Voltammetric Response of Hydrogen Adsorbates on Platinum in Acid Solutions . A Possible H-Adatom Subsurface State

Fo ram apli ca das ro ti nas com bi na das de po ten ci al, en vol ven do var re du ras vol ta mé tri cas e pa ra das de po ten ci al, na re gião dos ad-átomos de hi dro gê nio so bre ele tro dos de Pt, em di fe ren tes so lu ções áci das, para pro du zir um au men to da cor ren te de pico da ele tro-desorção do “ter ce i ro” áto mo de hi dro gê nio que apa re ce cer ca de 0.22 V vs. RHE. Este pico pode ser ob ser va do para ele tro dos de Pt de di fe ren tes to po gra fi as. Apa ren te men te, a con tri bu i ção ca tó di ca cor res pon den te apa re ce numa re gião de po ten ci a is li ge i ra men te mais po si ti vos que o po ten ci al li mi ar da re a ção de des pren di men to de hi dro gê nio. A di fe ren ça en tre os po ten ci a is de pico re fe ren tes as re a ções re dox con ju ga das é con sis ten te com uma apre ciá vel ir re ver si bi li da de do pro ces so. A pe que na car ga en vol vi da nes te par de pi cos é es pe ra da para es ta dos sub-superficiais e in ters ti ci a is dos ad-átomos de hi dro gê nio so bre Pt. Esse tipo de es tru tu ra tem sido pre di ta por cál cu los da quí mi ca quân ti ca.


Intro duc ti on
The hydro gen evo lu ti on re ac ti on ( HER), one of the most im por tant pro ces ses in elec tro ca taly sis, has been used as a pro toty pe for se ve ral elec tro de re ac ti ons [1][2][3][4][5][6][7] .De pen ding on the na tu re of the me tal/so lu ti on in ter fa ce, the ki ne tics of the HER has been ex pla i ned through dif fe rent re ac ti on path ways in volving the par ti ci pa ti on of H-adatoms as re ac ti on in ter me di a tes.Accor dingly, de pen ding on the type of ad sorp ti on isot herm which H-adatoms obey, ki ne tic equa ti ons de ri ved from dif ferent re ac ti on path ways ac count for spe ci fic po ten ti al and time de pen den ci es of θ, the de gree of elec tro de sur fa ce co ve ra ge by re ac ti on in ter me di a tes [1][2][3] .
Ho we ver, in con ven ti o nal me cha nis tic ap pro a ches to the HER un der ste ady-state con di ti ons, lit tle at ten ti on has been paid to the in flu en ce of the cha rac te ris tics of ad sorp tion si tes on the ki ne tics of the re ac ti on.In fact, as far as we know, the re is only one exam ple in which the pos si bi lity of the sur fa ce dif fu si on of H-adatoms oc cup ying dif fe rent adsorp ti on si tes of Pt has been con si de red 8 .Sin ce most of the work done at the me tal/aque ous so lu ti on in ter fa ce has focu sed on the eva lu a ti on of the isot herm for H-adatoms and Ar ti cle che mi sorp ti on energy 2,3,[7][8][9][10] , non-equilibrium ef fects due to sur fa ce dif fu si on pro ces ses have been dis re gar ded.
Va lu a ble in for ma ti on about the me cha nism of the HER has been ob ta i ned from the un der po ten ti al de po si ti on of H-adatoms at no ble and se mi-noble me tals, but lit tle has been ga i ned from tho se spe ci es which might act as ac tu al pre cur sors to H 2 mo le cu le for ma ti on at over po ten ti al condi ti ons [11][12][13][14] .This draw back is ca u sed by the fact that the steady H 2evo lu ti on cur rent gre atly ex ce eds tho se tran si ent cur rent con tri bu ti ons as so ci a ted with H-adatom re ac ti ons.In fact, AC im pe dan ce spec tros copy data have made the analy sis of H in ter me di a tes pos si ble in a po ten ti al ran ge clo se to the HER thres hold po ten ti al 15,16 .
On the ot her hand, the ap pli ca ti on of dif fe rent po ten ti al rou ti nes to no ble me tal elec tro des pro du ces chan ges in the sur fa ce morp ho logy, in clu ding crystal lo grap hic ori en ta tion [17][18][19] .The se chan ges in vol ve mo di fi ca ti ons in the ad sorba te cha rac te ris tics of the me tal elec tro de, as has been well es ta blis hed for H-adatoms on Pt 19 .In this case, the H-adatom elec tro sorp ti on vol tam mo gram acts as a sort of fin ger print of the ad sorp ti on energy cha rac te ris tics of the elec tro de sur fa ce, thus of fe ring the pos si bi lity of de ter mining the in flu en ce of a spe ci fic me tal to po graphy on a par ticu lar re ac ti on, as in the case of the H-adatom elec tro sorp ti on re ac ti on on Pt subs tra tes.
This pa per pro vi des ex pe ri men tal data on the pos si ble exis ten ce of a H-adatom sta te ac ting as a pre cur sor in the HER , yi el ding spe ci es which ap pe ar to be clo sely re la ted to the so-called "third" ano dic vol tam me tric peak for Pt in acid so lu ti ons.In situ in fra red data 20 and vi si ble-infrared sum fre quency ge ne ra ti on vi bra ti o nal spec tros copy 21,22 indi ca ted the pre sen ce of the se spe ci es, which was sup por ted by quan tum che mistry cal cu la ti ons 23 .

Expe ri men tal
Elec tro che mi cal runs were made in dif fe rent con ven tio nal elec tro che mi cal cells made of eit her glass or Te flon, with a Pt wor king elec tro de, a lar ge Pt ga u ze coun te re lectro de, and a re ver si ble hydro gen re fe ren ce elec tro de.The fol lo wing aque ous so lu ti ons were em plo yed: x M H 2SO 4 (0.05 ≤ x ≤ 1.0), 0.5 M HClO 4 , 0.3 M HF, and 1 M HF.So luti ons were pre pa red from a.r.che mi cals and Mil li pore-MilliQ* wa ter.All runs were per for med un der con ti nu ous oxy gen-free ni tro gen sa tu ra ti on at 25 °C.Poten ti als in the text are gi ven in the re ver si ble hydro gen electro de ( RHE ) sca le.
Three types of Pt wor king elec tro des were used.i) Smo oth polycrystal li ne ( pc ) Pt elec tro des, which were first im mer sed in a hot H 2SO 4-HNO 3 1:1 mix tu re, sub se quently rin sed with Mil li po re-MilliQ* wa ter, and finally pla ced in the wor king so lu ti on.
ii) Smo oth pc Pt elec tro des, which were sub jec ted to repe ti ti ve tri an gu lar po ten ti al cycling (rou ti ne I) at 0.1 V s -1 bet we en E sc = 0.05 V and E sa = 1.45 V un til a sta ble vol tammo gram (blank) was achi e ved.They were then sub jec ted to pre set re pe ti ti ve symme tric squa re wave po ten ti al cycling (rou ti ne II) to de ve lop a cer ta in pre fer red crystal lo grap hic ori en ta ti on ( pco ).This po ten ti al rou ti ne was cha rac te ri zed by an up per (E u ) and a lo wer swit ching po ten ti al (E l ) and a fre quency (f).De ta ils of the se tech ni ques have been gi ven el sew he re [17][18][19] .Two types of pco Pt elec tro des ( pco I and pco II) were em plo yed.The pre pa ra ti on con di ti ons un der rou ti ne II were -0.2 V ≤ E l ≤ 0.05 V, E u = 1.5 V , 4 kHz ≤ f ≤ 7 kHz for 120 s ≤ t ≤ 3600 s for pco I Pt, and 0.60 ≤ E l ≤ 0.70 V, E u = 1.5 V , 4 kHz ≤ f ≤ 7 kHz for 120 s ≤ t ≤ 3600 s for pco II Pt.The cyclic vol tam mo gram of pco I Pt run in 1 M H2SO 4 at 0.1 V s -1 was si mi lar to that of a Pt(100) sur fa ce af ter it has been cycled a few ti mes through the O-adatom po ten ti al re gi on [24][25][26] .Ho we ver, in con trast to pre vi ous results 18 , the elec tro re duc ti on swe ep for pco I Pt ex hi bi ted a cur rent hump very near the HER thres hold po ten ti al whe re the Pt sur fa ce was al most com ple tely co ve red by H-adatoms.On the ot her hand, the cyclic vol tam mo grams of pco II Pt clo sely re sem bled the cha rac te ris tics des cri bed in the li te ra tu re for Pt(111) af ter it has been po ten ti al cycled in the O-adatom po ten ti al ran ge 27 .
iii) Co lum nar struc tu red ( cs ) Pt elec tro des in vol ving rough ness fac tors in the ran ge of 10 to 150.The pre pa ra ti on tech ni que of this type of elec tro de has been des cri bed elsew he re 28 .Vol tam mo grams ob ta i ned for cs Pt elec tro des in 1 M H 2 SO 4 sho wed the same pair of con ju ga ted cur rent pe aks for the strongly and we akly bound H-adatoms.
A com bi ned cyclic vol tam metry tech ni que was em ployed to fol low the va ri ous H-adatom elec tro sorp ti on pro cesses.The first step con sis ted of the ap pli ca ti on of a re pe ti ti ve tri an gu lar po ten ti al swe ep co ve ring the ran ge E sc = 0.02 V to 0.05 V ≤ E sa ≤ 0.25 V (rou ti ne III), and the se cond step invol ved the ap pli ca ti on of tri an gu lar po ten ti al swe eps, inclu ding a po ten ti al hol ding at E h (0.02 V ≤ E h ≤ 0.25 V) in the po ten ti al swe ep run in the ne ga ti ve po ten ti al di rec ti on, for time t h (10 s ≤ t h ≤ 20 min) (rou ti ne IV).Both rou ti nes III and IV were fol lo wed by cyclic vol tam metry run in the range from E sc = 0.05 V to eit her E sa = 0.50 V or 1.45 V. Changes in the suc ces si ve vol tam mo grams al lo wed us to in fer pos si ble re ar ran ge ments of the H-adatom con fi gu ra ti on on Pt pro mo ted by the ap pli ca ti on of the po ten ti al rou ti nes.Finally, the po ten ti al cycling was con ti nu ed un til the sta ble cyclic vol tam mo gram was at ta i ned.The same rou ti ne was ap pli ed to all wor king so lu ti ons.
The real sur fa ce area of pc -Pt, pco -Pt, and cs -Pt elec trodes was me a su red through the chan ge of the H-adatom elec tro sorp ti on read from the vol tam mo gram run at 0.1 V s -1 , co ve ring the ran ge from E sc = 0.05 V to E sa = 0.50 V in aque ous 0.5 M H 2SO 4. For this pur po se, the H-adatom mo no la yer char ge den sity for each Pt sur fa ce was ta ken from the li te ra tu re as 210 µC cm -2 , 242 µC cm -2 , and 210 µC cm -2 for Pt (100), Pt (111), and pc -Pt, res pec tively 29 .

Ge ne ral fe a tu res
Cyclic vol tam mo grams run at 0.1 V s -1 for pco I-Pt and pco II-Pt in aque ous 0.5 M H 2SO 4 and 1 aque ous M HF (Fig. 1), as well as tho se run in aque ous 0.5 M HClO 4 in the ran ge of E sc = 0.05 to E sa = 1.45 V, ex hi bit qua li ta ti vely com pa ra ble fe a tu res.Thus, the H-adatom elec tro sorp ti on po ten ti al ran ge ex tends from 0.05 V to 0.45 V, and the O-atom elec tro sorp ti on and oxi de for ma ti on po ten ti al range co vers from ca. 0.70 V to 1.50 V.The charging-discharging dou ble la yer re gi on is lo ca ted in bet we en.The se re sults con firm the in flu en ce of the Pt sur fa ce morpho logy on the H-and O-adatom elec tro sorp ti on vol tam mograms in tho se elec troly tes.
Vol tam mo grams show that the H-Pt bond is so mew hat stron ger in aque ous 1 M HF, and that the H-adatom elec trode sorp ti on co vers a po ten ti al ran ge wi der than in aque ous 0.5 M H 2 SO 4 .Li ke wi se, it ap pe ars that in aque ous 1 M HF the O-Pt bond is stron ger, and the O 2 evo lu ti on thres hold po ten ti al is lo wer than in aque ous 0.5 M H 2 SO 4 .Then, the be ha vi or of the H-and O-atom elec tro de sorp ti on in aqueous 1 M HF is rat her si mi lar to that found ear li er in aque ous HBF 4 so lu ti on 30 , and can be ex pla i ned by the low ani on adsor ba bi lity on Pt in tho se so lu ti ons.

Re sults ob ta i ned using pco Pt elec tro des
H-adatom elec tro sorp ti on re ac ti ons on pc Pt dis play a mul ti pli city of cur rent pe aks, which are as so ci a ted with dif fe rent H-adatom sta tes, and the re la ti ve con tri bu ti on of the se pe aks chan ges ac cor ding to the elec tro de sur fa ce cha rac te ris tics.Thus, for pco I Pt in aque ous 1 M HF, the re is a re la ti vely lar ge con tri bu ti on of tho se re ac ti ons in volving strongly bound H-adatoms, the cor res pon ding pair of pe aks lying at 0.30 V, a po ten ti al which is po si ti vely shifted with res pect to that ob ser ved for the same re ac ti ons in aque ous 0.5 M H 2 SO 4 .It should be no ted that by set ting E sc ≅ 0 V, the vol tam mo gram ex hi bits a new cur rent contri bu ti on at ca. 0.05 V, a po ten ti al slightly more po si ti ve than the HER thres hold po ten ti al.This peak de cre a ses pro gres si vely with furt her cycling in the H-adatom po tenti al ran ge, but the con ju ga ted pair of pe aks at ca. 0.3 V beco mes shar per and hig her (Fig. 2).The H-adatom elec tro ad sorp ti on char ge de ri ved from the first and second vol tam mo gram is gre a ter than that de ri ved from the H-adatom elec tro de sorp ti on vol tam mo gram, but the anodic to cat ho dic char ge ra tio af ter the third cyclic vol tammo gram re ma ins the same.Con ver sely, when the po ten ti al rou ti ne II is ap pli ed in the ran ge of E l = 0.05 V to E u = 1.50 V with f = 5 kHz, the sub se quent vol tam mo gram Fi gu re 2. Cyclic vol tam mo grams run at 0.05 V s -1 for pco I Pt elec trodes in aque ous 0.5 M H 2SO 4 af ter ap plying rou ti ne III. 25 °C.Arrows in di ca te the di rec ti on of the chan ge in the vol tam me tric pe aks on the po ten ti al cycling.The small ar rows show the small cat ho dic vol tamme tric con tri bu ti on re la ted to the "third" ano dic cur rent peak.
shows that the cat ho dic hump at 0.05 V di sap pe ars, and then the ano dic to cat ho dic char ge ra tio re ma ins clo se to 1, ir res pec ti ve of the num ber of cycles.
Cyclic vol tam mo grams of pco II Pt in aque ous 1 M HF and aque ous 1 M H 2 SO 4 show a re la ti vely lar ge con tri buti on of we akly bound H-adatoms as a pair of re ver si ble peaks at 0.12 V and 0.10 V, res pec ti vely (Fig. 3).In this case, both H-and O-adatom elec tro ad sorp ti on are de la yed as the elec troly te con cen tra ti on is in cre a sed, due to the ap pea ran ce of the spe ci fic in flu en ce of ani on ad sorp ti on 31 .Other wi se, by set ting E l in the ran ge 0.40 ≤ E l ≤ 0.50 V, the vol tam mo gram shows a cat ho dic hump at ca. 0.05 V, which con ti nu es to be ob ser ved in the se cond scan, but disap pe ars la ter on.This chan ge is ac com pa ni ed by a sharpness of the pair of pe aks found at 0.12 V.After wards, the sta ble vol tam mo gram run in the H-adatom po ten ti al re gi -on shows aga in that the ano dic to cat ho dic char ge ra tio be co mes equal to one.
The vol tam me tric re so lu ti on of the "third" ano dic peak also de pends on the po ten ti al swe ep rate.For scan ra tes abo ve 0.5 V s -1 , no con tri bu ti on of this peak can be ob served.Ho we ver, hol ding the po ten ti al at E h = 0.064 V (rou tine IV) it re sults in a cle ar de fi ni ti on of the "third" ano dic peak, alt hough it lar gely over laps the strongly bound H-adatom elec tro oxi da ti on cur rent peak.The se re sults con firm that the ki ne tics of tho se re ac ti ons in vol ved in the "third" ano dic peak is rat her slow, as has been pre vi ously con clu ded by ot her aut hors 27,32 .
Vol tam me tric runs were also made with pco II Pt in aque ous 1 M H 2 SO 4 ap plying rou ti ne IV in the po ten ti al ran ge of 0.052 V ≤ Eh ≤ 0.123 V.The vol tam me tric fe a tu res re sul ting from the se elec tro des are si mi lar to tho se al re ady des cri bed for cs Pt.The op ti mal enhan ce ment of the "third" ano dic peak ap pe ars at E h = 0.049 V. (Fig. 4).Ho we ver, for po ten ti al hol dings ex ce e ding 30 min, a strong inhi bi ti on of both the we akly bound H-adatom elec tro sorp ti on peak and the "third" ano dic peak, as well as a sig ni fi cant in cre a se in the strongly bound H-adatom de sorp ti on peak fol lo wed by the typi cal hump al re ady des cri bed for pco II Pt at 0.35 V 18 can be seen.The se re sults can be ex pla i ned by the li kely sur fa ce dif fu si on of H-adatoms on dif fe rent crystal lo graphic si tes 8 .
Fol lo wing the H-adatom vol tam me tric fin ger prints on Pt sin gle crystals [24][25][26] , it ap pe ars that for short po ten ti al holding ti mes, the H-adatom spe ci es dif fu ses from the (111) to (110) si tes, i.e. , the "third" ano dic peak enhan ce ment is favo red (Fig. 4a).Ho we ver it ap pe ars that lon ger po ten ti al hol ding ti mes at E h = 0.05 V in aque ous 0.5 M H 2 SO 4 would fa vor the H-adatom sur fa ce dif fu si on to (100) si tes (Fig. 4b), re sul ting in the ap pe a ran ce of the cat ho dic shoulder near the HER.
The abo ve re sults, to get her with tho se ob ta i ned applying rou ti ne III bet we en E sc = 0 V and E sa = 0.05 V, give a furt her in sight into the na tu re of the cat ho dic con tri bu ti on re la ted to the "third" ano dic peak, alt hough the time re quired for achi e ving the same ef fect for rou ti ne III is much shor ter than that for rou ti ne IV (Fig. 5).

Re sults ob ta i ned using cs Pt elec tro des
The ap pli ca ti on of rou ti ne III to a cs Pt in aque ous 0.5 M H 2 SO 4 wit hin the H-adatom po ten ti al ran ge, fol lo wed by a se quen ce of tri an gu lar po ten ti al swe eps of in cre a sing E sa , pro du ces cle ar and spe ci fic vol tam me tric fe a tu res re la ted to both the strongly and we akly bound H-adatoms, as well as to the "third" ano dic peak and its con ju ga ted con tri bu tion.Thus, a po ten ti al cycling bet we en E sc = 0 V and E sa = 0.055 V at 0.05 V s -1 both enhan ces the "third" ano dic peak and de cre a ses the de sorp ti on peak of we akly bound H-adatoms, as can be seen du ring the first sub se quent electro o xi da ti on po ten ti al swe ep (Fig. 6a, b).Whe ne ver the poten ti al cycling is fol lo wed by a gra du al in cre a se in E sa wit hin the dou ble la yer po ten ti al ran ge, ke e ping E sc constant (Fig. 6c), a well-defined strongly bound H-adatom rever si ble pair of pe aks with a cons tant peak he ight can be ob ser ved.Other wi se, for E sa > 0.8 V, i.e. , when the in ci pient O-atom elec tro ad sorp ti on po ten ti al ran ge is co ve red, the con tri bu ti on of the pair of re ver si ble pe aks in cre a ses, whe re as that of the "third" ano dic peak turns out to be very small (Fig. 6d).Furt her mo re, when E sa > 1.0 V, a de cre a se in the he ight of the strongly bound H-adatom pair of pe aks, and an in cre a se in he ight of the "third" ano dic peak can be seen (Fig. 6e), as has al re ady been ob ser ved for Pt (110) sub se quent to a po ten ti al ex cur si on in the oxy gen atom elec tro ad sorp ti on-electrodesorption ran ge 32 .Li ke wi se, for Esa > 1.2 V, the he ight of the we akly bound H-adatom anodic con tri bu ti on be co mes al most cons tant.Furt her mo re, a pro gres si ve in cre a se in the cur rent con tri bu ti on on the cat -ho dic branch of the we akly bound elec tro re duc ti on peak, as well as that in the "third" ano dic peak, can be ob ser ved.The best de fi ni ti on of the "third" ano dic peak is ob ser ved un der rou ti ne III for lo wer po ten ti al swe ep ra tes.
Qu a li ta ti vely si mi lar re sults were ob ta i ned for aque ous 1 M HF and aque ous 0.5 M HClO 4 , alt hough in the se ca ses a we a ker vol tam me tric res pon se of the "third" ano dic peak was found.The se ef fects are no lon ger ob ser ved when routi ne III is ap pli ed at E sa > 0.15 V. Ho we ver, the in flu en ce of the na tu re and the con cen tra ti on of ani ons on the de ve lopment of the "third" ano dic peak de ser ves furt her study.
On the ot her hand, rou ti ne IV pro du ces dif fe rent voltam me tric con tri bu ti ons, de pen ding on the po ten ti al holding and time spent.Thus, lon ger ti mes and lo wer po ten ti al hol ding va lu es enhan ce the con tri bu ti on of the "third" anodic peak.Ho we ver, a li mi ting time to at ta in the ef fect found at each po ten ti al hol ding that de pends on the acid so lu ti on com po si ti on.
The com pa ri son of data de ri ved from the ap pli ca ti on of eit her rou ti ne III or IV to cs Pt in the acid aque ous so lu ti ons shows that in the for mer case, the gre a test enhan ce ment and de fi ni ti on of the "third" ano dic peak was achi e ved.It should be no ted, ho we ver, that the "third" peak for cs Pt is more po orly de fi ned in aque ous HF and HClO 4 than in aque ous H 2 SO 4 so lu ti on.

Des crip ti on of pos si ble H-adatom sta tes
It is well known that H-atom elec tro sorp ti on on Pt results ma inly in the for ma ti on of two dif fe rent ad sor ba tes, which cor res pond to the we akly and strongly bound ad sorbed H-atom.For Pt(111) sin gle crystal, the weak H-Pt bonding, in con trast to the strong H-Pt bon ding for Pt(100), should in vol ve the con tri bu ti on of a wa ter mo le cu le in the for ma ti on of the ad sor bed en sem ble [33][34][35][36][37] , which can be formally re pre sen ted as a [Pt N.H.OH 2] en sem ble, whe re N repre sents the num ber of Pt atoms in vol ved.In fact, de pen ding on whet her the elec tron energy le vel is lo wer or hig her than the Pt Fer mi le vel, eit her ne ga ti vely or po si ti -vely char ged H-adatoms re sult.This ex cess of char ge results in a chan ge in the sha pe of the po ten ti al energy cur ves, which in turn im pli es a va ri a ti on in both the H-Pt site in terac ti on for each pos si ble H-adatom co or di na ti on, and the po la ri za ti on of mo le cu les at the in ter fa ce.IR spec tros copy data show that the bond energy of we akly bound H-adatoms on Pt(111) de pends on the ap pli ed elec tric poten ti al, i.e. , on the char ge den sity on the me tal 14,34 .Otherwi se, strongly bound H-adatoms on Pt (100) imply an ad sor bed en sem ble in which the H-atom den sity is de lo cali zed on the Pt sur fa ce 33 .
Re cent re sults 23 have shown that the for ma ti on of H-adsorbates at sur fa ce Pt si tes and sub sur fa ce Pt si tes in the si mu la ted aque ous elec tro che mi cal en vi ron ment is possi ble on both Pt(111) and Pt(100) clus ters.The se re sults pre dict that a tran si ti on from a sur fa ce to a sub sur fa ce adsor ba te con fi gu ra ti on was fe a si ble by ade qua tely chan ging the ap pli ed elec tric po ten ti al, thus pro vi ding a new in sight into the na tu re of H-adatom spe ci es on Pt in both va cu um and aque ous en vi ron ments.This type of con fi gu ra ti o nal tran si ti on has been re por ted for Pd(111) 38 , and the pre sen ce of sub sur fa ce H-adatom sta tes at Pt, Pd, and Ni sin gle crystal elec tro des as well 39,40 .
It has been pro ven that H-adatom sub sur fa ce sta tes on Pt re sult from H-adatom sta bi li za ti on by an ex cess of ne gati ve sur fa ce char ge which fa vors a tran si ti on from a H-adatom brid ge co or di na ti on to a H-adatom hol low subsur fa ce co or di na ti on on Pt(100), and from a H-adatom (3-1) hol low co or di na ti on to a H-adatom hol low sub sur face co or di na ti on on Pt(111).Accor dingly, H-adatoms bound to a sur fa ce Pt and a sub sur fa ce Pt atom are elec troni cally dif fe rent as a re sult of the ex cess of ne ga ti ve char ge at the H-adatom bound to a sub sur fa ce Pt atom.The pos sible exis ten ce of H-adatoms at the sub sur fa ce le vel would then in cre a se the num ber of elec tro che mi cal re ac ti ons in which H-atom sta tes on Pt are in vol ved.

Inter pre ta ti on of ex pe ri men tal data
The fact that the enhan ce ment of the "third" H-atom elec tro de sorp ti on peak at ca. 0.22 V oc curs when the poten ti al rou ti ne in vol ving eit her rou ti ne (III) or rou ti ne (IV) is ap pli ed in the ran ge 0.02 V ≤ E ≤ 0.15 V sug gests that the "third" ano dic peak must re sult from spe ci es pro du ced in the cat ho dic pro cess which ta kes pla ce in the po ten ti al range bet we en the we akly bound H-atom elec tro sorp ti on peak and the HER thres hold po ten ti al.This me ans that the H-adatom sub sur fa ce sta te is pro du ced in the po ten ti al range whe re the cat ho dic cur rent hump ap pe ars, i.e. , at ca. 0.05 V.
In ad di ti on, the re sults show two ki ne ti cally re le vant facts, na mely, the po ten ti al dif fe ren ce bet we en the "third" ano dic peak and that of its con ju ga ted cat ho dic con tri bu tion, and the po ten ti al shift of the "third" ano dic peak in the po si ti ve di rec ti on for in cre a sing po ten ti al swe ep ra tes.In prin ci ple, the se facts are con sis tent with the ir re ver si bi lity of the ove rall pro cess in vol ving sub sur fa ce H-adatom, probably be ca u se the spe ci es in vol ved in the cat ho dic and anodic re ac ti ons are not exactly the same, a si tu a ti on which might ari se from a chan ge in the con fi gu ra ti on of the sur face spe ci es pro du ced cat ho di cally.Hen ce, the be ha vi or of the con ju ga ted pro ces ses re la ted to the "third" ano dic peak con trasts with the re ver si bi lity ex hi bi ted by both the strongly and we akly bound H-adatom con ju ga ted pair of pe aks, who se peak po ten ti als are in de pen dent of the po tenti al swe ep rate used in con ven ti o nal vol tam metry in the absen ce of oh mic po la ri za ti on.
The H-Pt sub sur fa ce sta te is enhan ced by eit her rou ti ne III or rou ti ne IV, as de mons tra ted abo ve by an ano dic poten ti al swe ep fol lo wing the se rou ti nes.Con se quently, the con tri bu ti on of the sub sur fa ce sta te and the "third" enhanced ano dic peak de pends strongly on the po ten ti al hol ding va lue and its du ra ti on, and it gra du ally di sap pe ars when the po ten ti al cycling is per for med from E sc = 0.02 V to E sa = 0.50 V.Then, the in ter me di a te H-adatom sta te is lar gely con su med by re ac ti on (1) (Fig. 7), and prac ti cally no subsur fa ce H-adatom sta te can be ob ser ved in the ano dic voltam me tric swe ep.
If one con si ders that the cat ho di cally for med ad sor bed spe ci es which are res pon si ble for the "third" ano dic peak ap pe ar for a H/Pt ra tio equal to 1 ( θ ⊗1), it is still pos si ble to in cor po ra te ad di ti o nal H-atoms at in ters ti ti al po si ti ons le ading to in ter me di a te ad sor bed spe ci es, as shown in Fig. 7.This spe ci es, ac ting as a pre cur sor to the HER , has a low sta bi lity, and the re fo re, the cor res pon ding va lue of θ re sults in only a small frac ti on of the H-adatom mo no la yer.The lat ter si tu a ti on has been con fir med by the analy sis of the cor res pon ding vol tam me tric char ges.The in ter me di a te adsor bed spe ci es could pro bably be re la ted to the ori gin of the Pt-H vi bra ti on fre quency re cor ded near 0.05 V by elec troche mi cally mo du la ted in fra red spec tros copy 20 and vi sible-infrared sum fre quency ge ne ra ti on vi bra ti o nal spec tros copy 21,22 .
The de com po si ti on of the new in ter me di a te would result in the for ma ti on of a H 2 mo le cu le and a Pt sur fa ce co vered by a H-adatom mo no la yer, as in di ca ted by re ac ti on 1 (Fig. 7).On the ot her hand, un der ade qua te po ten ti al pertur ba ti on con di ti ons, the new in ter me di a te sta te may re orga ni ze it self, le a ding to a more sta ble con fi gu ra ti on  in vol ving a stron ger in te rac ti on bet we en the H atom at the in ters ti ti al po si ti on and Pt atoms at the sub sur fa ce le vel.The H-adatom at the sub sur fa ce le vel ap pe ars to be elec troo xi di zed at a hig her po ten ti al, and would be res pon si ble for the exis ten ce of the "third" ano dic peak.Fi nally, the we a ker res pon se of the "third" ano dic peak on cs Pt de ri ves from the typi cal res pon se of co lumnar-structured elec tro des that, in this case, ma kes the HER pro ce ed ma inly at the tips of co lumns 28 , le a ving a rat her res tric ted frac ti on for the for ma ti on of the HER pre cur sor.

Fi gu re 1 .
Cyclic vol tam mo grams run at 0.1 V s -1 for pco I and pco II Pt elec tro des in aque ous (a) 0.5 M H 2SO 4 and aque ous (b) 1 M HF. 25 °C.

Fi gu re 3 .
Cyclic vol tam mo grams run at 0.1 V s -1 for pco II Pt elec trodes in (a) aque ous 1 M H 2SO 4 and (b) aque ous 1 M HF. 25 °C.Fi gu re 4. Cyclic vol tam mo grams run at 0.1 V s -1 for pco I Pt elec trodes in aque ous 1 M H 2SO 4 af ter ap plying rou ti ne III.(a) t h = 3 min; (b) th = 25 min.25 °C.

Fi gu re 5 .
Cyclic vol tam mo grams run at 0.1 V s -1 for pco I Pt elec trodes in aque ous 0.5 M HClO 4 af ter ap plying rou ti ne IV for (a) t h = 300 s, and rou ti ne III (b) for t h = 140 s.E h = 0.03 V. 25 °C.

Fi gu re 6 .
Cyclic vol tam mo grams run at 0.05 V s -1 on cs Pt elec tro des in aque ous 1 M H 2SO 4 af ter ap plying rou ti ne III for t h = 3 min and fol lo wed by cyclic vol tam metry with E sc = 0.02 V and a gra du al in cre a se of E sa .(a) E sa = 0.23 V; (b) E sa = 0.33 V; (c) E sa = 0.60 V; (d) E sa = 1.0 V; (e) Esa = 1.25 V. 25 °C.