteXSrsl that result XPS the with consistent is which inhibited, is 2 0 0 .Aogtetrepeae aayt,Ru/CeO catalysts, prepared three the Among C. togpa t40cm 460 at peak strong a : +Ru +Ru δ- 4 3+ 4+ h w ek t65cm 695 at peaks two The -O 2 δ- C5HadRu/CeO and -C250H ,i iewt h bevto vrA catalyst. Au over observation the with line in ), 3+ δ- 2 δ- V pce,adteohrsxC dpasaeascribed are peaks 3d Ce six other the and species, n Ru and C0Hctlss(iue1) hc scharacter- is which 1b), (Figure catalysts -C500H 2 )/(Ru -Ce +Ru H hc slwrta hto h corresponding the of that than lower is which -H, n xgnvcnyoe h Ru/CeO the over vacancy oxygen and 3+ V δ- n+ ,respectively. ), 0 asn hf fR 3d Ru of shift a causing , 6+ od.Rfrigt uecra h ekof peak the ceria, pure to Referring bonds. +Ru nest ratios. intensity ) ,teei e u3d Ru new a is there ), δ- +Ru n 2 + 2 C5HadRu/CeO and -C250H ,respectively, ), H(iue1d). (Figure -H n+ -1 2 Ru3d 53,41 35-36, C0Hcss niaigthat indicating cases, -C500H -1 ai nrae pt 71.6% to up increases ratio ) floieFgmd)adthree and mode) F2g (fluorite 2 n 7 cm 970 and /I 8 5 1 46-48 41, 35, 28, o h yrgnreduced hydrogen the for 8 5 51 35, 28, Ce3d oprdt h use the to Compared ai loincreases also ratio 5/2 7 39-40 37, 5/2 5/2 -1 h ubrof number The 804e and eV (880.4 ekt lower to peak r assignable are eka 279.8 at peak ,45 8, 2 h Raman The C0H It -C500H. 1 6 50-51 46, 41, indicating 2 2 -C250H -C500H leading 45 Posted on Authorea 28 Sep 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.160133580.03550052 — This a preprint and has not been peer reviewed. Data may be preliminary. nraeo ecinpesr om1t P ed oamr infiatehneeto h ciiyfor Ru/CeO activity of N performance the the of 3 affects property. mainly enhancement Figure activation adsorption/desorption significant CO hydrogen that more the deduced a changing be by to the also can catalysts Hence leads It MPa catalysts. S10). Ru 7 (Figure for catalyst to (Ru/CeO poisoning 1 catalysts hydrogen Ru form CO-activated of the pressure problem reaction the alleviate of can increase activation CO that suggesting N of Ru/CeO orders for (-0.53) reaction the The NH among energy. of activity activation orders of synthesis change ammonia Ru/CeO the for to in 1.3 attributed and discrepancy directly mol significant be kJ the cannot 72 three that and suggesting 67 respectively, S2). 60, (Table C500H, are literatures in energies activation reported catalysts estimated Ru/CeO Ru S9, of Figure those in to comparable are activation Ru/CeO CO of g rates mmol (4.06 The the H all over only. for orders reduction activities g catalytic reaction hydrogen mmol of the to enhancement and subjected to rate leads that Ru/CeO synthesis temperature the reaction ammonia and of of samples, increase dependence The temperature catalysts. prepared the and reveals reducibility 3 the Figure that Ru/CeO performance deduced of synthesis activation be Ammonia CO can 3.2 after it increase Ce results, significantly of would Raman enhancement species significant and Ru XPS of DRIFTS, exposure the combining Overall, ratios. 2 Figure rhdoe oeue(iueS1.ADHecag ecinwsdsge oepoeteasrto nature water adsorption of the form D explore the After to in designed catalysts. either was Ru 3.3%N reaction temperature the exchange raised D/H on a A hydrogen at groups). of S11). species OH (Figure hydrogen (two molecule of products hydrogen desorption homolytic or the and groups. facilitates OH) hydroxyl and species generate (Ce-H and Ru to products adsorption support heterolytic the form as the to well to as spillover catalysts can the atoms of H activation reactants. the of investigate Ru/CeO desorption to of employed performance were the techniques enhances activation ization CO why understand better catalysts To Ru of property Adsorption 3.3 h muto cieoye nteC ciae aayt r ihrta hto h hydrogen-treated the on and that analysis; than CO-TPR neighboring higher by with are confirmed reacting catalysts CO is by activated two catalysts sites CO Moreover, Ru Ru the from the S12). on HDO desorb on (Figure oxygen would of oxygen one active that active signals of former of the amount the presence Furthermore, the on The species phase. atoms. D gaseous oxygen are of from amount HDO species and larger hydrogen HD a the of concentrations and D the Ru and Because on D species. adsorbed of CeO D D/H species to those of during Compared than desorption species species. larger facilitates D D-containing much species of of adsorption Ru strong production of the D little presence to HD, due is of be there might production which the S11), degC, (Figure 50 at ceria reaction exchange on adsorb would species 2 H , 2 2 2 vlto vrRu/CeO over evolution O cat -10%H n NH and -1 a eprtr eedneo moi ytei ae(. ,10Ma 2 Lmin mL 120 MPa, 1.0 g, (0.2 rate synthesis ammonia of dependence Temperature (a) Lf)Rmnsetao aiu ape n Rgt I (Right) and samples various of spectra Raman (Left) h 3 -1 2 r 07,-.5ad-.9 nteohrhn,teetmtdH estimated the hand, other the On -0.79. and -0.75 -0.72, are A itr a nrdcdt h aayt Fgr ) lhuhalreaon fhydrogen of amount large a Although 4). (Figure catalysts the to introduced was mixture -Ar cat 3 n .4mo g mmol 9.24 and ecinorders. reaction -1 2 2 H u hne o03ad03 o Ru/CeO for 0.36 and 0.3 to changes but -H, h H Ru/CeO -H, -1 2 ne h aerato odtos h unvrfeunisfrR aayt with catalysts Ru for frequencies turnover The conditions. reaction same the under ) C5HadRu/CeO and -C250H 2 D n D and HDO , 2 2 aayt ujce oC ciainso ihramnasnhssrtsthan rates synthesis ammonia higher show activation CO to subjected catalysts oeue a iscaeo Ru on dissociate can molecules 2 3+ n D and cat xgnvcnyadRu and vacancy oxygen , 2 2 C5HadRu/CeO and -C250H -1 C0Haesrne hntoeoe Ru/CeO over those than stronger are -C500H h 2 -1 ,i a ecnlddta hr sdnmcecag fdeuterium of exchange dynamic is there that concluded be can it O, 2 2 t400 at 2 vlto ek t10dg n 6 eCcnb on vrthe over found be can degC 363 and degC 190 at peaks evolution ssgicnl ihroe h uctlss ofimn htthe that confirming catalysts, Ru the over higher significantly is O C5HadRu/CeO and -C250H 2 dopina 0 eCadA ugn t5 eCfr6 i,a min, 60 for degC 50 at purging Ar and degC 400 at adsorption 2 C0Hso tblt etrta hto Ru/CeO of that than better stability show -C500H ° n . P,wihaeruhytofl hto Ru/CeO of that two-fold roughly are which MPa, 1.0 and C 5 2 -1 C0H epciey n h orsodn reaction corresponding the and respectively, -C500H, δ- o Ru/CeO for 0 -O ealcstst omhdie,adte h H the then and hydrides, form to sites metallic V 2 C0H ncmaio ihteRu/CeO the with comparison in -C500H) -Ce 2 C5HadRu/CeO and -C250H 58-60 3+ 695+970 2 C5HadRu/CeO and -C250H concentrations. 2 oeua H Molecular H Ru/CeO -H, /I 460 2 n I and aayt,vroscharacter- various catalysts, 2 2 H eeln htteeis there that revealing -H, ecinodri negative is order reaction 2 2 C5HadRu/CeO and -C250H lodsoit nceria on dissociate also 2 587+1180 2 C0H respectively, -C500H, aayt eutn in resulting catalyst, 61-62 ,9 52-57 9, 7, 2 C0Hae8.03 are -C500H h rsneof presence The /I 2 460 r .,1.2 1.0, are -1 sshown As n (b) and ) 2 intensity H The -H. 2 -H 2 2 2 2 - - , Posted on Authorea 28 Sep 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.160133580.03550052 — This a preprint and has not been peer reviewed. Data may be preliminary. pce.()Naoso usraeratwt h egbrn tm o omamna lo atoms H Also, ammonia. form for atoms H neighboring Conclusions the with 4. generation. react water surface via Ru weakening desorb on ceria bond Ru atoms in N[?]N N electron-enriched (b) (c) surface, the ceria from species. on donation H metal electron with Ru Ru of together to of vacancies result increase oxygen a the and as ceria with reduced decreases partially synthesis from ammonia on 5 activation Figure CO envisioned of is S16). Ru/CeO effect it (Figure water hand, for positive in loading weakened other also the the be but that On would spillover, species shows reverse vacancies. effects hydrogen by oxygen spillover the formation of that the ammonia replenishment indicating that in to catalysts, only Ru leads al. not all that MgO participate for generation/desoprtion et oxygen nonpolar study Wu TPSR surface of during catalyst. on evolution instead located effect. Ru/MgO water MgO(111) is for poisoning There polar poisoning hydrogen S15). using hydrogen of N mobility of alleviation for NH species lessening sites and the hydrogen to active is of the lead outcome increase releasing could overall sites, the An Ru that on reported species synthesis. too hydrogen ammonia However, synthesis; surplus and ammonia the species. of remove oxygen reactions to by catalysts stabilized the are hence D and and of support Ru/CeO dissociation ceria pre-adsorption nitrogen the the hinder to thus would migrate species atoms hydrogen H much the of Ru some bond. of and N[?]N Ru enhancement electron-enriched of weakening of significant generation in to the resulting to leads leading Figure activation metal, Ru in CO Ru strong to and and proposed a electrons ceria, provide is exert would and catalysts ceria would metal reduced Ru sites Ru Ce ceria-supported active between exposure, the of EMSI species over nature is synthesis the There ammonia in 5. for difference mechanism the synthesis. possible series ammonia result, A of a a pathways removed, As reaction been NH the has catalysts. of on H catalysts desorption Ru influence of Ru and of adsorption the water sites of dissociative in Ru active formation ceria the on the or as adsorbed atoms, Ru such species observation nitrogen synthesis. on hydrogen hydrogen the ammonia steps, pre-adsorbed that to the with reaction contributed species report line that electride of deuterium was C12A7 in concluded the the It is in be of which catalyst. encaged can most hydride synthesis, electride deuterium the It Ru/C12A7 ammonia than the over rather for study. of species, responsible al. TPSR most D is et during that and Kammert phase removed HD suggesting of gaseous be are degC, the could there 300 from weaker, ceria below species significantly on catalysts Despite adsorbed Ru species ceria-supported species. deuterium the over of desorption D desorption the with facilitates pre-adsorbed species samples the over mixture Ru/CeO the D with comparison In reaction. exchange D/H the reduction during the for agents different 4 using Figure S8). of result (Figure a more catalysts as much Ru process would the treatment thermal of which the species during spillover oxygen oxygen of lattice surface are CO. Ru/CeO there with that react proving easily catalysts, Ru activated CO 2 inl r bevdoe ei ihters ftmeauedrn PRsuyi 3.3%N in study TPSR during temperature of rise the with ceria over observed are signals O δ- 2 2 2 -O C0H(iueS4.Nntees ihC ciain hr sapeatv xgni h Ru the in oxygen active ample is there activation, CO with Nonetheless, S14). (Figure -C500H pathways the to attributed be might oxygen lattice surface of property the in discrepancy The -H. inl vrRu/CeO over signals vlto rfie fH,D HD, of profiles Evolution osbeamnasnhssptwy vracraspotdR aayt a lcrntransfer Electron (a) catalyst. Ru ceria-supported a over pathways synthesis ammonia Possible V -Ce 2 3+ iscaieasrto nR ufc,adHao irto n tblzto yoxygen by stabilization and migration atom H and surface, Ru on adsorption dissociative ie.Teei lcrndnto rmRu from donation electron is There sites. 3+ 63-64 ocnrto,adnme foye aac.Teoye aace n partially and vacancies oxygen The vacancy. oxygen of number and concentration, h CO The 2 2 C0Ha oprdt hs vrRu/CeO over those to compared as -C500H ed ontbedces fNH of decrease notable to leads 2 HadRu/CeO and -H 2 2 vlto ek t10dg n 6 eCaeasn ntecs of case the in absent are degC 363 and degC 190 at peaks evolution 56 D,adD and HDO, , h H The 2 oeue a iscaeo umtlstst omhydrides, form to sites metal Ru on dissociate can molecules 2 Fgr 1) ute ofimn httepeec fRu of presence the that confirming further S13), (Figure 2 2 C0Hctlss uhsrne D D HD, stronger much catalysts, -C500H ihtm t5 eCdtce yms spectrometry mass by detected degC 50 at time with O 6 2 2 aaytwt ag uprils n h result the and particles, Ru large with catalyst n N and x δ- δ- nemdaeseis ol otneo the on continue would species, intermediate oteatbnigobtlo dobdN adsorbed of orbital antibonding the to x pce oteatbnigobtlo N of orbital antibonding the to species assgas(/=5 6ad1)over 17) and 16 (m/z=15, signals mass 2 h ecino yrgnaosand atoms hydrogen of reaction the , 66 enie hr r togrNH stronger are there Meantime, 2 Hdrn PRsuy(Figure study TPSR during -H 2 2 2 D and HDO , dissociation -10%H 65 δ- Despite species 2 -Ar 2 2 2 , , Posted on Authorea 28 Sep 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.160133580.03550052 — This a preprint and has not been peer reviewed. Data may be preliminary. .Go . hn . aayt NH Catalyst: photo(electro)catalysts P., and Chen, electrocatalysts J.; of Guo, design 3. Rational (NH S.-Z., ammonia Qiao, to A.; reduction Vasileff, nitrogen J.; for Ran, C.; explosion. Guo, population 2. the of Detonator V., Smil, 1. XRC-18033). (Grant University Fuzhou 21825801, of 21776047, Scholar (Nos. References Qishan China for of Foundation Program Science the National and the by 21978051) supported financially was work This O1s Acknowledgments spectra, Ce3d references. related XPS and HAADF-STEM spectra, elsewhere of DRIFTS rates, dependence images, synthesis temperature TEM ammonia H D from orders, mappings, of obtained signals element reaction dependence mass corresponding spectra, transfer, time the heat plots, and and Arrhenius image transport rates, mass synthesis of ammonia results of design calculation the sites. The for active important metallic are on findings based Information These are Supporting alleviated. that on the is reactions oxygen and the catalysts for increase, active Ru releasing catalysts two-fold for of sites, metal a poisoning Ru supported amount roughly hydrogen the showing larger of activity, on a synthesis effect species ammonia ill of hydrogen the presence surplus enhances The adsorbed significantly the electron- remove catalyst species N phase. help of hydrogen for can gaseous of formation sites catalysts exchange the active the Ru dynamic from activated to is that CO there lead with the that catalysts would show Ru vacancies experiments that on TPSR oxygen reveals and investigations and exchange Raman ceria D/H and reduced XPS Ce Ru DRIFTS, of partially increase enriched of of significant combination to evolution A leads exposure also high the treatment concentration. and CO oxygen reduction The active of activation. degree and CO high by with species catalysts Ru Ru of ceria-supported prepared successfully have We .Ptl .S;Wn,Q;Hse,V;Ln,J,Pam N Plasma J., Lang, V.; Hessel, Q.; Wang, S.; B. 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