Surface enhanced Raman spectroscopy(SERS) has been applied to obtain structural information of surface species adsorbed at electrode surface in the electrode potential range of severe hydrogen evolution, which is very difficult to be gained by using most of spectroelectrochemical and conventional electrochemical methods

Li, WH

Ren, B

Tian, ZQ

Zou, SZ

任斌

田中群

Chinese Chemical Letters

Xiamen University Institutional Repository

肠 in撰 C加e m i司 t月. 的 V d·7,NO.2,PP 165一l“ 19 6 l65C AN‘AD S OR PT 10 N B E S T U D IE I) IN I’}IE E L EC fR O D E PO’l’EN T IA L R A N G EO F SE V E R E H YD R O G E N E V O L U T IO NW u H u Li,Sh o u Z h o n g Z O U,B in R E N a n d Z h o n g Q u n T IA N.S一a te K e y 助bo ra to ry fo r Ph 师ca l Chem ist ty o f肠Iid 加rfac es,De Parr能n t o f Che而stry.为 amen Uni ve 俪 ty.为a能n 书 11叉巧幼盯R A CT Su r fa e e e n l一a n e e d R a m a n sPe e tro se o Py (SE R S ) I一a s b e e n a PPlie d to o b ta in s tr鱿tu r a lin fo r m a tio n o f su rfa e e sPe e ie s a d so rb e d a t ele e tro d e su r fa c e in the ele e tr o d e Po te n tia l r a n g e o f se v e rehyd ro g e n e v o lu t io n,w hie h 15 v e r y d iffic u lt to b e ga in ed by us in g m o s t o f s pe e tr o e !e e tr o ehe m ie a l a n de o n v e n tio n a l e !e e tr o eliem ie a l m e th o d s.It 15 e x tre m e ly d iffie u lt to s tu d y a d so rPtio n in e le e tro d e Po te n tial ra n g e o f sev e re hyd ro g e几e v o lu tio n, e.g. ,in the ele e tr司 e po te n tia l r egio n n e g a tiv e o f 一 1.2 v (SC E )in a e id ie a q u e o u s so lu t一o n so r 一 1.6 V in n e u tr al a q u e o us so lu tio n s, eithe r b y e o n v e n tio n a l ele e tr o eh e m ie a l m e thod s o r bys沐 e tr o ele e tr o eh e m ie a l te e h n iq ues.In the d iffe r e n tial e a Pa eita n e e,im Pe d a n e e a n d el r o n o a m Pe ro·m e tri e st u d ie s,the in fo rm a tio n a bo u t a ds o rPtio n a re su b m e rg ed in e vita b ly in a 11 u g e Far adai e eu r re n to f hyd ro g e n ev o lu tio n.T h e v a s t hyd ro g e n bu b b le s g e n e r a te d a t th e s u r fa c e c a n c h a n g e th ee o m Po sitio n o f the ele e tr o lyte n e a r tlle su r fa , e a n d a lte r tl、e lig h t in te n sity ir re g u la rly,w hieh ing e n e r a l m a k e s a fa ta l in te r fe re n e e to the sPe e tro e le e t ro e he m ie a l m e a su r e m e n ts o r ev e n m a k e s th em e a su r em e n ts im Pos sib le.T h er e m a y be se v e ra lw ays to s u r m o u n t th e abo v e P ro b le m s, a t le a s t to so m e e x te n d.(i) T o u seth e o Pt ie al in te r n a l r efle e tio n sPee tr o se o Pie m e th o ds.T his m e tho d e a n o n ly red u e e th e in te r fe r e n e e o fth . hydroge n b u b b le s to so m e e x te n d s in e e the Pe n e tra tio n d ePt l、 o f the so lu tio n o v e r w hie h o Ptie alsa m 州in .一“ 15 500 to 2 00 0 人,(11) T o pr e ss th e o le e tr o d e a吕a in s t th e e ell w in d o w.W ith th e h e lpo fsuc ha 犯 ry th in la yer ee ll eo n fig u r a tio n the hyd ro ge n g a s ea n o n ly fo r m ve ry fin e bu bb le s 5 0 tha tn eithe r 一he in c id e n t n o r the scatter in g (o r r efle e tin g ) lig ht in te n s ities w o u ld be a lte r ed se rio u sly b yv igoro u s hyd r o g e n e v o lu tio n.H owev e r . the o hm ie d ro P in th e thin Iaye r sh o u ld be ta k e n in toa e eoun t.(111) T o u tiliz e th e su r fa e e e n ha n e ed e ffe e t.W he n the su rfa e e e n ha n e e d fa c to r 15 10弓,itm e a n s tha t a m o n o la ye r ad so r b a te e a n b e e o n sid e red a s e qu a l to a m illio n la ye r, u n de r n o r m a le o n d itio n.T h e e o m pos itio n o f th is‘ a m illio n Iaye r s’ a n d the e o r res PO n d in g s ig n al a r e o o t in flu e n ee dat allby the hyd ro g o n b u bb lin g.T h e d r aw ba c k 15 tha t the su r fa e e e n h a n e e d e ffe e r has o n ly t, e e n fo u n df o r a few m e ta ls.By ta k in g a d v a n ta ges o f (11) a n d (111),1.e. ,us in g a thin la ye r e ell e o n fig u ra tio n a n d s u r fa e ee n ha n e ed R am a n sPe etrosco Py (SE R s ),w e h a v e s tu d ie d the fo llo w in g th r e e syste m s in this Pa r rie u la r16e .e e tro d e Po te n tia l r e g io n.(a ) T h e a d so rPtio n w a te r m o le e u le s a t a ro u n d 一 1in v e s tig a te d in so lu tio n s〕r v a r io u s e a tjo n s.T h ee o n t : in in g e一。不o r s碳-th v a r io u s e o n e e n tr a t io n s (0.1一8..SV h孟5 be e no m o l/ L ) a n d /臼奋月⋯OWin t罗r e st in g re s u lts 曲ta in ed re v , 1 tha t th e a d s o rb e d w a te rs炙ru c tu r e m a y o rie n t w it h o n e hyd ro g e n su r fa e e a t v e r yw ith hig hly orde rdn e g a tiv e e le e tr o d e卯 te n tia一s〔1·2 1.(b ) T h e e o a d so rp tio n o f越to 币 e n d in g to theth io u r e a w ith C 10 扩 a t A ge le e tr o d e in a w id e r e le e tro d ePo te n tial ra n g e e a n b e o b s e r v e d in a eid ie s o lu tio n s.A t a r o u n d 一 1.1 V tlz e SE R S b a n d a t 93 4 e m一 tfro m th e e o a d so r b e d CIO犷 d e e r e a se s m u e h sh a r Ply th a n o th e r ba n d s fr o m th io u r e a (F ig.1 (A )),in d ie a tin g th a t th e e o a d so r b e d a n io n 15 m o re s tro n g ly re pe lle d o u t by t he n e g a tiv e eh a rg e o f t h esu rfa e e.In e o n t ra s t,it 15 im Po S ib le to o b ta in th e s am e in for ma t io n u s in g e le e troc h e m ie ald iffe r e n tia le a Pa e ita n e e m e th o d d u e to the hu g e Fa口da ic e u r re n t o f hyd ro g e n e vo lu tio n a t a r o u n d 一 1.I V (Fig.l(B )).(e ) 2 一 m e r e a Pto Pyr im id in e (ZM P) ha s be e n fo u n d to be a d s o rbe d a t silv e r ele e t ro de s in a w id ee le etrodePO te n tia l ra n g e (一 0.3一 一 1.8 v ).It 15 o f s p e c ia l in te烈tha t th e S E R S sp e e tr a b e e o m ed r a m a tie a lly d iffe r e n t a s th e e le c tro d e Po te n tia l 15 m ov e d to th e r e g io n o f hyd ro g e n e v o lu tio n.B y th esys te m a tie SE R S st u d y o n e e a n a s su m e t ha t hyd r o o lig o m e r iz a tio n o f ZM P ta ke s Pla e e a t th e e le e tro d e卯te n tials o f hyd ro g e n e v o lu tio n 〔3 1It 15 n e eesa r y to Po in t o u t th a t th e SE RSres u lts a re m o re r elia b le a n d e a sie r to in te rPr e t b e c a u seso m e sPe eial s u r fa e e e o m Ple x e s w ll e n the SE R S a c tiv e site s a re d e e o m Po s e d o r r e m ov e d in th e v e ryn e g a tive e le c tr回 e po te n tialre g io n, a n d o n ly th e e le c tro m a g n e tic e n h a n e e m e n t m e c h a n ism Pla ys a ke yr o l己 It h a , be e n d e m o n st ra te d tha t so m e im Po r ta n t in fo r m a tio n e a n b e e x tra ct e d to d e s e r ib e tlles rru e tu r e o f th e d o u ble la ye r a n d u n d e rs ta n d its e ffe e t o n th e m e e h a n ism s o f ele e tro d e re a e tio n s in th ee lc e trodepo te n tia l ra n g e o f se v e re nyo ro g e n e vo lu tio n.+ZH : 0+ + Ze 一 H Z + ZH 之0(A )4.0 名曰勺(SC E)(B )Fig.1 (A ) SE R S sPe e tra o f silv e r e lee tro de a t v a rio u s ele e tro d e Po te n tials : (a ) 一 O.3 V,(b )一 0.7 Va n d (e ) 一 1.I V (SC E ).(B ) Cyelie vo lta m m o g ra m o f silv弓r e le e tro d e w ith a sw e e p ra te o f 50 m V 厂5.So lu t io n 15 lm o l/ L T h io u r e a + 0.0 1m o l/ L H CIO 一 + 0.lm o l/ L N a C10;.A e k n o w l川g m . tT h is Pro iee r 15 su Pp o r ted by th e N a tu ral Sc ie n c e Fou n d a七io n a n d tl, c S ta te E d ue a tio n C o m m iss io n o f C hin a.R efe re o c巴1.Z.Q.T ia n.S.K.S ig a la e v.5.2.Z o u c t a l二 E le e tro e him iea A eta. ,19 9 4,3 9,2 1 9 5.2.5.2.Z o u,Y.H.Z ha n g,Y.X.C I一e n a n d Z.Q.T ia n.C he m.J.Cbj”e se U n iv 二 1 9 9 5,1 6 (公).2 4 5.3.W.H.Li,B.W.M ao a n d Z·Q·T ian.J·R a m a n SPe e t r o se. ,19 9 5,2 6,2 3 3.扭代d v ed 13 Ju n e 199 5 )

Can adsorption be studied in the electrode potential range of severe hydrogen evolution

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Can adsorption be studied in the electrode potential range of severe hydrogen evolution

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