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Mechanistic insights into solution-phase oxidative esterification of primary alcohols on Pd(111) from first-principles microkinetic modeling Eric D Hermes, Aurora N Janes, and Jordan R. Schmidt ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b02329 • Publication Date (Web): 20 Nov 2017 Downloaded from http://pubs.acs.org on November 20, 2017
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ACS Catalysis
▼❡❝❤❛♥✐st✐❝ ✐♥s✐❣❤ts ✐♥t♦ s♦❧✉t✐♦♥✲♣❤❛s❡ ♦①✐❞❛t✐✈❡ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r✐♠❛r② ❛❧❝♦❤♦❧s ♦♥ P❞✭✶✶✶✮ ❢r♦♠ ✜rst✲♣r✐♥❝✐♣❧❡s ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✐♥❣ ∗
❊r✐❝ ❉✳ ❍❡r♠❡s✱ ❆✉r♦r❛ ◆✳ ❏❛♥❡s✱ ❛♥❞ ❏✳❘✳ ❙❝❤♠✐❞t
❉❡♣❛rt♠❡♥t ♦❢ ❈❤❡♠✐str② ❛♥❞ ❚❤❡♦r❡t✐❝❛❧ ❈❤❡♠✐str② ■♥st✐t✉t❡✱ ❯♥✐✈❡rs✐t② ♦❢ ❲✐s❝♦♥s✐♥✕▼❛❞✐s♦♥✱ ✶✶✵✶ ❯♥✐✈❡rs✐t② ❆✈❡✳✱ ▼❛❞✐s♦♥✱ ❲■ ✺✸✼✵✻✱ ❯♥✐t❡❞ ❙t❛t❡s ❊✲♠❛✐❧✿ s❝❤♠✐❞t❅❝❤❡♠✳✇✐s❝✳❡❞✉
❆❜str❛❝t ❲❡ ♣r❡s❡♥t ❛♥ ❛❜ ✐♥✐t✐♦ ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ❢♦r t❤❡ ♦①✐❞❛t✐✈❡ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ✶✲ ♣r♦♣❛♥♦❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ♦✈❡r P❞✭✶✶✶✮✳ ❚❤❡ ♠♦❞❡❧ ❢✉❧❧② ❛❝❝♦✉♥ts ❢♦r s♦❧✈❛t✐♦♥ ♦❢ s♦❧✉t✐♦♥✲♣❤❛s❡ s♣❡❝✐❡s ❛♥❞ ❛❞❞❡❞ ❝❛t❛❧②t✐❝ ❜❛s❡✱ ❛♥❞ ♣r♦✈✐❞❡s ❦❡② ✐♥s✐❣❤ts ✐♥t♦ t❤❡ ❢❛❝t♦rs ✇❤✐❝❤ ❧✐♠✐t t❤❡ ❛❝t✐✈✐t② ♦❢ ✉♥♣r♦♠♦t❡❞ P❞ ❛❡r♦❜✐❝ ♦①✐❞❛t✐♦♥ ❝❛t❛❧②sts✳ ■♥ ♣❛r✲ t✐❝✉❧❛r✱ ✇❡ ✜♥❞ t❤❛t ❛❝t✐✈✐t② ✐s ❧✐♠✐t❡❞ ❜② t❤❡ ❧❛r❣❡ st❡❛❞② st❛t❡ s✉r❢❛❝❡ ❍ ❝♦✈❡r❛❣❡✱ ✇❤✐❝❤ ❞❡st❛❜✐❧✐③❡s ♦t❤❡r ❛❞s♦r❜❡❞ ✐♥t❡r♠❡❞✐❛t❡s ✈✐❛ ❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥s✱ ❛♥❞ s✉❜st❛♥t✐❛❧ ❜❛rr✐❡rs ❣♦✈❡r♥✐♥❣ t❤❡ ❢♦r♠❛t✐♦♥ ♦❢ ❖−❍ ❜♦♥❞s✱ ✇❤✐❝❤ ✐s r❡q✉✐r❡❞ ❢♦r t❤❡ r❡❞✉❝t✐♦♥ ♦❢ ❖✷ ❛♥❞ r❡♠♦✈❛❧ ♦❢ ❍ ❜②♣r♦❞✉❝ts ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳
❑❡②✇♦r❞s ❞❡♥s✐t② ❢✉♥❝t✐♦♥❛❧ t❤❡♦r②✱ ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✐♥❣✱ ♣❛❧❧❛❞✐✉♠✱ ❝❛t❛❧②s✐s✱ ❞❡❤②❞r♦❣❡♥❛t✐♦♥✱ ❡s✲ t❡r✐✜❝❛t✐♦♥✱ ❛❧❝♦❤♦❧ ♦①✐❞❛t✐♦♥
✶
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
✶
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■♥tr♦❞✉❝t✐♦♥
❙❡❧❡❝t✐✈❡ ♦①✐❞❛t✐♦♥ ♦❢ ❛❧❝♦❤♦❧s t♦ ❝❛r❜♦♥②❧ ❝♦♠♣♦✉♥❞s ✐s ❛♥ ✐♠♣♦rt❛♥t ❝❧❛ss ♦❢ ❝❤❡♠✐❝❛❧ tr❛♥s❢♦r♠❛t✐♦♥s ✉s❡❞ ✐♥ ❛ ✇✐❞❡ ✈❛r✐❡t② ♦❢ s②♥t❤❡t✐❝ ❛♣♣❧✐❝❛t✐♦♥s r❛♥❣✐♥❣ ❢r♦♠ ♣❤❛r♠❛❝❡✉t✐✲ ❝❛❧s t♦ ✐♥❞✉str✐❛❧✲s❝❛❧❡ ❜✉❧❦ ❝❤❡♠✐❝❛❧s✳
✶
❆❧❞❡❤②❞❡s ❛♥❞ ❡st❡rs✱ ✐♥ ♣❛rt✐❝✉❧❛r✱ ❛r❡ ❤✐❣❤❧② ✈❛❧✉❡❞
❢♦r ❜♦t❤ t❤❡✐r ✐♥tr✐♥s✐❝ ♣r♦♣❡rt✐❡s ❛♥❞ ❛s r❡❛❣❡♥ts ✐♥ ♦t❤❡r s②♥t❤❡t✐❝ ♣❛t❤✇❛②s✳
✷
❚❤❡s❡ ❝♦♠✲
♣♦✉♥❞s ❛r❡ t②♣✐❝❛❧❧② ❛❝❝❡ss❡❞ t❤r♦✉❣❤ ♦①✐❞❛t✐♦♥ ♦❢ t❤❡✐r ❛❧❝♦❤♦❧ ❛♥❛❧♦❣✉❡s✱ ❢r❡q✉❡♥t❧② ✈✐❛ st♦✐❝❤✐♦♠❡tr✐❝ r❡❛❝t✐♦♥ ✇✐t❤ ❛♥ ♦①✐❞✐③✐♥❣ ❛❣❡♥t ✐♥ tr❛♥s❢♦r♠❛t✐♦♥s ✇❤✐❝❤ ❛r❡ ❜♦t❤ ✐♥❡✣❝✐❡♥t ❛♥❞ ❣❡♥❡r❛t❡ ❛ s✉❜st❛♥t✐❛❧ ❛♠♦✉♥t ♦❢ ❜②♣r♦❞✉❝t✳
✸
❍❡t❡r♦❣❡♥❡♦✉s ❝❛t❛❧②s✐s ♣r♦✈✐❞❡s ❛♥ ❛❧t❡r✲
♥❛t✐✈❡ r♦✉t❡ ❢♦r t❤❡ s❡❧❡❝t✐✈❡ ♦①✐❞❛t✐♦♥ ♦❢ ❛❧❝♦❤♦❧s ✉s✐♥❣ ♠♦❧❡❝✉❧❛r ♦①②❣❡♥✱ ✇❤✐❝❤ ✐♠♣r♦✈❡s ❜♦t❤ ❡✣❝✐❡♥❝② ❛♥❞ ♣r♦s♣❡❝ts ❢♦r s❝❛❧❡✲✉♣✳
✹
❲❤✐❧❡ ♣✉r❡ ♣❧❛t✐♥✉♠ ❣r♦✉♣ ♠❡t❛❧s ✭P●▼✮ s✉❝❤ ❛s Pt ❛♥❞ P❞ ❛r❡ ❝❛♣❛❜❧❡ ♦❢ ❝❛t❛❧②③✐♥❣ t❤❡ ❛q✉❡♦✉s✲♣❤❛s❡ ❛❡r♦❜✐❝ ♦①✐❞❛t✐♦♥ ♦❢ ❛❧❝♦❤♦❧s✱
✺
✈✐❛ ❛❞❞✐t✐♦♥ ♦❢ ♣r♦♠♦t❡rs✱ s✉❝❤ ❛s ❇✐✱ ❚❡✱ ♦r P❜✳
❝❛t❛❧②st ❛❝t✐✈✐t② ❝❛♥ ❜❡ ❣r❡❛t❧② ✐♠♣r♦✈❡❞
✻✕✾
Pr♦♠♦t❡rs ❛r❡ ❡s♣❡❝✐❛❧❧② ✉s❡❢✉❧ ✐♥ t❤❡
♦①✐❞❛t✐✈❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ❛❧✐♣❤❛t✐❝ ♣r✐♠❛r② ❛❧❝♦❤♦❧s✱ ✇❤✐❝❤ t②♣✐❝❛❧❧② ❡①❤✐❜✐t ♣♦♦r ②✐❡❧❞s ✐♥ t❤❡ ❛❜s❡♥❝❡ ♦❢ ♠❛✐♥ ❣r♦✉♣ ♣r♦♠♦t❡rs✳
✶✵
❆❧t❤♦✉❣❤ t❤❡ ♠❡❝❤❛♥✐s♠ ♦❢ ❛❝t✐♦♥ ♦❢ t❤❡ ♣r♦♠♦t✲
❡rs ✐s ✉♥❦♥♦✇♥✱ ❛ ♥✉♠❜❡r ♦❢ ❤②♣♦t❤❡s❡s ❤❛✈❡ ❜❡❡♥ ♣✉t ❢♦rt❤✳
✶✶✕✶✻
❋✉rt❤❡r♠♦r❡✱ ✐t ❤❛s ❜❡❡♥
s❤♦✇♥ t❤❛t ♠❡t❛❧❧✐❝ ✭r❛t❤❡r t❤❛♥ ♦①✐❞✐③❡❞✮ P●▼ s✐t❡s ❛r❡ r❡s♣♦♥s✐❜❧❡ ❢♦r t❤❡ ❜✉❧❦ ♦❢ ❝❛t❛❧②t✐❝ ❛❝t✐✈✐t② ✐♥ t❤❡s❡ s②st❡♠s✳
✶✼✕✷✷
❊①♣❡r✐♠❡♥t❛❧ ♠❡❛s✉r❡♠❡♥ts ♦❢ Pt ♠❡t❛❧ ❝❛t❛❧②st ✇♦r❦✐♥❣ ♣♦✲
t❡♥t✐❛❧s ✐♥❞✐❝❛t❡ t❤❛t t❤❡ ❝❛t❛❧②st ❜❡❝♦♠❡s r❡❞✉❝❡❞ ✉♣♦♥ ❡①♣♦s✉r❡ t♦ t❤❡ ❛❧❝♦❤♦❧ s✉❜str❛t❡ r❡❧❛t✐✈❡ t♦ t❤❡ ♦①✐❞✐③❡❞ ❛✐r✲❡①♣♦s❡❞ r❡st✐♥❣ ❝❛t❛❧②st✳
✶✻✱✷✸
▼♦r❡♦✈❡r✱ ❝②❝❧✐❝ ✈♦❧t❛♠♠❡tr② ❡①♣❡r✲
✐♠❡♥ts s❤♦✇ t❤❛t ❇✐✲♣r♦♠♦t✐♦♥✱ ✇❤✐❝❤ ✐♠♣r♦✈❡s ❝❛t❛❧②st ❛❝t✐✈✐t②✱ s✉♣♣r❡ss❡s ❍ s♦r♣t✐♦♥ ♦♥ Pt ❝❛t❛❧②sts✱ ✇❤✐❝❤ ✐♥❞✐❝❛t❡s ❛ ♥❡❣❛t✐✈❡ ❝♦rr❡❧❛t✐♦♥ ❜❡t✇❡❡♥ s✉r❢❛❝❡ ❍ ❝♦✈❡r❛❣❡ ❛♥❞ ❝❛t❛❧②st ❛❝t✐✈✐t②✳
✶✻
❚❤❡s❡ ♦❜s❡r✈❛t✐♦♥s s✉❣❣❡st t❤❛t ✉♥♣r♦♠♦t❡❞ ❝❛t❛❧②sts ❛r❡ ❧✐❦❡❧② ❛t ❧❡❛st ♣❛rt✐❛❧❧②
❤②❞r♦❣❡♥✲❝♦✈❡r❡❞ ✉♥❞❡r ♦♣❡r❛t✐♥❣ ❝♦♥❞✐t✐♦♥s✱ ✐♥ ❝♦♥tr❛st t♦ t❤❡ ♣❛rt✐❛❧❧② ♦①②❣❡♥✲❝♦✈❡r❡❞ r❡st✐♥❣ ✭❛✐r✲❡①♣♦s❡❞✮ ❝❛t❛❧②st✳ ❜② t❤❡ ❞✐✣❝✉❧t② ♦❢ ♣❡r❢♦r♠✐♥❣
✶✵✱✶✻
❋✉rt❤❡r ❝❤❛r❛❝t❡r✐③❛t✐♦♥ ♦❢ t❤❡s❡ ❝❛t❛❧②sts ✐s ❝♦♠♣❧✐❝❛t❡❞
✐♥ s✐t✉
♠❡❛s✉r❡♠❡♥ts ♦❢ ❧✐q✉✐❞✲♣❤❛s❡ ❤❡t❡r♦❣❡♥❡♦✉s ❝❛t❛❧②sts✳
❚❤❡ ❡①❛❝t ♠❡❝❤❛♥✐s♠ ❢♦r t❤❡ ♦①✐❞❛t✐✈❡ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r✐♠❛r② ❛❧❝♦❤♦❧s ♦✈❡r P●▼ ✐s
✷
ACS Paragon Plus Environment
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ACS Catalysis
❛ ♠❛tt❡r ♦❢ s♦♠❡ ❞❡❜❛t❡✳ ❋♦r ❛t ❧❡❛st s♦♠❡ ❛❧❝♦❤♦❧s✱ s✉❝❤ ❛s ❜❡♥③②❧ ❛❧❝♦❤♦❧✱ ❛♥ ❛❧❞❡❤②❞❡ ✐♥t❡r♠❡❞✐❛t❡ ❝❛♥ ❜❡ ✐s♦❧❛t❡❞✳ ■♥ ❝♦♥tr❛st✱ ❢♦r ♦t❤❡r ❛❧❝♦❤♦❧s s✉❝❤ ❛s ✶✲♦❝t❛♥♦❧✱ t❤❡ ❛❧❞❡❤②❞❡ ✐♥t❡r♠❡❞✐❛t❡ ❡✐t❤❡r r❡❛❝ts t♦♦ r❛♣✐❞❧② t♦ ❜❡ ❞❡t❡❝t❡❞✱ ♦r ❞♦❡s ♥♦t ❢♦r♠ ❛t ❛❧❧✳ ♣r♦❝❡ss ❜② ✇❤✐❝❤ t❤❡ ❛❧❞❡❤②❞❡ ❢♦r♠s ✐s ♥♦t ❦♥♦✇♥✳
✾
❚❤❡ ❡①❛❝t
❯♥❞❡r ❜❛s✐❝ ❝♦♥❞✐t✐♦♥s✱ ✐t ❤❛s ❜❡❡♥
♣r♦♣♦s❡❞ t❤❛t t❤❡ ❛❧❝♦❤♦❧ ❜❡❝♦♠❡s ❞❡♣r♦t♦♥❛t❡❞ ✐♥ s♦❧✉t✐♦♥ ❛♥❞ ✉♥❞❡r❣♦❡s ❤②❞r✐❞❡ ❡❧✐♠✐✲ ♥❛t✐♦♥ ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ t♦ ❢♦r♠ t❤❡ ❛❧❞❡❤②❞❡✳
✷✹✱✷✺
❚❤✐s ❤②♣♦t❤❡s✐s ❤❛s ❜❡❡♥ ❞✐s♣✉t❡❞
❞✉❡ t♦ t❤❡ ♦❜s❡r✈❛t✐♦♥ t❤❛t ♦①✐❞❛t✐♦♥ ❛❧s♦ ♦❝❝✉rs ✉♥❞❡r ❛❝✐❞✐❝ ❝♦♥❞✐t✐♦♥s✱ ♣r♦♣♦s❡❞ ✐♥st❡❛❞ t❤❛t t❤❡ ❛❧❦♦①✐❞❡ ✐s ❢♦r♠❡❞ ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳
✷✼✱✷✽
✷✻
❛♥❞ ✐t ❤❛s ❜❡❡♥
❖t❤❡r ❛✉t❤♦rs ❤❛✈❡
s✉❣❣❡st❡❞ t❤❛t ✐t ✐s t❤❡ ❈−❍ ❜♦♥❞ t❤❛t ✐s ❜r♦❦❡♥ ✜rst ❞✉❡ t♦ ✐ts ✇❡❛❦❡r ❜♦♥❞ str❡♥❣t❤✳
✷✾✱✸✵
❚❤❡ s✉❜s❡q✉❡♥t ♦①✐❞❛t✐♦♥ ♦❢ ❛❧❞❡❤②❞❡ t♦ ❡st❡r ✐s ❛❧s♦ ♣♦♦r❧② ✉♥❞❡rst♦♦❞✳ ❚❤❡ ❛❧❞❡❤②❞❡ ✐♥t❡r♠❡❞✐❛t❡ ♠❛② ❞❡s♦r❜ ❢r♦♠ t❤❡ s✉r❢❛❝❡ ❛♥❞ r❡❛❝t ✇✐t❤ ❛❧❝♦❤♦❧ ✐♥ s♦❧✉t✐♦♥ t♦ ❢♦r♠ ❛ ❤❡♠✐✲ ❛❝❡t❛❧ s♣❡❝✐❡s✳
✸✶✕✸✸
❚❤❡ ♣✉t❛t✐✈❡ ❤❡♠✐❛❝❡t❛❧ ✐♥t❡r♠❡❞✐❛t❡ ♠✉st ❜❡ ❢✉rt❤❡r ❞❡❤②❞r♦❣❡♥❛t❡❞
t♦ t❤❡ ✜♥❛❧ ❡st❡r ♣r♦❞✉❝t✱ ❛♥❛❧♦❣♦✉s t♦ t❤❡ ✐♥✐t✐❛❧ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ t❤❡ ❛❧❝♦❤♦❧ t♦ t❤❡ ❛❧❞❡❤②❞❡✳ ❍♦✇❡✈❡r✱ s✉❝❤ ❛♥ ❛❧❞❡❤②❞❡ ✐♥t❡r♠❡❞✐❛t❡ ❝❛♥♥♦t ❛❧✇❛②s ❜❡ ✐❞❡♥t✐✜❡❞✱ s✉❣❣❡st✐♥❣ t❤❛t ❛❧t❡r♥❛t✐✈❡ ♣❛t❤✇❛②s ♠❛② ❛❧s♦ ❡①✐st✳
✸✹
❈♦♥s❡q✉❡♥t❧②✱ t❤❡ ❞❡t❛✐❧❡❞ ❛❧❞❡❤②❞❡ ❡st❡r✐✜❝❛t✐♦♥
♠❡❝❤❛♥✐s♠ ✐s ❛❧s♦ ❤✐❣❤❧② ♥♦♥✲tr✐✈✐❛❧✳ ■♥ ❛ ♣r✐♦r ❝♦♠♣✉t❛t✐♦♥❛❧ ✇♦r❦✱ ❍✐❜❜✐tts ❛♥❞ ◆❡✉r♦❝❦ s✉❣❣❡st ✈❛r✐♦✉s ♣❛t❤✇❛②s ❢♦r t❤❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ❛♥❞ ♦①✐❞❛t✐♦♥ ♦❢ ❡t❤❛♥♦❧ t♦ ❛❝❡t❛t❡ ❜❛s❡❞ ♦♥ t❤❡ ❉❋❚✲❝❛❧❝✉❧❛t❡❞ ❡♥❡r❣❡t✐❝s ❛♥❞ ❜❛rr✐❡r ❤❡✐❣❤ts ❢♦r ❛ s❡r✐❡s ♦❢ r❡❛❝t✐♦♥s ♦♥ t❤❡ ✇❛t❡r✲s♦❧✈❛t❡❞ P❞✭✶✶✶✮ s✉r❢❛❝❡✳
✸✺
❍♦✇❡✈❡r✱
❞✉❡ t♦ t❤❡ ❝♦♠♣❧❡①✐t② ♦❢ t❤❡✐r s❡t✉♣✱ t❤❡② ✇❡r❡ ✉♥❛❜❧❡ t♦ ♣❡r❢♦r♠ ❛ ❢✉❧❧ ♠✐❝r♦❦✐♥❡t✐❝ ❛♥❛❧✲ ②s✐s✱ ❛♥❞ t❤✉s t❤❡✐r ❝♦♥❝❧✉s✐♦♥s r❡❣r❛❞✐♥❣ t❤❡ ♣r❡❞♦♠✐♥❛♥t r❡❛❝t✐♦♥ ♣❛t❤✇❛②s r❡❧✐❡❞ ✉♣♦♥ ❛ss✉♠♣t✐♦♥s ❛❜♦✉t t❤❡ ❝♦♥❞✐t✐♦♥ ♦❢ t❤❡ ✇♦r❦✐♥❣ ❝❛t❛❧②st s✉r❢❛❝❡ ✭❡✳❣✳ ❤②❞r♦❣❡♥ ❝♦✈❡r❛❣❡✮✳ ■♥ t❤✐s ✇♦r❦✱ ✇❡ ✉s❡ P❞✭✶✶✶✮✲❝❛t❛❧②③❡❞ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ✶✲♣r♦♣❛♥♦❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ✉♥❞❡r ❜❛s✐❝ ❝♦♥❞✐t✐♦♥s ❛s ❛ ♠♦❞❡❧ ♦❢ ❛❧✐♣❤❛t✐❝ ♣r✐♠❛r② ❛❧❝♦❤♦❧ ❡st❡r✐✜❝❛t✐♦♥✳ ❲❡ ✉t✐❧✐③❡ ✜rst✲ ♣r✐♥❝✐♣❧❡s ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✐♥❣ ✐♥❢♦r♠❡❞ ❜② ❞❡♥s✐t② ❢✉♥❝t✐♦♥❛❧ t❤❡♦r② ✭❉❋❚✮ ❝❛❧❝✉❧❛t✐♦♥s ♦❢ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❛♥❞ t❤❡ s♦❧✉t✐♦♥✲♣❤❛s❡ s♣❡❝✐❡s✳ ▼✐❝r♦❦✐♥❡t✐❝ ❛♥❛❧②s✐s ♦❢ t❤❡ r❡❛❝t✐♦♥ ♥❡t✇♦r❦ ❛❧❧♦✇s ✉s t♦ ✐❞❡♥t✐❢② t❤❡ ❞♦♠✐♥❛♥t r❡❛❝t✐♦♥ ♣❛t❤✇❛②s t❤❛t ❝♦♥tr✐❜✉t❡ t♦ t❤❡ ❝❛t❛❧②t✐❝
✸
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 4 of 35
❛❝t✐✈✐t② ❢r♦♠ t❤❡ ❧❛r❣❡ ♥✉♠❜❡r ♦❢ ♣♦ss✐❜❧❡ r♦✉t❡s ❢r♦♠ ♣r♦♣❛♥♦❧ t♦ t❤❡ ✜♥❛❧ ❡st❡r ♣r♦❞✉❝t✳ ■t ❛❧s♦ ❢❛❝✐❧✐t❛t❡s ❛ ❞✐r❡❝t ❡①❛♠✐♥❛t✐♦♥ ♦❢ t❤❡ st❛t❡ ♦❢ t❤❡ ❝❛t❛❧②st ✉♥❞❡r ✇♦r❦✐♥❣ ❝♦♥❞✐t✐♦♥s ❛♥❞ t❤❡ r♦❧❡ ♦❢ ✈❛r✐♦✉s r❡❛❝t❛♥ts✱ ✐♥❝❧✉❞✐♥❣✱ ✐♥ ♣❛rt✐❝✉❧❛r✱ t❤❡ r♦❧❡ ♦❢ ❝❛t❛❧②t✐❝ ❜❛s❡✳ ■♥ ♦r❞❡r t♦ ❛❝❤✐❡✈❡ t❤❡s❡ ❣♦❛❧s✱ ✇❡ ❞❡✈❡❧♦♣ s❡✈❡r❛❧ ♥♦✈❡❧ ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✐♥❣ t❡❝❤♥✐q✉❡s ❢♦r t❤❡ ❛♥❛❧②s✐s ♦❢ ❧✐q✉✐❞✲♣❤❛s❡ ❤❡t❡r♦❣❡♥❡♦✉s ❝❛t❛❧②t✐❝ r❡❛❝t✐♦♥ ♥❡t✇♦r❦s✳ ❚❤✐s ✇♦r❦ ✐s ♦♥❡ ♦❢ t❤❡ ✜rst ❝♦♠♣r❡❤❡♥s✐✈❡ ❛♣♣❧✐❝❛t✐♦♥ ♦❢ ✜rst✲♣r✐♥❝✐♣❧❡s ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✐♥❣ t♦ ❛ ❧✐q✉✐❞✲♣❤❛s❡ ❤❡t❡r♦❣❡♥❡♦✉s r❡❛❝t✐♦♥ ♥❡t✇♦r❦ ❝♦♥t❛✐♥✐♥❣ ❝❤❛r❣❡❞ r❡❛❝t❛♥ts✱ ❛❝❝♦✉♥t✐♥❣ ❢♦r t❤❡ ❡✛❡❝ts ♦❢ s♦❧✈❛t✐♦♥ ♦♥ ❜♦t❤ t❤❡r♠♦❞②♥❛♠✐❝s ❛♥❞ ♠❛ss tr❛♥s♣♦rt✳ ❆❞❞✐t✐♦♥❛❧❧②✱ ✇❡ ✐♥tr♦❞✉❝❡ ❛ ♠❡t❤♦❞ t♦ ❛❝❝♦✉♥t ❢♦r ❛❞s♦r♣t✐♦♥ ❛♥❞ ❞❡s♦r♣t✐♦♥ ♦❢ ❝❤❛r❣❡❞ r❡❛❝t❛♥ts ❛♥❞ t❤❡✐r ✐♥✢✉❡♥❝❡ ♦♥ s✉❜s❡✲ q✉❡♥t ❛❞s♦r♣t✐♦♥ ✴ r❡❛❝t✐♦♥✳ ■♥t❡r❡st✐♥❣❧②✱ ✇❤✐❧❡ ✇❡ ✜♥❞ ✐♥t❡r♠❡❞✐❛t❡ ❛♥❞ tr❛♥s✐t✐♦♥ st❛t❡ ❡♥❡r❣✐❡s ❢♦r ♦✉r s②st❡♠ t❤❛t ❛r❡ ✐♥ q✉❛❧✐t❛t✐✈❡ ❛❣r❡❡♠❡♥t ✇✐t❤ t❤❡ ♣r✐♦r ✜♥❞✐♥❣s ♦❢ ❍✐❜❜✐tts ❛♥❞ ◆❡✉r♦❝❦✱ t❤❡ ♣r❡❞♦♠✐♥❛♥t r❡❛❝t✐♦♥ ♣❛t❤✇❛②s ❞✐✛❡r✱ ❧✐❦❡❧② ❞✉❡ t♦ t❤❡ str♦♥❣ ✐♥✢✉❡♥❝❡ ♦❢ t❤❡ ❝❛t❛❧②sts s✉r❢❛❝❡ ❝♦✈❡r❛❣❡ ✉♥❞❡r st❡❛❞②✲st❛t❡ ✇♦r❦✐♥❣ ❝♦♥❞✐t✐♦♥s✱ t❤✉s ❤✐❣❤❧✐❣❤t✐♥❣ t❤❡ ✐♠♣♦rt❛♥❝❡ ❛ ❞❡t❛✐❧❡❞ ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ❢♦r t❤✐s r❡❛❝t✐♦♥ ♥❡t✇♦r❦✳
✷
❚❤❡♦r❡t✐❝❛❧ ♠❡t❤♦❞s
❚❤❡ ❡♥❡r❣✐❡s ❛♥❞ ❣❡♦♠❡tr✐❡s ♦❢ s✉r❢❛❝❡✲❜♦✉♥❞ s♣❡❝✐❡s ✇❡r❡ ❞❡t❡r♠✐♥❡❞ ✇✐t❤ t❤❡ ♣❡r✐♦❞✐❝ ❞❡♥s✐t② ❢✉♥❝t✐♦♥❛❧ t❤❡♦r② ✭❉❋❚✮ ❝♦❞❡ ❱❆❙P ✐♥ ❛ ❜❛s✐s ♦❢ ♣❧❛♥❡ ✇❛✈❡s ✉♣ t♦ ❛ ❝✉t♦✛ ❡♥✲ ❡r❣② ♦❢
450 eV✳ ✸✻✕✸✾
❆❧❧ ❝❛❧❝✉❧❛t✐♦♥s ✇❡r❡ r✉♥ ✉s✐♥❣ t❤❡ P②t❤♦♥ ❡♥✈✐r♦♥♠❡♥t ❆❙❊✳
✹✵
●❡✲
♦♠❡tr② ♦♣t✐♠✐③❛t✐♦♥s ❛♥❞ ✈✐❜r❛t✐♦♥❛❧ ❢r❡q✉❡♥❝② ❝❛❧❝✉❧❛t✐♦♥s ✇❡r❡ ♣❡r❢♦r♠❡❞ ✇✐t❤ t❤❡ P❇❊✲ ❉✸✭❆❇❈✮ ❞✐s♣❡rs✐♦♥✲❝♦rr❡❝t❡❞ ❞❡♥s✐t② ❢✉♥❝t✐♦♥❛❧ ♠❡t❤♦❞✱ ❛♥❞ s✐♥❣❧❡✲♣♦✐♥t ❡♥❡r❣✐❡s ✇❡r❡ ❡✈❛❧✉❛t❡❞ ✇✐t❤ t❤❡ r❛♥❣❡✲s❡♣❛r❛t❡❞ ❍❙❊✵✻✲❉✸✭❇❏✱❆❇❈✮ ♠❡t❤♦❞ ❛t t❤❡ P❇❊✲❉✸✭❆❇❈✮ ❣❡✲ ♦♠❡tr✐❡s✳
✹✶✕✺✶
❲❤✐❧❡ ❉❋❚ ❝❛❧❝✉❧❛t✐♦♥s ✉s✐♥❣ ❤②❜r✐❞ ❢✉♥❝t✐♦♥❛❧s s✉❝❤ ❛s ❍❙❊✵✻ ❛r❡ s✐❣♥✐✜✲
❝❛♥t❧② ♠♦r❡ ❝♦♠♣✉t❛t✐♦♥❛❧❧② ❡①♣❡♥s✐✈❡ t❤❛♥ t②♣✐❝❛❧ s❡♠✐❧♦❝❛❧ ❢✉♥❝t✐♦♥❛❧s s✉❝❤ ❛s P❇❊✱ t❤❡ ✐♥❝❧✉s✐♦♥ ♦❢ ❡①❛❝t ❡①❝❤❛♥❣❡ ❤❛s ❛ s✉❜st❛♥t✐❛❧ ❡✛❡❝t ♦♥ r❡❛❝t✐♦♥ ❜❛rr✐❡r ❤❡✐❣❤ts ❛♥❞ ✐♥t❡r✲ ♠❡❞✐❛t❡ ❜✐♥❞✐♥❣ ❡♥❡r❣✐❡s✳
✺✷✕✺✹
P❇❊✲❉✸✭❆❇❈✮ ②✐❡❧❞s ❛ ❧❛tt✐❝❡ ❝♦♥st❛♥t ♦❢
✹
ACS Paragon Plus Environment
3.90 ➴
❢♦r ❜✉❧❦
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ACS Catalysis
P❞✱ ✇❤✐❝❤ ❝♦♠♣❛r❡s ❢❛✈♦r❛❜❧② t♦ t❤❡ ❡①♣❡r✐♠❡♥t❛❧ ❧❛tt✐❝❡ ❝♦♥st❛♥t ♦❢ s✉r❢❛❝❡ ✇❛s ♠♦❞❡❧❡❞ ❛s ❛ ✹✲❧❛②❡r ✸①✸ s❧❛❜ ✇✐t❤ ❛
15 ➴
3.89 ➴✳ ✺✺
❚❤❡ P❞✭✶✶✶✮
✈❛❝✉✉♠ ❣❛♣✱ ❛♥❞ t❤❡ ❇r✐❧❧♦✉✐♥ ③♦♥❡
✇❛s s❛♠♣❧❡❞ ✇✐t❤ ❛ ✸①✸①✶ ▼♦♥❦❤♦rst✲P❛❝❦ ❦✲♣♦✐♥t ♠❡s❤✳
✺✻
❚❤❡ ❜♦tt♦♠ t✇♦ ❧❛②❡rs ♦❢ t❤❡
s❧❛❜ ✇❡r❡ ✜①❡❞ t♦ t❤❡ P❇❊✲❉✸✭❆❇❈✮ ❧❛tt✐❝❡ ❝♦♥st❛♥t✱ ✇❤✐❧❡ t❤❡ t♦♣ t✇♦ ❧❛②❡rs ✇❡r❡ ❛❧✲ ❧♦✇❡❞ t♦ r❡❧❛① ✐♥ ❛❧❧ ❣❡♦♠❡tr② ♦♣t✐♠✐③❛t✐♦♥s✳ ❚❤❡ ❡✛❡❝t ♦❢ s♦❧✈❛t✐♦♥ ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❛♥❞ ❛❞s♦r❜❡❞ ✐♥t❡r♠❡❞✐❛t❡s ✇❡r❡ ✐♥❝❧✉❞❡❞ t❤r♦✉❣❤ t❤❡ ✉s❡ ♦❢ s✐♥❣❧❡✲♣♦✐♥t ●▲❙❙❆✶✸ ❝♦♥t✐♥✲ ✉✉♠ s♦❧✈❛t✐♦♥ ♠♦❞❡❧ ❝❛❧❝✉❧❛t✐♦♥s ✉s✐♥❣ ❱❆❙Ps♦❧ ✇✐t❤ ♠❡t❤❛♥♦❧ ❛s t❤❡ s♦❧✈❡♥t ❛t t❤❡ P❇❊ ❧❡✈❡❧ ♦❢ t❤❡♦r②✳ ♠❡t❤♦❞✱
✻✵✕✻✷
✺✼✕✺✾
P❛t❤✇❛②s ❢♦r ❛❧❧ r❡❛❝t✐♦♥s ✇❡r❡ ❧♦❝❛t❡❞ ✉s✐♥❣ t❤❡ ♥✉❞❣❡❞ ❡❧❛st✐❝ ❜❛♥❞
❛♥❞ tr❛♥s✐t✐♦♥ st❛t❡s ✇❡r❡ ♦♣t✐♠✐③❡❞ ✉s✐♥❣ t❤❡ ❞✐♠❡r ♠❡t❤♦❞✳
✹✺✱✻✸✱✻✹
❆❧❧ tr❛♥s✐✲
t✐♦♥ st❛t❡s ✇❡r❡ ✈❡r✐✜❡❞ t♦ ❤❛✈❡ ❡①❛❝t❧② ♦♥❡ ✐♠❛❣✐♥❛r② ✈✐❜r❛t✐♦♥❛❧ ❢r❡q✉❡♥❝② ❝♦rr❡s♣♦♥❞✐♥❣ t♦ t❤❡ ❡①♣❡❝t❡❞ r❡❛❝t✐♦♥ ❝♦♦r❞✐♥❛t❡✳ ❙♦❧✉t✐♦♥✲♣❤❛s❡ s♣❡❝✐❡s ✇❡r❡ ♦♣t✐♠✐③❡❞ ✐♥ ●❛✉ss✐❛♥ ✵✾ ✉s✐♥❣ t❤❡ ❛✉❣✲❝❝✲♣❱❚❩ ❜❛s✐s s❡t
✻✻
✻✺
✇✐t❤ t❤❡ P❇❊✲❉✸✭❆❇❈✮ ♠❡t❤♦❞
❛♥❞ t❤❡ ❙▼❉ ❝♦♥t✐♥✉✉♠ s♦❧✈❛t✐♦♥ ♠♦❞❡❧
✻✼
✇✐t❤ ♠❡t❤❛♥♦❧
s♦❧✈❡♥t✳ ❙▼❉ ✇❛s ❝❤♦s❡♥ s✐♥❝❡ ✐t ✇❛s ♣❛r❛♠❡t❡r✐③❡❞ t♦ r❡♣r♦❞✉❝❡ ❡①♣❡r✐♠❡♥t❛❧ t♦t❛❧ ❢r❡❡ ❡♥❡r❣✐❡s ♦❢ s♦❧✈❛t✐♦♥✱ ✐♥❝❧✉❞✐♥❣ t❤❡ ❝❛✈✐t❛t✐♦♥ ❡♥❡r❣②✳
◆♦t❡ t❤❛t ❢♦r ♣❡r✐♦❞✐❝ ❝❛❧❝✉❧❛t✐♦♥s
✐♥✈♦❧✈✐♥❣ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✱ t❤❡ ●▲❙❙❆✶✸ P❈▼ ✐s ✉s❡❞ ✐♥st❡❛❞ ♦❢ ❙▼❉✳ ❚❤✐s ✐s ❜❡❝❛✉s❡ ❙▼❉ ✐s ♣❛r❛♠❡t❡r✐③❡❞ t♦ r❡♣r♦❞✉❝❡ ❡①♣❡r✐♠❡♥t❛❧
❢r❡❡ ❡♥❡r❣✐❡s
♦❢ s♦❧✈❛t✐♦♥✱ ✇❤✐❝❤ ✐♥❝❧✉❞❡s
❝♦♥tr✐❜✉t✐♦♥s ❛r✐s✐♥❣ ❢r♦♠ t❤❡ ❧♦ss ♦❢ tr❛♥s❧❛t✐♦♥❛❧ ❡♥tr♦♣② ♦❢ ❣❛s✲♣❤❛s❡ s♣❡❝✐❡s✳ ♥♦t r❡❧❡✈❛♥t ❢♦r ✐♠♠♦❜✐❧❡ s②st❡♠s✱ s✉❝❤ ❛s ❛❞s♦r❜❛t❡s ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳
❚❤✐s ✐s
❙✐♠✐❧❛r❧②✱
●▲❙❙❆✶✸ ✇♦✉❧❞ ♣r❡❞✐❝t ✐♥❛❝❝✉r❛t❡ s♦❧✈❛t✐♦♥ ❢r❡❡ ❡♥❡r❣✐❡s ♦❢ s♣❡❝✐❡s ✐♥ s♦❧✉t✐♦♥ ❞✉❡ t♦ ✐ts ♥❡❣❧❡❝t ♦❢ tr❛♥s❧❛t✐♦♥❛❧ ❡♥tr♦♣② ❧♦ss✳ ❍❙❊✵✻✲❉✸✭❇❏✱❆❇❈✮ ♠❡t❤♦❞
✺✶
❙✐♥❣❧❡✲♣♦✐♥t ❝❛❧❝✉❧❛t✐♦♥s ✇❡r❡ ♣❡r❢♦r♠❡❞ ✇✐t❤ t❤❡
❛♥❞ t❤❡ r❡s✉❧t✐♥❣ ❡♥❡r❣✐❡s ✇❡r❡ ❡①tr❛♣♦❧❛t❡❞ t♦ t❤❡ ❝♦♠♣❧❡t❡
❜❛s✐s s❡t ❧✐♠✐t ✉s✐♥❣ t❤❡ ❛✉❣✲❝❝✲P❱♥❩ ❜❛s✐s s❡ts ✭♥ ❂
2
t♦
5✮✳
❈❛❧❝✉❧❛t✐♦♥s ✇❡r❡ ♣❡r❢♦r♠❡❞
✇✐t❤ ❛♥❞ ✇✐t❤♦✉t s♦❧✈❛t✐♦♥ ❝♦rr❡❝t✐♦♥ t♦ ❞❡t❡r♠✐♥❡ t❤❡ ❢r❡❡ ❡♥❡r❣② ♦❢ s♦❧✈❛t✐♦♥✱ ✇❤✐❝❤ ✇❛s ✉s❡❞ t♦ ❝♦rr❡❝t t❤❡ ❡♥❡r❣② ♦❢ t❤❡ ❣❛s✲♣❤❛s❡ s♣❡❝✐❡s ❛s ❞❡t❡r♠✐♥❡❞ ✐♥ ❱❆❙P ✭s❡❡ ❋✐❣✉r❡ ✶✮✳ ❆❞❞✐t✐♦♥❛❧❧②✱ t❤❡ ❡♥❡r❣② ♦❢ s♣❡❝✐❡s t❤❛t ❝❛rr② ❛ ❢♦r♠❛❧ ♥❡❣❛t✐✈❡ ❝❤❛r❣❡ ✇❛s ❞❡t❡r♠✐♥❡❞ ❜② ♣❡r❢♦r♠✐♥❣ ❝❛❧❝✉❧❛t✐♦♥s ♦❢ t❤❡ ❝♦rr❡s♣♦♥❞✐♥❣ ♥❡✉tr❛❧ r❛❞✐❝❛❧ ✐♥ ❱❆❙P✱ ❛♥❞ ❛❞❞✐♥❣ t♦ t❤❛t
✺
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Paragon Plus Environment
Page 6 of 35
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ACS Catalysis
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 8 of 35
♣❤❛s❡ s♣❡❝✐❡s✳ ◆♦t❡ t❤❛t t❤✐s ❝❤♦✐❝❡ ❛✛❡❝ts t❤❡ r❡♣♦rt❡❞ ❢r❡❡ ❡♥❡r❣② ♦❢ ❛❞s♦r♣t✐♦♥✱ ❜✉t ❞♦❡s ♥♦t ❛✛❡❝t ❛♥② t❤❡r♠♦❞②♥❛♠✐❝ ♦r ❦✐♥❡t✐❝ ♣❛r❛♠❡t❡rs ♦❢ t❤❡ ♠♦❞❡❧✳ ♦❢
2 × 10−9 m2 /s
❆ ❞✐✛✉s✐♦♥ ❝♦♥st❛♥t
✇❛s ✉s❡❞ ❢♦r ❛❧❧ s♦❧✉t✐♦♥✲♣❤❛s❡ s♣❡❝✐❡s✳ ❲❡ ✜♥❞ t❤❛t ✇❤✐❧❡ ❛❞s♦r♣t✐♦♥ ✐s
❞✐✛✉s✐♦♥✲❧✐♠✐t❡❞✱ ✐t ✐s ♥♦t r❛t❡ ❧✐♠✐t✐♥❣✱ ❛♥❞ ❛s s✉❝❤ t❤❡ r❡s✉❧ts ♦❢ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ❛r❡ ✐♥✈❛r✐❛♥t t♦ t❤❡ ❝❤♦✐❝❡ ♦❢ ❞✐✛✉s✐♦♥ ❝♦♥st❛♥t t♦ ✇✐t❤✐♥ ❛♥ ♦r❞❡r ♦❢ ♠❛❣♥✐t✉❞❡ ❢♦r ❛❧❧ s♣❡❝✐❡s✳ ❲❡ ❛ss✉♠❡ t❤❛t t❤❡ ❜❛s❡ r❡❛❝ts ✇✐t❤ t❤❡ s♦❧✈❡♥t ✭♠❡t❤❛♥♦❧✮ q✉❛♥t✐t❛t✐✈❡❧② t♦ ❢♦r♠ ♠❡t❤♦①✐❞❡✱ ❛♥❞ ✇❡ ✐❣♥♦r❡ t❤❡ ♣r❡s❡♥❝❡ ♦❢ ❛♥② r❡s✉❧t✐♥❣ ❝♦♥❥✉❣❛t❡ ❛❝✐❞✳
■♥ t❤✐s ✇❛②✱ ✇❡
❝♦♥tr♦❧ t❤❡ ❝♦♥❝❡♥tr❛t✐♦♥ ♦❢ t❤❡ ❜❛s❡ ❜② ❝❤❛♥❣✐♥❣ t❤❡ ❝♦♥❝❡♥tr❛t✐♦♥ ♦❢ ♠❡t❤♦①✐❞❡ ✐♥ s♦✲ ❧✉t✐♦♥✳
❲❡ ❢✉rt❤❡r s❡t t❤❡ ❝♦♥❝❡♥tr❛t✐♦♥ ♦❢ t❤❡ ♣r♦♣♦①✐❞❡ ❛♥✐♦♥ ✐♥ s♦❧✉t✐♦♥ t♦ ♦❜❡② t❤❡
♣r❡❞✐❝t❡❞ ❡q✉✐❧✐❜r✐✉♠ ❢♦r ♣r♦t♦♥ tr❛♥s❢❡r ❢r♦♠ ♣r♦♣❛♥♦❧ t♦ ♠❡t❤♦①✐❞❡✳ ❋♦r ❛❞s♦r♣t✐♦♥ ♦❢ ❛♥✐♦♥s t♦ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✱ ✇❡ ❛ss✉♠❡ t❤❛t t❤❡ ❡❧❡❝tr♦♥ ✐s tr❛♥s❢❡rr❡❞ ❢r♦♠ t❤❡ ❛♥✐♦♥ t♦ t❤❡ ♠❡t❛❧✱ r❡s✉❧t✐♥❣ ✐♥ ❛ ❝❤❛♥❣❡ ✐♥ ❡♥❡r❣② t❤❛t ❞❡♣❡♥❞s ♦♥ t❤❡ ✇♦r❦ ❢✉♥❝t✐♦♥ ♦❢ t❤❡ ♠❡t❛❧✳
❚♦ ❛❝❝♦✉♥t ❢♦r ❛ ❜✉✐❧❞✉♣ ♦❢ ❝❤❛r❣❡ ♦♥ t❤❡ ❝❛t❛❧②st✱ ✇❡ ✐♥tr♦❞✉❝❡
❛♥ ❡❧❡❝tr♦♥✲❡❧❡❝tr♦♥ r❡♣✉❧s✐♦♥ ❡♥❡r❣② t❤❛t ❢✉rt❤❡r ♠♦❞✉❧❛t❡s t❤❡ ❜✐♥❞✐♥❣ ❡♥❡r❣② ♦❢ ❛♥✐♦♥s✳ ❚❤✐s ❡❧❡❝tr♦♥✲❡❧❡❝tr♦♥ r❡♣✉❧s✐♦♥ ❡♥❡r❣② ❝♦rr❡s♣♦♥❞s t♦ t❤❡ ❞✐✛❡r❡♥t✐❛❧ ❡♥❡r❣② ♦❢ ✐♥tr♦❞✉❝✐♥❣ ❝❤❛r❣❡ t♦ ❛ ❝❛♣❛❝✐t♦r✱ ❛s ❛ ❝❤❛r❣❡❞ s✉r❢❛❝❡ ❢♦r♠s ❛ ❞♦✉❜❧❡✲❧❛②❡r ❝❛♣❛❝✐t♦r ✐♥ s♦❧✉t✐♦♥ ✇✐t❤ ❝♦✉♥t❡r✐♦♥s✱ ✇❤✐❝❤ ❛❝❝✉♠✉❧❛t❡ ♥❡❛r t❤❡ s✉r❢❛❝❡✳ ❆ ♠♦r❡ ❞❡t❛✐❧❡❞ ❞✐s❝✉ss✐♦♥ ♦♥ ♦✉r ❞♦✉❜❧❡✲ ❧❛②❡r ❝❛♣❛❝✐t♦r ♠♦❞❡❧ ❝❛♥ ❜❡ ❢♦✉♥❞ ✐♥ t❤❡ ❙■✳ ❇♦t❤ P❇❊✲❉✸✭❆❇❈✮ ❛♥❞ ❍❙❊✵✻✲❉✸✭❇❏✱❆❇❈✮ ♣r❡❞✐❝t t❤❡ ❞✐ss♦❝✐❛t✐✈❡ ❛❞s♦r♣t✐♦♥ ♦❢ ❍✷ t♦ P❞✭✶✶✶✮ t♦ ❜❡ s✉❜st❛♥t✐❛❧❧② ♠♦r❡ ❡①♦t❤❡r♠✐❝ t❤❛♥ ❡①♣❡r✐♠❡♥ts ❤❛✈❡ s❤♦✇♥✳ ❈♦♥s❡q✉❡♥t❧②✱ t❤❡ ❡♥❡r❣② ♦❢ s✉r❢❛❝❡✲❜♦✉♥❞ ❤②❞r♦❣❡♥ ❛t♦♠s ✇❛s ♦✛s❡t ❜② ❛ ❝♦♥st❛♥t ✈❛❧✉❡ t♦ ❛❝❝✉r❛t❡❧② ♠❛t❝❤ t❤❡ ❡①♣❡r✐♠❡♥t❛❧ ❜✐♥❞✐♥❣ ❡♥t❤❛❧♣② ♠❡❛s✉r❡❞ ❜② ❙✐❧❜❛✉❣❤ ❛♥❞ ❈❛♠♣❜❡❧❧✳
✼✵
❚❤❡ ❜✐♥❞✐♥❣ ❡♥❡r❣② ♦❢ ❛❧❧ st❛❜❧❡ ✐♥t❡r♠❡❞✐❛t❡s ✇❡r❡ ❛❧s♦ ❝❛❧❝✉❧❛t❡❞ ♦♥ ❛♥ ❍✲s❛t✉r❛t❡❞ s✉r❢❛❝❡ ✇✐t❤ ❛ s✐♥❣❧❡ ❤②❞r♦❣❡♥ ❛t♦♠ r❡♠♦✈❡❞ t♦ ♠❛❦❡ r♦♦♠ ❢♦r t❤❡ ❛❞s♦r❜❛t❡✳ ❚❤❡ r❡s✉❧t✲ ✐♥❣ ❜✐♥❞✐♥❣ ❡♥❡r❣② ✇❛s ✉s❡❞ t♦ ❝♦♥str✉❝t ❛ ❧✐♥❡❛r ❞❡♣❡♥❞❡♥❝❡ ♦❢ t❤❡ ❜✐♥❞✐♥❣ ❡♥❡r❣② ♦❢ ❛❧❧ ✐♥t❡r♠❡❞✐❛t❡s t♦ t❤❡ ❍ ❝♦✈❡r❛❣❡✳
❙✐♠✐❧❛r ❝❛❧❝✉❧❛t✐♦♥s ✇❡r❡ ❞♦♥❡ t♦ ❞❡t❡r♠✐♥❡ t❤❡ ❧❛t❡r❛❧
✽
ACS Paragon Plus Environment
Page 9 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Catalysis
s❡❧❢✲✐♥t❡r❛❝t✐♦♥s ♦❢ ❖ ❛♥❞ ❖✷ ✳ ❚❤❡ ❧❛t❡r❛❧ s❡❧❢✲✐♥t❡r❛❝t✐♦♥s ♦❢ ❍✱ ❖✱ ❛♥❞ ❖✷ ✇❡r❡ ✜tt❡❞ t♦
E(slab + nX) − E(slab) = nE(slab + X) +
✇❤❡r❡
E(slab + X)
n2 E(X···X), m
✐s t❤❡ ❡♥❡r❣② ♦❢ ❳ ♦♥ t❤❡ s✉r❢❛❝❡ ❛t ✐♥✜♥✐t❡ ❞✐❧✉t✐♦♥✱
♦❢ ❜✐♥❞✐♥❣ s✐t❡s ✐♥ t❤❡ ♣❡r✐♦❞✐❝ s❧❛❜ ♠♦❞❡❧ ✭✐♥ ♦✉r ♠♦❞❡❧✱
m = 9✮✱
❛♥❞
✭✶✮
m
✐s t❤❡ ♥✉♠❜❡r
E(X···X)
❛r❡ t❤❡
♠❡❛♥✲✜❡❧❞ ❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥s ♦❢ s♣❡❝✐❡s ❳ ✇✐t❤ ✐ts❡❧❢✳ ❲❡ ✜t t❤❡ ③❡r♦✲❝♦✈❡r❛❣❡ ❡♥❡r❣② ❛♥❞ ❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥ ❡♥❡r❣✐❡s ♦❢ ❍✱ ❖✱ ❛♥❞ ❖✷ ❜② s♦❧✈✐♥❣ t❤✐s ❡q✉❛t✐♦♥ ❡①❛❝t❧② ❢♦r
n = 9✳
n=1
❛♥❞
❋♦r t❤❡ ❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥ ♦❢ ♦t❤❡r s♣❡❝✐❡s ✇✐t❤ ❍✱ ✇❡ s♦❧✈❡ ❛ s✐♠✐❧❛r ❡q✉❛t✐♦♥✱
E(slab + X + nH) − E(slab) − nE(slab + H) −
❚❤✐s ❡q✉❛t✐♦♥ ✐s s♦❧✈❡❞ ❡①❛❝t❧② ❢♦r
n=0
❛♥❞
n n2 E(H···H) = E(slab + X) + E(H···X). m m
✭✷✮
n = 8✳
❈♦rr❡❝t✐♦♥s t♦ t❤❡ ❢r❡❡ ❡♥❡r❣② ♦❢ tr❛♥s✐t✐♦♥ st❛t❡s ✇❡r❡ ❝❛❧❝✉❧❛t❡❞ ❛s
∆Ets = α∆Eprod + (1 − α) ∆Ereact ,
✇❤❡r❡
∆Ei
❡✛❡❝ts✱ ❛♥❞
✐s t❤❡ ❝♦rr❡❝t✐♦♥ t♦ t❤❡ ❢r❡❡ ❡♥❡r❣② ♦❢ s♣❡❝✐❡s
α
✐♥❝❧✉❞✐♥❣ ❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥s
✐s t❤❡ ❧❛t❡♥❡ss ♦❢ t❤❡ tr❛♥s✐t✐♦♥ st❛t❡✱ ✇❤✐❝❤ ✇❡ ❛♣♣r♦①✐♠❛t❡ ❛s
α=
✇❤❡r❡
i
✭✸✮
∆G‡for ∆G‡for + ∆G‡rev
,
∆G‡ ✐s t❤❡ ❢♦r✇❛r❞ ♦r r❡✈❡rs❡ ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡r ❡①❝❧✉❞✐♥❣
✭✹✮
❝♦✈❡r❛❣❡ ❡✛❡❝ts✳ ■❢ ❛ s♣❡❝✐❡s
✐♥❝❧✉❞❡s ❛ ❝♦♥st❛♥t ❝♦rr❡❝t✐♦♥ t♦ t❤❡ ❢r❡❡ ❡♥❡r❣② ✭s✉❝❤ ❛s ❛❞s♦r❜❡❞ ❍✱ t♦ ♠❛t❝❤ ❡①♣❡r✐♠❡♥t❛❧ ✈❛❧✉❡s✮✱ ❡q✉❛t✐♦♥s ✸ ❛♥❞ ✹ ❛r❡ s♦❧✈❡❞ s❡❧❢✲❝♦♥s✐st❡♥t❧②✳ ❚❤❡ r❡❛❝t♦r ✇❛s ♠♦❞❡❧❡❞ ❛s ❛♥ ✐❞❡❛❧✐③❡❞ ❝♦♥t✐♥✉♦✉s st✐rr❡❞✲t❛♥❦ r❡❛❝t♦r ✭❈❙❚❘✮ ❛t
330 K✳
❚❤❡ ❣❛s✲ ❛♥❞ s♦❧✉t✐♦♥✲♣❤❛s❡ ❝♦♥❝❡♥tr❛t✐♦♥ ♦❢ ❛❧❧ r❡❛❝t❛♥ts ❛♥❞ ♣r♦❞✉❝ts ✇❡r❡ ✜①❡❞ t♦ t❤❡✐r ✐♥✐t✐❛❧ ✈❛❧✉❡s✳ ❚❤❡ ❝♦✉♣❧❡❞ ❞✐✛❡r❡♥t✐❛❧ ❡q✉❛t✐♦♥s ✇❡r❡ s♦❧✈❡❞ ✉♥t✐❧ t❤❡ r❛t❡ ♦❢ ❝❤❛♥❣❡ ♦❢ ❛❧❧
✾
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
❝♦♥❝❡♥tr❛t✐♦♥s ❛♥❞ ❝♦✈❡r❛❣❡s ✇❛s ❧❡ss t❤❛♥
Page 10 of 35
1 × 10−6 s−1 ✳
❙❡♥s✐t✐✈✐t② ❛♥❛❧②s✐s ✇❛s ♣❡r❢♦r♠❡❞
❜② ♥✉♠❡r✐❝❛❧❧② ♣❡rt✉r❜✐♥❣ ♠♦❞❡❧ ♣❛r❛♠❡t❡rs ❛♥❞ r❡✲r✉♥♥✐♥❣ t❤❡ ♠♦❞❡❧ t♦ ✜♥❞ t❤❡ ♥❡✇ st❡❛❞② st❛t❡ ❝♦♥❞✐t✐♦♥s✳
❋♦r ❡❛❝❤ r❡❛❝t✐♦♥✱ ❈❛♠♣❜❡❧❧✬s ❞❡❣r❡❡ ♦❢ r❛t❡ ❝♦♥tr♦❧ ✭χRC ✮ ✇❛s
❞❡t❡r♠✐♥❡❞ ❜② ✐♥❝r❡❛s✐♥❣ ❛♥❞ ❞❡❝r❡❛s✐♥❣ t❤❡ ❢♦r✇❛r❞ ❛♥❞ r❡✈❡rs❡ r❛t❡ ❝♦♥st❛♥ts ❜②
0.1 %✳
❋♦r ❡❛❝❤ s♣❡❝✐❡s✱ t❤❡ t❤❡r♠♦❞②♥❛♠✐❝ r❛t❡ ❝♦♥tr♦❧ ✭χTRC ✮ ✇❛s ❞❡t❡r♠✐♥❡❞ ❜② ✐♥❝r❡❛s✐♥❣ ❛♥❞ ❞❡❝r❡❛s✐♥❣ t❤❡ ❢r❡❡ ❡♥❡r❣② ♦❢ t❤❡ s♣❡❝✐❡s ❜②
0.001kB T ✳
❚❤❡ ❡✛❡❝t✐✈❡ ❛❝t✐✈❛t✐♦♥ ❜❛rr✐❡r ♦❢ t❤❡
♠♦❞❡❧ ✇❛s ❞❡t❡r♠✐♥❡❞ ❜② ✐♥❝r❡❛s✐♥❣ ❛♥❞ ❞❡❝r❡❛s✐♥❣ t❤❡ r❡❛❝t♦r t❡♠♣❡r❛t✉r❡ ❜②
0.01 K✳ ✼✶✕✼✸
◆♦t❡ t❤❛t ♦✉r ❞❡✜♥✐t✐♦♥ ♦❢ t❤❡ ❞❡❣r❡❡ ♦❢ t❤❡r♠♦❞②♥❛♠✐❝ r❛t❡ ❝♦♥tr♦❧ ❞✐✛❡rs ❢r♦♠ t❤❡ ❞❡✜♥✐t✐♦♥ ❣✐✈❡♥ ❜② ❈❛♠♣❜❡❧❧ ✐♥ ✇❤✐❝❤ t❤❡ ❢r❡❡ ❡♥❡r❣② ♦❢ ❛❧❧ ♦t❤❡r s♣❡❝✐❡s ❛♥❞ ❛❧❧ tr❛♥s✐t✐♦♥ st❛t❡s ❛r❡ ❦❡♣t ✜①❡❞✳ ❚❤✐s ✐s ❜❡❝❛✉s❡ ✐♥ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✱ t❤❡ ❡♥❡r❣② ♦❢ ❛ tr❛♥s✐t✐♦♥ st❛t❡ ❞❡♣❡♥❞s ♦♥ t❤❡ ❡♥❡r❣② ♦❢ t❤❡ r❡❛❝t❛♥ts ❛♥❞ ♣r♦❞✉❝ts ♦❢ r❡❛❝t✐♦♥s t❤❛t ♣❛ss t❤r♦✉❣❤ t❤❛t tr❛♥s✐t✐♦♥ st❛t❡✳ ❋♦r ❛ ♠♦r❡ t❤♦r♦✉❣❤ ❞✐s❝✉ss✐♦♥ ♦❢ ♦✉r s❡♥s✐t✐✈✐t② ❛♥❛❧②s✐s ✐♠♣❧❡♠❡♥t❛t✐♦♥✱ s❡❡ t❤❡ ❙■✳
✸
❘❡s✉❧ts ❛♥❞ ❉✐s❝✉ss✐♦♥
✸✳✶
❉❋❚ r❡s✉❧ts
❘❡❛❝t✐♦♥ ❢r❡❡ ❡♥❡r❣✐❡s ❛♥❞ ❜❛rr✐❡rs ✇❡r❡ ❝❛❧❝✉❧❛t❡❞ ❢♦r ❛❧❧ ♣❧❛✉s✐❜❧❡ ❡❧❡♠❡♥t❛r② st❡♣s ❢♦r t❤❡ ♦①✐❞❛t✐✈❡ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡✳
❆ s✉❜s❡t ♦❢ t❤❡s❡ ❡♥❡r❣✐❡s
✉♥❞❡r st❡❛❞② st❛t❡ ✭t❤♦s❡ ❢♦✉♥❞ t♦ ❜❡ ❦✐♥❡t✐❝❛❧❧② r❡❧❡✈❛♥t✱ ✈✐❞❡ ✐♥❢r❛✮ ❛r❡ ❣✐✈❡♥ ✐♥ ❚❛❜❧❡ ✶❀ ❛ ❝♦♠♣r❡❤❡♥s✐✈❡ ❧✐st✐♥❣ ♦❢ ❛❧❧ ❝♦♥s✐❞❡r❡❞ r❡❛❝t✐♦♥s ❛♥❞ t❤❡ ❝♦rr❡s♣♦♥❞✐♥❣ ❉❋❚✲❝❛❧❝✉❧❛t❡❞ r❡s✉❧ts ❢♦r ❜♦t❤ t❤❡ ♣r✐st✐♥❡ ❛♥❞ st❡❛❞②✲st❛t❡ s✉r❢❛❝❡ ❝❛♥ ❜❡ ❢♦✉♥❞ ✐♥ t❤❡ ❙■✳ ❚❤❡ ❢r❡❡ ❡♥❡r❣✐❡s ♦❢ r❡❛❝t✐♦♥ ❛♥❞ ❜❛rr✐❡r ❤❡✐❣❤ts ♦♥ t❤❡ ♣r✐st✐♥❡ s✉r❢❛❝❡ ❛r❡ ✐♥ q✉❛❧✐t❛t✐✈❡ ❛❣r❡❡♠❡♥t ✇✐t❤ t❤❡ r❡s✉❧ts ♦❢ ❍✐❜❜✐tts ❛♥❞ ◆❡✉r♦❝❦
✸✺
✭♣r✐st✐♥❡ r❡s✉❧ts ♥♦t s❤♦✇♥ ❤❡r❡✱ s❡❡
t❛❜❧❡ ❙✸✮✳ ■♥ ♣❛rt✐❝✉❧❛r✱ ✇❡ ✜♥❞ t❤❛t ♦①②❣❡♥ ❛ss✐st❛♥❝❡ ❣r❡❛t❧② ❧♦✇❡rs t❤❡ ❜❛rr✐❡r t♦ ❝❧❡❛✈❛❣❡ ♦❢ ❖−❍ ❜♦♥❞s✱ ❜✉t ♥♦t ❈−❍ ❜♦♥❞s ✭t❤❡s❡ r❡❛❝t✐♦♥s ❛r❡ ♦♠✐tt❡❞ ❢r♦♠ ❚❛❜❧❡ ✶ ✐♥ t❤❡ ♠❛✐♥ t❡①t✱ ❛s t❤❡② ❛r❡ ♥♦t ❢♦✉♥❞ t♦ ❜❡ ❦✐♥❡t✐❝❛❧❧② r❡❧❡✈❛♥t✮✳ ❙✐♠✐❧❛r❧②✱ ✇❡ ✜♥❞ ❞❡❤②❞r♦❣❡♥❛t✐♦♥
✶✵
ACS Paragon Plus Environment
Page 11 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Catalysis
❚❛❜❧❡ ✶✿
❋r❡❡ ❡♥❡r❣✐❡s ♦❢ r❡❛❝t✐♦♥ ❛♥❞ ❢♦r✇❛r❞ ❛♥❞ r❡✈❡rs❡ ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡rs ❢♦r t❤❡
r❡❛❝t✐♦♥s ❢♦✉♥❞ t♦ ❜❡ r❡❧❡✈❛♥t ✐♥ t❤❡ ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ✭❞✐s❝✉ss❡❞ ❧❛t❡r✮ ✉♥❞❡r st❡❛❞② st❛t❡ ❝♦♥❞✐t✐♦♥s✳ ❘❡s✉❧ts ❢♦r ❛❧❧ r❡❛❝t✐♦♥s ❝♦♥s✐❞❡r❡❞ ✐♥ ♦✉r ♠♦❞❡❧ ✉♥❞❡r ❜♦t❤ ♣r✐st✐♥❡ ❛♥❞ st❡❛❞② ‡ ‡ st❛t❡ ❝♦♥❞✐t✐♦♥s ❝❛♥ ❜❡ ❢♦✉♥❞ ✐♥ t❤❡ ❙■✳ ▼✐ss✐♥❣ ✈❛❧✉❡s ❢♦r ∆Gfor ❛♥❞ ∆Grev ✐♥❞✐❝❛t❡ t❤❛t t❤❡ r❡❛❝t✐♦♥ ✐s ❜❛rr✐❡r❧❡ss✳ ❘❡❛❝t✐♦♥
+ ∗ ←−→ ❘❈❍✷ ❖❍∗ + ∗ ←−→ ❘❈❍✷ ❖∗ + ❡ ✕ ✕ ❈❍✸ ❖✭s♦❧✬♥✮ + ∗ ← −→ ❈❍✸ ❖∗ + ❡ ✕ ❖✷✭❣✮ + ∗ ← −→ ❖✷ ∗ ❘❈❍✷ ❖❍∗ + ❖❍∗ ← −→ ❘❈❍✷ ❖∗ + ❍✷ ❖∗ ❘❈❍✷ ❖❍∗ + ∗ ← −→ ❘❈❍❖❍∗ + ❍∗ ❘❈❍✷ ❖∗ + ∗ ← −→ ❘❈❍❖∗ + ❍∗ ❘❈❍❖❍∗ + ❖✷ ∗ ← −→ ❘❈❍❖∗ + ❖❖❍∗ ❘❈❍❖∗ ← −→ ❘❈❍❖✭s♦❧✬♥✮ + ∗ ❘❈❍❖∗ + ∗ ← −→ ❘❈❖∗ + ❍∗ ❘❈❖∗ + ❈❍✸ ❖∗ ← −→ ❘❈❖❖❈❍✸ ∗ + ∗ ✕ −→ ❘❈❍❖❖❈❍✸ ✕ ✭s♦❧✬♥✮ ❘❈❍❖✭s♦❧✬♥✮ + ❈❍✸ ❖✭s♦❧✬♥✮ ← ✕ ❘❈❍❖❖❈❍✸ ✭s♦❧✬♥✮ + ∗ ← −→ ❘❈❍❖❖❈❍✸ ∗ + ❡ ✕ ❘❈❍❖❖❈❍✸ ∗ + ∗ ← −→ ❘❈❖❖❈❍✸ ∗ + ❍∗ ❘❈❖❖❈❍✸ ∗ ← −→ ❘❈❖❖❈❍✸✭s♦❧✬♥✮ + ∗ ❖❖❍∗ + ∗ ← −→ ❖∗ + ❖❍∗ ✕ ✕ ❖❍∗ + ❡ ← −→ ❖❍✭s♦❧✬♥✮ +∗ ❍✷ ❖∗ ← −→ ❍✷ ❖✭s♦❧✬♥✮ + ∗ ❈❍✸ ❖∗ + ❍∗ ← −→ ❈❍✸ ❖❍∗ + ∗ ❈❍✸ ❖❍∗ + ❖∗ ← −→ ❈❍✸ ❖∗ + ❖❍∗ ❈❍✸ ❖❍∗ + ❖❍∗ ← −→ ❈❍✸ ❖∗ + ❍✷ ❖∗ ❈❍✸ ❖❍∗ ← −→ ❈❍✸ ❖❍✭❧✮ + ∗ ✷ ❍∗ ← −→ ❍✷✭s♦❧✬♥✮ + ✷ ∗ ❘❈❍✷ ❖❍✭s♦❧✬♥✮
✕
❘❈❍✷ ❖✭s♦❧✬♥✮
∆G ✭eV✮ −0.01 0.44 0.34 0.24 −0.06 0.25 −0.92 −0.06 −0.03 −0.04 −1.89 −0.20 0.36 −1.51 0.29 −1.18 −0.75 −0.22 −0.86 0.23 −0.31 −0.11 0.49
∆G‡for ✭eV✮
∆G‡rev ✭eV✮
0.81 0.27
0.56 1.20
0.22 0.08
0.26 1.77
0.30
1.81
0.09
1.27
0.47
1.33
♦❢ ♣r♦♣❛♥♦❧ t♦ ❢♦r♠ t❤❡ ❤②❞r♦①②♣r♦♣②❧ ✐♥t❡r♠❡❞✐❛t❡ ✐s t❤❡ ♠♦st t❤❡r♠♦❞②♥❛♠✐❝❛❧❧② ❛♥❞ ❦✐♥❡t✐❝❛❧❧② ❢❛✈♦r❛❜❧❡ ✜rst st❡♣ ✐♥ t❤❡ ❛❜s❡♥❝❡ ♦❢ s✉r❢❛❝❡ ♦①②❣❡♥ s♣❡❝✐❡s✳ ■♥ ❣❡♥❡r❛❧✱ ✇❡ ✜♥❞ t❤❛t ♠♦st ❦✐♥❡t✐❝❛❧❧② r❡❧❡✈❛♥t st❡♣s ✐♥ t❤❡ ♠♦❞❡❧ ❛r❡ ❡①♦t❤❡r♠✐❝ ❛♥❞ ❤❛✈❡ s♠❛❧❧ ♦r ♥♦ ❜❛rr✐❡rs✱ ✇✐t❤ t❤❡ ❡①❝❡♣t✐♦♥ ♦❢ t❤❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ❤②❞r♦①②♣r♦♣②❧ ❛♥❞ t❤❡ ❞❡s♦r♣t✐♦♥ ♦❢ ♣r♦♣❛♥❛❧ ❛♥❞ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡✳ ❲❤✐❧❡ ❚❛❜❧❡ ✶ ✐♥❞✐❝❛t❡s t❤❛t ❛❞s♦r♣t✐♦♥ ♦❢ ❛♥✐♦♥s ✐s str♦♥❣❧② ❞✐s❢❛✈♦r❡❞✱ t❤✐s ✐s ♦♥❧② t❤❡ ❝❛s❡ ✉♥❞❡r st❡❛❞② st❛t❡ ❝♦♥❞✐t✐♦♥s ❞✉❡ t♦ t❤❡ ❜✉✐❧❞✉♣ ♦❢ ❡①❝❡ss ♥❡❣❛t✐✈❡ ❝❤❛r❣❡ ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳
■♥ ❢❛❝t✱ ❛♥✐♦♥s ❜✐♥❞ t♦ t❤❡ ♣r✐st✐♥❡ s✉r❢❛❝❡ ✈❡r② str♦♥❣❧②✱ ❛r♦✉♥❞
✶✶
ACS Paragon Plus Environment
1.5 eV
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
t♦
2.0 eV✱
Page 12 of 35
❜❡❝♦♠✐♥❣ ❧❡ss ❡①♦t❤❡r♠✐❝ ✇✐t❤ ✐♥❝r❡❛s✐♥❣ ❛♥✐♦♥ ❛❞s♦r♣t✐♦♥ ❞✉❡ t♦ s✉r❢❛❝❡ ❝❤❛r❣❡
❛❝❝✉♠✉❧❛t✐♦♥✳
✸✳✷
▼✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ r❡s✉❧ts
❚❛❜❧❡ ✷✿ ❙t❡❛❞② st❛t❡ r❛t❡s ❛♥❞ ❞❡❣r❡❡ ♦❢ r❛t❡ ❝♦♥tr♦❧ ❢♦r ❛❧❧ r❡❛❝t✐♦♥s ❢♦✉♥❞ t♦ ❜❡ r❡❧❡✈❛♥t ✐♥ t❤❡ ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✳ ❘❡s✉❧ts ❢♦r ❛❧❧ r❡❛❝t✐♦♥s ❝♦♥s✐❞❡r❡❞ ✐♥ ♦✉r ♠♦❞❡❧ ❝❛♥ ❜❡ ❢♦✉♥❞ ✐♥ t❤❡ ❙■✳ ❙t❡❛❞② st❛t❡ r❛t❡ ✭h
❘❡❛❝t✐♦♥
+ ∗ ←−→ ❘❈❍✷ ❖❍∗ ✕ ❘❈❍✷ ❖✭s♦❧✬♥✮ + ∗ ← −→ ❘❈❍✷ ❖∗ + ❡ ✕ ✕ ❈❍✸ ❖✭s♦❧✬♥✮ + ∗ ← −→ ❈❍✸ ❖∗ + ❡ ✕ ❘❈❍✷ ❖❍✭s♦❧✬♥✮
+ ∗ ←−→ ❖✷ ∗ ❘❈❍✷ ❖❍∗ + ❖❍∗ ← −→ ❘❈❍✷ ❖∗ + ❍✷ ❖∗ ❘❈❍✷ ❖❍∗ + ∗ ← −→ ❘❈❍❖❍∗ + ❍∗ ❘❈❍✷ ❖∗ + ∗ ← −→ ❘❈❍❖∗ + ❍∗ ❘❈❍❖❍∗ + ❖✷ ∗ ← −→ ❘❈❍❖∗ + ❖❖❍∗ ❘❈❍❖∗ ← −→ ❘❈❍❖✭s♦❧✬♥✮ + ∗ ❘❈❍❖∗ + ∗ ← −→ ❘❈❖∗ + ❍∗ ❘❈❖∗ + ❈❍✸ ❖∗ ← −→ ❘❈❖❖❈❍✸ ∗ + ∗ ✕ −→ ❘❈❍❖❖❈❍✸ ✕ ✭s♦❧✬♥✮ ❘❈❍❖✭s♦❧✬♥✮ + ❈❍✸ ❖✭s♦❧✬♥✮ ← ✕ −→ ❘❈❍❖❖❈❍✸ ∗ + ❡ ✕ ❘❈❍❖❖❈❍✸ ✭s♦❧✬♥✮ + ∗ ← ❘❈❍❖❖❈❍✸ ∗ + ∗ ← −→ ❘❈❖❖❈❍✸ ∗ + ❍∗ ❘❈❖❖❈❍✸ ∗ ← −→ ❘❈❖❖❈❍✸✭s♦❧✬♥✮ + ∗ ❖❖❍∗ + ∗ ← −→ ❖∗ + ❖❍∗ ✕ ✕ ❖❍∗ + ❡ ← −→ ❖❍✭s♦❧✬♥✮ +∗ ❍✷ ❖∗ ← −→ ❍✷ ❖✭s♦❧✬♥✮ + ∗ −→ ❈❍✸ ❖❍∗ + ∗ ❈❍✸ ❖∗ + ❍∗ ← ❈❍✸ ❖❍∗ + ❖∗ ← −→ ❈❍✸ ❖∗ + ❖❍∗ ❈❍✸ ❖❍∗ + ❖❍∗ ← −→ ❈❍✸ ❖∗ + ❍✷ ❖∗ ❈❍✸ ❖❍∗ ← −→ ❈❍✸ ❖❍✭❧✮ + ∗ ✷ ❍∗ ← −→ ❍✷✭s♦❧✬♥✮ + ✷ ∗ ❖✷✭❣✮
−1
✮
❉❡❣r❡❡ ♦❢ r❛t❡ ❝♦♥tr♦❧
95.6 −7.2 105.1 81.9 13.7 81.9 6.5 81.9 46.8 41.6 41.6 46.8 46.8 46.8 88.4 81.9 144.7 19.2 150.8 81.9 5.4 63.5 12.9
0.000 0.000 0.000 0.000 0.000 0.619 −0.256 0.005 −0.001 0.000 −0.001 0.000 0.000 −0.001 −0.024 0.000 0.000 0.000 0.427 0.002 0.000 0.000 0.452
❖✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ②✐❡❧❞s ❛♥ ♦✈❡r❛❧❧ t✉r♥♦✈❡r ❢r❡q✉❡♥❝② ♦❢ ❛❜♦✉t
88.4 h−1 ✱ ❝♦♥s✐st❡♥t
✇✐t❤ t❤❡ ❧♦✇ ❡①♣❡r✐♠❡♥t❛❧❧②✲♦❜s❡r✈❡❞ ❛❝t✐✈✐t② ♦❢ t❤❡ ✉♥♣r♦♠♦t❡❞ ❝❛t❛❧②st✳ ❇❛s❡❞ ♦♥ t❤❡s❡ r❡s✉❧ts✱ ✇❡ ✜♥❞ t❤❛t t✇♦ ♣❛t❤✇❛②s t♦ t❤❡ ❢♦r♠❛t✐♦♥ ♦❢ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ❝♦♥tr✐❜✉t❡ t♦ t❤❡ ♠❛❥♦r✐t② ♦❢ t❤❡ ❛❝t✐✈✐t② ✭s❡❡ ❚❛❜❧❡ ✷✮✳ ❚❤❡ ✜rst ♣❛t❤✇❛② ✐♥✈♦❧✈❡s ✐♥✐t✐❛❧ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ❛❞s♦r❜❡❞ ♣r♦♣❛♥♦❧ ✭❘❈❍✷ ❖❍✮ t♦ ❤②❞r♦①②♣r♦♣②❧ ✭❘❈❍❖❍✮✱ ✇❤✐❝❤ r❡❛❝ts ✇✐t❤ ❛❞s♦r❜❡❞ ❖✷ ✶✷
ACS Paragon Plus Environment
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ACS Catalysis
❚❛❜❧❡ ✸✿ ❙t❡❛❞② st❛t❡ ❝♦♥❝❡♥tr❛t✐♦♥s ❛♥❞ ❞❡❣r❡❡ ♦❢ t❤❡r♠♦❞②♥❛♠✐❝ r❛t❡ ❝♦♥tr♦❧ ❢♦r ❛❧❧ ❛❞✲ s♦r❜❛t❡s ❝♦♥s✐❞❡r❡❞ ✐♥ ♦✉r ♠♦❞❡❧✳ ❙♣❡❝✐❡s ❍ ❘❈❍✷ ❖❍ ❘❈❖❖❈❍✸ ❈❍✸ ❖❍ ❘❈❍❖❍❖❈❍✸ ❈❍✸ ❖ ❘❈❖ ❖✷ ❘❈❍❖ ❘❈❍❖❖❈❍✸ ❘❈❍❖❍ ❍✷ ❖ ❖ ❘❈❍✷ ❖ ❖❖❍ ❖❍ ❘❈❖❍❖❈❍✸
∗
❙t❡❛❞② st❛t❡ ❝♦♥❝❡♥tr❛t✐♦♥
❚❤❡r♠♦❞②♥❛♠✐❝ r❛t❡ ❝♦♥tr♦❧
0.7352 0.1049 0.0572 0.0376 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 0.0650
−1.368 0.453 0.048 0.182 0.000 0.552 −0.003 0.010 −0.167 −0.002 0.769 0.000 −0.005 −0.525 0.002 0.005 0.000
t♦ ❢♦r♠ ♣r♦♣❛♥❛❧ ✭❘❈❍❖✮ ❛♥❞ ❤②❞r♦♣❡r♦①②❧ ✭❖❖❍✮✳ ❖❖❍ ❞✐ss♦❝✐❛t❡s t♦ ❖ ❛♥❞ ❤②❞r♦①②❧ ✭❖❍✮✱ ❛♥❞ ❖❍ ❛❝❝❡♣ts ❛♥ ❡❧❡❝tr♦♥ ❢r♦♠ t❤❡ s✉r❢❛❝❡ ❛♥❞ ❧❡❛✈❡s t❤❡ ❝❛t❛❧②st ❛s ❤②❞r♦①✐❞❡
✕
✭❖❍ ✮✳ Pr♦♣❛♥❛❧ ❞❡s♦r❜s ❢r♦♠ t❤❡ s✉r❢❛❝❡ ❛♥❞ r❡❛❝ts ✐♥ s♦❧✉t✐♦♥ ✇✐t❤ ♠❡t❤♦①✐❞❡ t♦ ❢♦r♠
✕
❛ ❞❡♣r♦t♦♥❛t❡❞ ❤❡♠✐❛❝❡t❛❧ ❛♥✐♦♥ ✭❘❈❍❖❖❈❍✸ ✮✳ ❚❤✐s ❛♥✐♦♥ t❤❡♥ ❛❞s♦r❜s t♦ t❤❡ s✉r❢❛❝❡ ❛♥❞ ✉♥❞❡r❣♦❡s
β✲❤②❞r✐❞❡
❡❧✐♠✐♥❛t✐♦♥ t♦ ❢♦r♠ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ✭❘❈❖❖❈❍✸ ✮✳ ❚❤❡ s❡❝♦♥❞
♣❛t❤✇❛② ✐s ✐❞❡♥t✐❝❛❧ ✉♣ t♦ t❤❡ ❢♦r♠❛t✐♦♥ ♦❢ ♣r♦♣❛♥❛❧✱ ❛t ✇❤✐❝❤ ♣♦✐♥t ♣r♦♣❛♥❛❧ ❜❡❝♦♠❡s ❢✉rt❤❡r ❞❡❤②❞r♦❣❡♥❛t❡❞ ❜② t❤❡ ❝❛t❛❧②st t♦ ♣r♦♣❛♥♦②❧ ✭❘❈❖✮✱ ✇❤✐❝❤ r❡❛❝ts ✇✐t❤ ❝❛t❛❧②st✲ ❜♦✉♥❞ ♠❡t❤♦①② t♦ ❢♦r♠ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡✳ ❇♦t❤ ♣❛t❤✇❛②s ❝♦♥tr✐❜✉t❡ ❛♥ ❡ss❡♥t✐❛❧❧② ❡q✉❛❧ ❛♠♦✉♥t t♦ t❤❡ ♦✈❡r❛❧❧ ❢♦r♠❛t✐♦♥ ♦❢ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ✭s❡❡ ❋✐❣✉r❡ ✼✮✳ ❙✐♥❝❡ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ❛❝❝♦✉♥ts ❢♦r ❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥s ❜❡t✇❡❡♥ ❛❞s♦r❜❛t❡s✱ r❡❛❝✲ t✐♦♥ ❡♥❡r❣✐❡s ❛♥❞ ❜❛rr✐❡r ❤❡✐❣❤ts ❞❡♣❡♥❞ ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❝♦✈❡r❛❣❡✳ ■♥ t❤❡ ❞✐s❝✉ss✐♦♥ t❤❛t ❢♦❧❧♦✇s✱ ❛❧❧ r❡♣♦rt❡❞ ❡♥❡r❣✐❡s ❝♦rr❡s♣♦♥❞ t♦ t❤❡ st❡❛❞②✲st❛t❡ ❝❛t❛❧②st ❝♦✈❡r❛❣❡✳ ■♥ ❣❡♥✲ ❡r❛❧✱ t❤✐s t❡♥❞s t♦ r❛✐s❡ ❜❛rr✐❡r ❤❡✐❣❤ts ❛♥❞ ❞❡st❛❜✐❧✐③❡ ✐♥t❡r♠❡❞✐❛t❡s t❤❛t ❢♦r♠ str♦♥❣ ❜♦♥❞s
✶✸
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 14 of 35
t♦ t❤❡ ❝❛t❛❧②st r❡❧❛t✐✈❡ t♦ t❤❛t ♦❢ t❤❡ ♣r✐st✐♥❡ ❝❛t❛❧②st✳ ■♥ ♣❛rt✐❝✉❧❛r✱ ✇❡ ✜♥❞ t❤❛t t❤❡ st❡❛❞② st❛t❡ ❝❛t❛❧②st ❤❛s ❛ ❧❛r❣❡ ❜✉✐❧❞✉♣ ♦❢ ❛❞s♦r❜❡❞ ❍ ✭s❡❡ ❚❛❜❧❡ ✸✮✳ ■♥ t❤❡ ❢♦❧❧♦✇✐♥❣ s❡❝t✐♦♥s✱ ✇❡ ✇✐❧❧ ❞✐s❝✉ss t❤❡ r❡s✉❧ts ♦❢ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ❜② ❢♦❝✉s✐♥❣ ♦♥ s♣❡❝✐✜❝ r❡❛❝t✐♦♥s t❤❛t ♦❝❝✉r ✐♥ t❤❡ ♦✈❡r❛❧❧ r❡❛❝t✐♦♥ ♥❡t✇♦r❦✳ ❲❡ ❜❡❣✐♥ ❜② ❞✐s❝✉ss✐♥❣ t❤❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♣r♦♣❛♥❛❧✱ ❢♦❧❧♦✇❡❞ ❜② t❤❡ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r♦♣❛♥❛❧ t♦ ❢♦r♠ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡✳
❲❡ s✉❜s❡q✉❡♥t❧② ❞✐s❝✉ss t❤❡ ♣r❡❞♦♠✐♥❛♥t ♣❛t❤✇❛②✭s✮ ❜② ✇❤✐❝❤ ❍ ✐s
r❡♠♦✈❡❞ ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✱ t❤❡ r❡❞✉❝t✐♦♥ ♦❢ ❖✷ t♦ ❢♦r♠ ❍✷ ❖✱ ❛♥❞ ✜♥❛❧❧② t❤❡ r♦❧❡ ♦❢ ❝❛t❛❧②t✐❝ ❜❛s❡✳ ❲❡ ❡♥❞ ❜② ♦✉t❧✐♥✐♥❣ t❤❡ ♣♦ss✐❜❧❡ r♦❧❡ ♦❢ ♠❛✐♥✲❣r♦✉♣ ❡❧❡♠❡♥t ❛❞❞✐t✐✈❡s ✐♥ ♣r♦♠♦t✐♥❣ t❤❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ❛♥❞ ♦①✐❞❛t✐♦♥ ♦❢ ❛❧❝♦❤♦❧s✳
✸✳✷✳✶ ❉❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♣r♦♣❛♥❛❧ ❚❤❡ ✜rst st❡♣ t♦✇❛r❞s ❢♦r♠❛t✐♦♥ ♦❢ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ✐s t❤❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♣r♦♣❛♥❛❧✳ ❋♦r♠❛t✐♦♥ ♦❢ ♣r♦♣❛♥❛❧ ✐♥✈♦❧✈❡s s❡q✉❡♥t✐❛❧ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ❛t t❤❡ ❛❧❝♦❤♦❧ ♦①②❣❡♥ ❛♥❞ t❤❡ ❛❞❥❛❝❡♥t ❝❛r❜♦♥✳
❚❤❡s❡ st❡♣s ❤❛✈❡ ❞✐✛❡r❡♥t ❜❛rr✐❡rs ❞❡♣❡♥❞✐♥❣ ♦♥ t❤❡ ♦r❞❡r ✐♥
✇❤✐❝❤ t❤❡② ♦❝❝✉r✱ r❡s✉❧t✐♥❣ ✐♥ t✇♦ ♣♦ss✐❜❧❡ ♣❛t❤✇❛②s ✇✐t❤ ❞✐✛❡r❡♥t ❦✐♥❡t✐❝s✳ ❲❡ r❡❢❡r t♦ t❤❡ ♣❛t❤✇❛② ✐♥ ✇❤✐❝❤ t❤❡ ❖−❍ ❜♦♥❞ ✐s ❜r♦❦❡♥ ✜rst ❛s t❤❡ ✏♣r♦♣♦①②✑ ♣❛t❤✇❛②✱ ❛♥❞ t❤❡ ♣❛t❤✇❛② ✐♥ ✇❤✐❝❤ t❤❡ ❈−❍ ❜♦♥❞ ✐s ❜r♦❦❡♥ ✜rst t❤❡ ✏❤②❞r♦①②♣r♦♣②❧✑ ♣❛t❤✇❛②✱ ❛❢t❡r t❤❡ ♣❛rt✐❛❧❧② ❞❡❤②❞r♦❣❡♥❛t❡❞ ✐♥t❡r♠❡❞✐❛t❡s ✐♥✈♦❧✈❡❞ ✐♥ t❤❡ r❡s♣❡❝t✐✈❡ ♣❛t❤✇❛②s✳ ■♥ ❜♦t❤ ♣❛t❤✇❛②s✱ ✇❡ ✜♥❞ t❤❛t t❤❡ ❜❛rr✐❡r t♦ ❖−❍ ❜♦♥❞ s❝✐ss✐♦♥ ❝❛♥ ❜❡ ❡✛❡❝t✐✈❡❧② ❡❧✐♠✲ ✐♥❛t❡❞ ❜② ❝♦♦♣❡r❛t✐✈❡ r❡❞✉❝t✐♦♥ ♦❢ ♦♥✲s✉r❢❛❝❡ ♦①②❣❡♥ s♣❡❝✐❡s ✐♥ t❤❡ ❢♦r♠ ♦❢ ❖✱ ❖❍✱ ❛♥❞ ❖✷ ✳ ❲❡ ❞♦ ♥♦t ✜♥❞ t❤❡ s❛♠❡ ❝♦♦♣❡r❛t✐✈✐t② ❢♦r t❤❡ ❈−❍ ❜♦♥❞ s❝✐ss✐♦♥ st❡♣s✳
❲❤✐❧❡ ♦①②❣❡♥✲
❛ss✐st❡❞ ❈−❍ ❜♦♥❞ s❝✐ss✐♦♥ ❝❛♥ ♦❝❝✉r✱ ✐♥ ❛❧❧ ❝❛s❡s ✇❡ ✜♥❞ t❤❡s❡ r❡❛❝t✐♦♥s t♦ ❤❛✈❡ ❛ s✉❜st❛♥✲ t✐❛❧❧② ❤✐❣❤❡r ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡r t❤❛♥ ✉♥❛ss✐st❡❞ ❈−❍ ❜♦♥❞ s❝✐ss✐♦♥✳ ❚❤✐s ✐s ❧✐❦❡❧② ❜❡❝❛✉s❡ t❤❡ ❈−❍ ❜♦♥❞s ✐♥ t❤❡ s✉r❢❛❝❡✲❜♦✉♥❞ ✐♥t❡r♠❡❞✐❛t❡s ✐♥ ♦✉r ♠♦❞❡❧ ❢♦r♠ ❛❣♦st✐❝ ✐♥t❡r❛❝t✐♦♥s ✇✐t❤ ✉♥❞❡r❧②✐♥❣ P❞ ❛t♦♠s✱ ✇❤✐❝❤ ❢❛❝✐❧✐t❛t❡s ❈−❍ ❜♦♥❞ s❝✐ss✐♦♥ ♦♥t♦ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ✭s❡❡ ❋✐❣✉r❡ ✸✮✳
■♥ ♦r❞❡r ❢♦r ❛ ❝♦❛❞s♦r❜❡❞ ♦①②❣❡♥ s♣❡❝✐❡s t♦ ❛❜str❛❝t ❍ ❞✐r❡❝t❧② ❢r♦♠ t❤❡
❈−❍ ❜♦♥❞✱ t❤✐s ❛❣♦st✐❝ ✐♥t❡r❛❝t✐♦♥ ♠✉st ❜❡ ❜r♦❦❡♥✱ ✇❤✐❝❤ ❞❡st❛❜✐❧✐③❡s t❤❡ tr❛♥s✐t✐♦♥ st❛t❡
✶✹
ACS Paragon Plus Environment
Page 15 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Catalysis
ACS Paragon Plus Environment
ACS Catalysis
2.0 +
1.64
1.5
+
1.38
Free energy (eV)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 16 of 35
+
1.38
+
1.0
1.10
1.11 +
0.74
0.5
0.52
0.47
+
+
0.21
0.0
−0.5
Unassisted O2 -assisted O-assisted OH-assisted
0.18
−0.06
+
−1.0
0.18
−0.45 −0.99
Reaction coordinate
❋✐❣✉r❡ ✹✿ ❋r❡❡ ❡♥❡r❣② ♣r♦✜❧❡ ♦❢ t❤❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♣r♦♣❛♥❛❧ t❤r♦✉❣❤ t❤❡ ❛❞s♦r❜❡❞ ♣r♦♣♦①② ✐♥t❡r♠❡❞✐❛t❡ ✉♥❞❡r st❡❛❞② st❛t❡ ❝♦♥❞✐t✐♦♥s ✈✐❛ t❤❡ ✉♥❛ss✐st❡❞ ✭❜❧❛❝❦✮✱ ❖✷ ✲ ❛ss✐st❡❞ ✭♦r❛♥❣❡✮✱ ❖✲❛ss✐st❡❞ ✭❜❧✉❡✮✱ ❛♥❞ ❖❍✲❛ss✐st❡❞ ✭❣r❡❡♥✮ ♠❡❝❤❛♥✐s♠s✳ ❚❤❡ ③❡r♦ ♦❢ ❢r❡❡ ❡♥❡r❣② ❝♦rr❡s♣♦♥❞s t♦ ❛❧❧ ❝♦✲r❡❛❝t❛♥ts s❡♣❛r❛t❡❞ ❜✉t ♣r❡✲❛❞s♦r❜❡❞ ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳ ❚❤❡ ❡♥❡r❣❡t✐❝s ♦❢ t❤✐s ♣❛t❤✇❛② ♦♥ t❤❡ ♣r✐st✐♥❡ s✉r❢❛❝❡ ❛r❡ ✐❧❧✉str❛t❡❞ ✐♥ ❋✐❣✉r❡ ❙✷✳
t❤❡ ❜❛rr✐❡r t♦ ❖−❍ ❜♦♥❞ s❝✐ss✐♦♥✳ ❲❤✐❧❡ ❖−❍ ❜♦♥❞ s❝✐ss✐♦♥ ♦❢ ❤②❞r♦①②♣r♦♣②❧ t♦ ♣r♦♣❛♥❛❧ ✐s ❡①♦t❤❡r♠✐❝ ✐♥ ❛❧❧ ❝❛s❡s✱ ❖−❍ ❜♦♥❞ s❝✐ss✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♣r♦♣♦①② r❡♠❛✐♥s ❡♥❞♦t❤❡r✲ ♠✐❝ ✐♥ ♠♦st ❝❛s❡s✱ ✇✐t❤ t❤❡ ❡①❝❡♣t✐♦♥ ♦❢ t❤❡ ❖❍✲❛ss✐st❡❞ ♠❡❝❤❛♥✐s♠✱ ✇❤✐❝❤ ✐s ✈❡r② s❧✐❣❤t❧② ❡①♦t❤❡r♠✐❝✳ ❇❛s❡❞ ♦♥❧② ♦♥ t❤❡r♠♦❞②♥❛♠✐❝ ❝♦♥s✐❞❡r❛t✐♦♥s✱ ✐t ✐s ♥♦t t✇♦ ♣❛t❤✇❛②s ✇✐❧❧ ♣r❡❞♦♠✐♥❛t❡ t❤❡ ❝❛t❛❧②st✬s ❛❝t✐✈✐t②✳
❛ ♣r✐♦r✐
♦❜✈✐♦✉s ✇❤✐❝❤ ♦❢ t❤❡s❡
■t ✐s ❝❧❡❛r t❤❛t ♦①②❣❡♥ ❛ss✐st❛♥❝❡
❧♦✇❡rs t❤❡ ❜❛rr✐❡r t♦ ❖−❍ ❜♦♥❞ s❝✐ss✐♦♥✱ ❛♥❞ t❤❛t t❤❡ ❢♦r✇❛r❞ ❜❛rr✐❡rs ❛r❡ ♦✈❡r❛❧❧ ❧♦✇❡r ✐♥ t❤❡ ♦①②❣❡♥✲❛ss✐st❡❞ ♣r♦♣♦①② ♣❛t❤✇❛②✳
❍♦✇❡✈❡r✱ t❤❡ ❦✐♥❡t✐❝s ♦❢ t❤❡ r❡❛❝t✐♦♥ ❛r❡ ❣♦✈❡r♥❡❞
❜♦t❤ ❜② t❤❡ t❤❡r♠♦❞②♥❛♠✐❝s ♦❢ t❤❡ r❡❛❝t❛♥ts ❛♥❞ tr❛♥s✐t✐♦♥ st❛t❡ ❛♥❞ ❜② t❤❡ ❝♦♥❝❡♥tr❛t✐♦♥ ♦❢ t❤❡ r❡❛❝t❛♥ts ♦♥ t❤❡ s✉r❢❛❝❡✳
■♥ ♣❛rt✐❝✉❧❛r✱ t❤❡ r❡❛❝t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ ✭❤②❞r♦①②♣r♦♣②❧✮
✇✐t❤ s✉r❢❛❝❡✲❜♦✉♥❞ ❖ ❛♥❞ ❖❍ ✐s ❧❡ss ❡♥❞♦t❤❡r♠✐❝ ✭♠♦r❡ ❡①♦t❤❡r♠✐❝✮ t❤❛♥ r❡❛❝t✐♦♥ ✇✐t❤ s✉r❢❛❝❡✲❜♦✉♥❞ ❖✷ ✳ ❍♦✇❡✈❡r✱ s✉r❢❛❝❡✲❜♦✉♥❞ ❖ ❛♥❞ ❖❍ ❛r❡ ❢♦r♠❡❞ ♣r✐♠❛r✐❧② ❜② ❞❡❝♦♠♣♦s✐t✐♦♥ ♦❢ s✉r❢❛❝❡✲❜♦✉♥❞ ❖❖❍ ✭❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡r ♦❢
✶✻
0.09 eV✮✱
❛s t❤❡ ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡r ❢♦r ❖✷
ACS Paragon Plus Environment
Page 17 of 35
2.0
1.5
Free energy (eV)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Catalysis
+
1.0
+
0.93
0.81 0.5 +
0.25 0.0
−0.5
0.18
+
Unassisted O2 -assisted O-assisted OH-assisted
0.18
−0.45
+
−0.99
−1.0
Reaction coordinate
❋✐❣✉r❡ ✺✿ ❋r❡❡ ❡♥❡r❣② ♣r♦✜❧❡ ♦❢ t❤❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♣r♦♣❛♥❛❧ t❤r♦✉❣❤ t❤❡ ❛❞✲ s♦r❜❡❞ ❤②❞r♦①②♣r♦♣②❧ ✐♥t❡r♠❡❞✐❛t❡ ✉♥❞❡r st❡❛❞② st❛t❡ ❝♦♥❞✐t✐♦♥s ✈✐❛ t❤❡ ✉♥❛ss✐st❡❞ ✭❜❧❛❝❦✮✱ ❖✷ ✲❛ss✐st❡❞ ✭♦r❛♥❣❡✮✱ ❖✲❛ss✐st❡❞ ✭❜❧✉❡✮✱ ❛♥❞ ❖❍✲❛ss✐st❡❞ ✭❣r❡❡♥✮ ♠❡❝❤❛♥✐s♠s✳ ❚❤❡ ③❡r♦ ♦❢ ❢r❡❡ ❡♥❡r❣② ❝♦rr❡s♣♦♥❞s t♦ ❛❧❧ ❝♦✲r❡❛❝t❛♥ts s❡♣❛r❛t❡❞ ❜✉t ♣r❡✲❛❞s♦r❜❡❞ ♦♥ t❤❡ ❝❛t❛❧②st s✉r✲ ❢❛❝❡✳ ❚❤❡ ❡♥❡r❣❡t✐❝s ♦❢ t❤✐s ♣❛t❤✇❛② ♦♥ t❤❡ ♣r✐st✐♥❡ s✉r❢❛❝❡ ❛r❡ ✐❧❧✉str❛t❡❞ ✐♥ ❋✐❣✉r❡ ❙✸✳
❞❡❝♦♠♣♦s✐t✐♦♥ ✐s ❛ ✈❡r② s✉❜st❛♥t✐❛❧ s✉r❢❛❝❡ r❡❛❝t✐♦♥ ♦❢ ❖✷ ∗
+ ❍∗
1.24 eV✳
▼♦r❡♦✈❡r✱ ❢♦r♠❛t✐♦♥ ♦❢ ❖❖❍ ❜② t❤❡ ♣✉r❡❧② ♦♥✲
❤❛s ❛ ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡r ♦❢
0.77 eV✱
✇❤✐❝❤ ✐s ♠♦r❡ ✉♥❢❛✈♦r❛❜❧❡
t❤❛♥ t❤❡ ❡♥❞♦t❤❡r♠✐❝ r❡❛❝t✐♦♥ ♦❢ ❖✷ ✇✐t❤ ♣r♦♣❛♥♦❧ t♦ ❢♦r♠ ❖❖❍ ❛♥❞ ♣r♦♣♦①✐❞❡✳
❚❤✐s
s✉❣❣❡sts t❤❛t ❖✷ ✲❛ss✐st❡❞ ❖−❍ ❜♦♥❞ s❝✐ss✐♦♥ ✐s ❛ ♣r❡r❡q✉✐s✐t❡ ❢♦r t❤❡ ❖✲❛ss✐st❡❞ ❛♥❞ ❖❍✲ ❛ss✐st❡❞ ♣❛t❤✇❛②s✱ ❛♥❞ t❤❡r❡❢♦r❡ ✐t ♠✉st ♦❝❝✉r ❛t s♦♠❡ ♣♦✐♥t ✐♥ t❤❡ r❡❛❝t✐♦♥ ♥❡t✇♦r❦✳ ▼✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✐♥❣ ❣✐✈❡s ✉s t❤❡ ❛❜✐❧✐t② t♦ ✐❞❡♥t✐❢② ✇❤✐❝❤ ♦❢ t❤❡ ♠❛♥② ♣❧❛✉s✐❜❧❡ r❡❛❝✲ t✐♦♥ ♣❛t❤✇❛②s ♦✉t❧✐♥❡❞ ❛❜♦✈❡ ❛r❡✱ ✐♥ ❢❛❝t✱ ❦✐♥❡t✐❝❛❧❧② r❡❧❡✈❛♥t✳ ❇❛s❡❞ ♦♥ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✱ ✇❡ ✜♥❞ t❤❛t t❤❡ ✐♥✐t✐❛❧ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ❢♦r♠ ♣r♦♣❛♥❛❧ ♣r♦❝❡❡❞s ❧❛r❣❡❧② t❤r♦✉❣❤ ❛ s✐♥❣❧❡ ♣❛t❤✇❛②✿ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ t❤❡ ❤②❞r♦①②♣r♦♣②❧ ✐♥t❡r♠❡❞✐❛t❡✱ ✇❤✐❝❤ r❡❛❝ts ✇✐t❤ ❝♦❛❞s♦r❜❡❞ ❖✷ t♦ ❢♦r♠ ♣r♦♣❛♥❛❧ ❛♥❞ ❖❖❍ ✭s❡❡ ❋✐❣✉r❡ ✻✮✳ ■♥✐t✐❛❧ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ t❤❡ ❤②❞r♦①②♣r♦♣②❧ ✐♥t❡r♠❡❞✐❛t❡ ✭✈✐❛ ❈−❍ ❜♦♥❞ ❝❧❡❛✈❛❣❡✮ ❤❛s t❤❡ ❧❛r❣❡st ❜❛rr✐❡r ❛♥❞ t❤❡ ❤✐❣❤❡st ❞❡❣r❡❡ ♦❢ r❛t❡ ❝♦♥tr♦❧ ♦❢ ❛❧❧ ❡❧❡♠❡♥t❛r② st❡♣s ✐♥ t❤❡ r❡❛❝t✐♦♥ ♥❡t✇♦r❦✳
❚❤✐s r❡❛❝t✐♦♥ ✐s ❡♥❞♦t❤❡r♠✐❝ ❜②
✶✼
ACS Paragon Plus Environment
0.13 eV
♦♥ t❤❡ ♣r✐st✐♥❡
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Paragon Plus Environment
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ACS Catalysis
t❤❡ ❤②❞r♦①②♣r♦♣②❧ ✐♥t❡r♠❡❞✐❛t❡ ✇✐t❤ ❖✷ t♦ ❢♦r♠ ♣r♦♣❛♥❛❧ ❛♥❞ ❖❖❍ ✐s ❜❛rr✐❡r❧❡ss✳
❚❤❡
♣❛t❤✇❛② ✐♥ ✇❤✐❝❤ ♣r♦♣♦①✐❞❡ ❛♥✐♦♥s ❛❞s♦r❜ t♦ t❤❡ ❝❛t❛❧②st ❛♥❞ ❜❡❝♦♠❡ ❞❡❤②❞r♦❣❡♥❛t❡❞ t♦ ♣r♦♣❛♥❛❧ ❝♦♠♣❧❡t❡❧② ❜②♣❛ss❡s t❤❡ ❤②❞r♦①②♣r♦♣②❧ ✐♥t❡r♠❡❞✐❛t❡✱ t❤❡r❡❜② ✐♥❤✐❜✐t✐♥❣ ❝r✉❝✐❛❧ ❖✷ r❡❞✉❝t✐♦♥ t♦ ❖❖❍✳ ◆♦t❡ t❤❛t t❤❡ ♣r❡❞♦♠✐♥❛♥t ♣❛t❤✇❛② ♣r❡❞✐❝t❡❞ ❜② ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ❢♦r ❞❡❤②❞r♦✲ ❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♣r♦♣❛♥❛❧ ❞✐✛❡rs ❢r♦♠ t❤❡ ♣❛t❤✇❛②s ♣r♦♣♦s❡❞ ❜② ❍✐❜❜✐tts ❛♥❞ ◆❡✉r♦❝❦ ❢♦r ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ❡t❤❛♥♦❧ t♦ ❛❝❡t❛❧❞❡❤②❞❡✱ ❞❡s♣✐t❡ t❤❡ s✐♠✐❧❛r ❡♥❡r❣❡t✐❝s ♦❢ t❤❡s❡ t✇♦ s②st❡♠s✳
❍✐❜❜✐tts ❛♥❞ ◆❡✉r♦❝❦ ♣r❡❞✐❝t t❤❛t ✉♥❞❡r ❜❛s✐❝ ❝♦♥❞✐t✐♦♥s✱ t❤❡ ❛❧❝♦❤♦❧ ✇✐❧❧ ♣r✐✲
♠❛r✐❧② ❛❞s♦r❜ t♦ t❤❡ ❝❛t❛❧②st ❛s t❤❡ ❞❡♣r♦t♦♥❛t❡❞ ❛❧❦♦①✐❞❡✱ ✇❤✐❝❤ ✐s ✐♥ ❞✐s❛❣r❡❡♠❡♥t ✇✐t❤ t❤❡ r❡s✉❧ts ♦❢ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✳ ❖✉r r❡s✉❧ts ❝❛♥ ❜❡ ❡①♣❧❛✐♥❡❞ ❜♦t❤ ❜② t❤❡ ✉♥❢❛✈♦r✲ ❛❜❧❡ t❤❡r♠♦❞②♥❛♠✐❝s ♦❢ ❛❞s♦r♣t✐♦♥ ♦❢ t❤❡ ❛❧❦♦①✐❞❡ ❞✉❡ t♦ t❤❡ ♥❡❣❛t✐✈❡ st❡❛❞②✲st❛t❡ ❝❤❛r❣❡ ❛❝q✉✐r❡❞ ❜② t❤❡ ❝❛t❛❧②st ✉♥❞❡r ✇♦r❦✐♥❣ ❝♦♥❞✐t✐♦♥s✱ ❛♥❞ ❜② t❤❡ ❝r✐t✐❝❛❧ r♦❧❡ ♣❧❛②❡❞ ❜② t❤❡ ❤②❞r♦①②♣r♦♣②❧ ✐♥t❡r♠❡❞✐❛t❡ ✐♥ r❡❞✉❝t✐♦♥ ♦❢ ❖✷ ✳ ❚❤❡s❡ ❢❛❝t♦rs ❛r❡ ❞✐✣❝✉❧t t♦ ♣r❡❞✐❝t ✐♥ t❤❡ ❛❜s❡♥❝❡ ♦❢ ❦✐♥❡t✐❝ ♠♦❞❡❧✐♥❣✳
✸✳✷✳✷ ❉❡❤②❞r♦❣❡♥❛t✐♦♥ ❛♥❞ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r♦♣❛♥❛❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ❙✉❜s❡q✉❡♥t ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r♦♣❛♥❛❧ ❝❛♥ ♣r♦❝❡❡❞ t❤r♦✉❣❤ ♦♥❡ ♦❢ t✇♦ ♣♦t❡♥t✐❛❧ ♣❛t❤✇❛②s✱ ❜♦t❤ ✐♥✈♦❧✈✐♥❣ ♦♥❡ ❈−❖ ❜♦♥❞ ❢♦r♠❛t✐♦♥ st❡♣ ❛♥❞ ♦♥❡ ❈−❍ ❜♦♥❞ ❝❧❡❛✈❛❣❡ st❡♣✳ ❚❤❡ ♠♦st ❞✐✲ r❡❝t ♣❛t❤✇❛② ♣r♦❝❡❡❞s t❤r♦✉❣❤ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ s✉r❢❛❝❡✲❜♦✉♥❞ ♣r♦♣❛♥❛❧ t♦ t❤❡ ♣r♦♣❛♥♦②❧ ✐♥t❡r♠❡❞✐❛t❡✱ ✇❤✐❝❤ r❡❛❝ts ✇✐t❤ s✉r❢❛❝❡✲❜♦✉♥❞ ♠❡t❤♦①② t♦ ❢♦r♠ t❤❡ ❡st❡r✳ ❚❤❡ ❛❧t❡r♥❛t✐✈❡ ♣❛t❤✇❛② ✐♥✈♦❧✈❡s ❞❡s♦r♣t✐♦♥ ♦❢ ♣r♦♣❛♥❛❧✱ ✇❤✐❝❤ r❡❛❝ts ✇✐t❤ ♠❡t❤♦①✐❞❡ ✐♥ s♦❧✉t✐♦♥ t♦ ❢♦r♠ ❛ ❞❡♣r♦t♦♥❛t❡❞ ❤❡♠✐❛❝❡t❛❧ ❛♥✐♦♥✳ ❚❤❡ ❞❡♣r♦t♦♥❛t❡❞ ❤❡♠✐❛❝❡t❛❧ ❛♥✐♦♥ t❤❡♥ ❛❞s♦r❜s t♦ t❤❡ ❝❛t❛❧②st ❛♥❞ ✉♥❞❡r❣♦❡s
β✲❤②❞r✐❞❡
❡❧✐♠✐♥❛t✐♦♥ t♦ t❤❡ ✜♥❛❧ ❡st❡r ♣r♦❞✉❝t✳ ■♥ ❜♦t❤ ♣❛t❤✇❛②s✱
♦♥❡ ❍ ❛t♦♠ ✐s ❞❡♣♦s✐t❡❞ ♦♥t♦ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❛♥❞ ♦♥❡ ❛♥✐♦♥ ✕ ❡✐t❤❡r ♠❡t❤♦①✐❞❡ ♦r t❤❡ ❞❡♣r♦t♦♥❛t❡❞ ❤❡♠✐❛❝❡t❛❧ ❛♥✐♦♥ ✕ ❛❞s♦r❜s t♦ t❤❡ s✉r❢❛❝❡✳ ❇❛s❡❞ ♦♥ t❤❡ r❡s✉❧ts ♦❢ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✱ ✇❡ ✜♥❞ t❤❛t ❜♦t❤ ♣❛t❤✇❛②s ❛r❡ ❢❡❛s✐❜❧❡ ❛♥❞ ❝♦♥tr✐❜✉t❡ t♦ t❤❡ ♦✈❡r❛❧❧ ❝❛t❛❧②st ❛❝t✐✈✐t② ✭s❡❡ ❋✐❣✉r❡ ✼✮✳ ❆ s❧✐❣❤t ♠❛❥♦r✐t② ✭53 %✮ ♦❢
✶✾
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Paragon Plus Environment
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ACS Catalysis
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
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❖♥❝❡ ❛♥ ❍ ❛t♦♠ ❜❡❝♦♠❡s ❛❞s♦r❜❡❞ t♦ t❤❡ ❝❛t❛❧②st✱ t❤❡r❡ ❛r❡ s❡✈❡r❛❧ ♣❛t❤✇❛②s ❜② ✇❤✐❝❤ ✐t ❝❛♥ ❜❡ r❡♠♦✈❡❞✳
❚❤❡ ♠♦st ❞✐r❡❝t ♣❛t❤✇❛② ✐s ❞❡s♦r♣t✐♦♥ ♦❢ ❍✷ ✱ t❤♦✉❣❤ t❤❡ r❛t❡ ♦❢ t❤✐s
♣❛t❤✇❛② ✐s ❡①♣❡❝t❡❞ t♦ ❜❡ s♠❛❧❧✱ ❛s ✐t ❞♦❡s ♥♦t ❝♦♥tr✐❜✉t❡ t♦ t❤❡ r❡❞✉❝t✐♦♥ ♦❢ ❖✷ ❛♥❞ ✐t ✐s ♥♦t ♦❜s❡r✈❡❞ t♦ ❜❡ ❛ ♠❛❥♦r ♣r♦❞✉❝t ❡①♣❡r✐♠❡♥t❛❧❧②✳ ❚❤❡ ♠❛❥♦r✐t② ♦❢ s✉r❢❛❝❡✲❜♦✉♥❞ ❍ ✇✐❧❧ r❡❛❝t t♦ ❡✈❡♥t✉❛❧❧② ❢♦r♠ ❍✷ ❖✳ ❍♦✇❡✈❡r✱ ❞✐r❡❝t ❛❜str❛❝t✐♦♥ ♦❢ ❍ ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❜② ❖✷ ✱ ❖✱ ♦r ❖❍ ❛r❡ ❢♦✉♥❞ t♦ ❤❛✈❡ ✈❡r② ❧❛r❣❡ ❜❛rr✐❡rs✳ ■♥st❡❛❞✱ ✇❡ ✜♥❞ t❤❛t ♠❡t❤♦①✐❞❡ ❛❞s♦r❜s t♦ t❤❡ ❝❛t❛❧②st ❛♥❞ ❛❜str❛❝ts ❛ ♣r♦t♦♥✱ t❤❡♥ ✐t ❡✐t❤❡r ❞❡s♦r❜s ❛s ♠❡t❤❛♥♦❧ ♦r s✉❜s❡q✉❡♥t❧② r❡❛❝ts ✇✐t❤ s✉r❢❛❝❡✲❜♦✉♥❞ ❖ ♦r ❖❍ t♦ ❢♦r♠ ❖❍ ♦r ❍✷ ❖ ✭s❡❡ ❋✐❣✉r❡ ✽✮✳ ❆♥② ❖❍ t❤❛t ✐s ❢♦r♠❡❞
✕
r❛♣✐❞❧② ♣✐❝❦s ✉♣ ❛♥ ❡❧❡❝tr♦♥ ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❛♥❞ ❞❡s♦r❜s ❛s ❖❍ ✱ ✇❤✐❝❤ ❝❛♥ ✐♥ t✉r♥ ❛❜str❛❝t ❛ ♣r♦t♦♥ ❢r♦♠ t❤❡ ♠❡t❤❛♥♦❧ s♦❧✈❡♥t t♦ ❢♦r♠ ❍✷ ❖ ❛♥❞ r❡❣❡♥❡r❛t❡ ♠❡t❤♦①✐❞❡✳ ■♥ t❤✐s ✇❛②✱ ♠❡t❤♦①✐❞❡ s❤✉tt❧❡s ❍ ❛t♦♠s ♦✛ t❤❡ s✉r❢❛❝❡ ❛♥❞ ♦♥t♦ ♦①②❣❡♥✱ ✇❤✐❝❤ ✐s ❧❡ss ❛❜❧❡ t♦ ❞✐r❡❝t❧② ❛❜str❛❝t ❍ ❢r♦♠ t❤❡ s✉r❢❛❝❡ ✐ts❡❧❢✱
CH3 O− + 2 H∗ + O∗ −−→ CH3 OH + OH− −−→ CH3 O− + H2 O.
✭✺✮
❲❡ ✜♥❞ t❤❛t ❍ ❤❛s t❤❡ ♠♦st str♦♥❣❧② ♥❡❣❛t✐✈❡ ❞❡❣r❡❡ ♦❢ t❤❡r♠♦❞②♥❛♠✐❝ r❛t❡ ❝♦♥tr♦❧ ♦❢ ❛❧❧ s♣❡❝✐❡s ✐♥ t❤❡ r❡❛❝t✐♦♥ ♥❡t✇♦r❦✱ ✇✐t❤
χT RC = −1.37✳
❆s s✉❝❤✱ t❤❡ ♣r❡s❡♥❝❡ ♦❢ ❍ ♦♥ t❤❡
❝❛t❛❧②st s✉r❢❛❝❡ str♦♥❣❧② s✉♣♣r❡ss❡s ❝❛t❛❧②t✐❝ ❛❝t✐✈✐t②✳ ❍♦✇❡✈❡r✱ t❤❡ ♥❡❣❛t✐✈❡ ❞❡❣r❡❡ ♦❢ r❛t❡ ❝♦♥tr♦❧ ♦❜s❡r✈❡❞ ❢♦r ❍ ❞♦❡s ♥♦t ♥❡❝❡ss❛r✐❧② ❛r✐s❡ ❢r♦♠ ❝❛t❛❧②st ♣♦✐s♦♥✐♥❣ ✈✐❛ s✐t❡ ❜❧♦❝❦✐♥❣✱ ❛s ❛r♦✉♥❞
7 % ♦❢ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ r❡♠❛✐♥s ✉♥♦❝❝✉♣✐❡❞
✐♥ t❤❡ st❡❛❞② st❛t❡✳ ■♥st❡❛❞✱ ✇❡ ✜♥❞ t❤❛t t❤❡ ♣r❡s❡♥❝❡ ♦❢ ❍
❞❡st❛❜✐❧✐③❡s
❝♦✲❛❞s♦r❜❛t❡s t❤r♦✉❣❤
❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥s✳ ■♥❞❡❡❞✱ t❤❡ ❤✐❣❤ ❍ ❝♦✈❡r❛❣❡ ♦❢ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ r❛✐s❡s t❤❡ ❜✐♥❞✐♥❣ ❡♥❡r❣② ♦❢ ♦t❤❡r ❛❞s♦r❜❛t❡s ❜② ❛s ♠✉❝❤ ❛s
0.83 eV
✐♥ t❤❡ st❡❛❞② st❛t❡ ✭✐♥ t❤❡ ❝❛s❡ ♦❢ t❤❡
❞❡♣r♦t♦♥❛t❡❞ ❤❡♠✐❛❝❡t❛❧ ✐♥t❡r♠❡❞✐❛t❡✮✳ ❲❡ ✜♥❞ t❤❛t ❛❧❧ ❛❞s♦r❜❛t❡s ❛r❡ ❞❡st❛❜✐❧✐③❡❞ ✉♥❞❡r ❤✐❣❤ ❍ ❝♦✈❡r❛❣❡ ❝♦♥❞✐t✐♦♥s✱ ❜✉t ❝❧♦s❡❞✲s❤❡❧❧ ❛♥❞ ♣❤②s✐s♦r❜❡❞ ♠♦❧❡❝✉❧❡s ❛r❡ ❞❡st❛❜✐❧✐③❡❞ t♦ ♠✉❝❤ ❧❡ss❡r ❡①t❡♥t t❤❛♥ ♦♣❡♥✲s❤❡❧❧ r❡❛❝t✐♦♥ ✐♥t❡r♠❡❞✐❛t❡s✳ ❋♦r ❡①❛♠♣❧❡✱ ❖❖❍ ✐s ❞❡st❛❜✐❧✐③❡❞ t♦ ❛ ♠✉❝❤ ❣r❡❛t❡r ❡①t❡♥t t❤❛♥ ❛❞s♦r❜❡❞ ❖✷ ✱ ❛♥❞ ❝♦♥s❡q✉❡♥t❧② r❡❞✉❝t✐♦♥ ♦❢ ❖✷ t♦ ❖❖❍ ✐s
✷✷
ACS Paragon Plus Environment
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ACS Catalysis
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 24 of 35
✇❤❡r❡❛s ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ ♦r ♠❡t❤❛♥♦❧ ♣r♦❞✉❝❡s ❧❡ss st❛❜❧❡ ♦♣❡♥✲s❤❡❧❧ ❛❧❦♦①② ✐♥t❡r♠❡❞✐❛t❡s✳ ❖♥❝❡ ❖❖❍ ✐s ❢♦r♠❡❞ ♦♥ t❤❡ s✉r❢❛❝❡✱ ✐t r❛♣✐❞❧② ❞❡❝♦♠♣♦s❡s t♦ ❖ ❛♥❞ ❖❍✳ ❲❡ ✜♥❞ t❤❛t ♠♦st ❖❍ t❤❛t ❢♦r♠s ♦♥ t❤❡ s✉r❢❛❝❡ r❛♣✐❞❧② ❛❝❝❡♣ts ❛♥ ❡❧❡❝tr♦♥ ❢r♦♠ t❤❡ ❝❛t❛❧②st ❛♥❞ ❞❡s♦r❜s
✕
❛s ❖❍ ✳ ❆ s♠❛❧❧ ❛♠♦✉♥t ♦❢ ❖❍ r❡❛❝ts ✇✐t❤ ♣r♦♣❛♥♦❧ t♦ ❢♦r♠ ♣r♦♣♦①② ❛♥❞ ❍✷ ❖✱ ✇❤✐❝❤ t❤❡♥ ❞❡s♦r❜s✳ ❚❤❡ r❡♠❛✐♥✐♥❣ ❖ ❛t♦♠ ♠✉st ❛❜str❛❝t ❛t ❧❡❛st ♦♥❡ ♠♦r❡ ❍ ❛t♦♠ ❜❡❢♦r❡ ❞❡s♦r❜✐♥❣ ❢r♦♠ t❤❡ s✉r❢❛❝❡ ❛s ❖❍
✕
♦r ❍✷ ❖✳ ❍♦✇❡✈❡r✱ ❛s ✇✐t❤ ❖✷ ✱ ❞✐r❡❝t ❛❜str❛❝t✐♦♥ ♦❢ s✉r❢❛❝❡ ❍ ❜② ❖
❤❛s ❛ ❧❛r❣❡ ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡r ✭0.73 eV✮✳ ❍♦✇❡✈❡r✱ ❖ ✐s ❛❧s♦ ❝❛♣❛❜❧❡ ♦❢ ❛❜str❛❝t✐♥❣ ❍ ❛t♦♠s ❞✐r❡❝t❧② ❢r♦♠ t❤❡ ❖−❍ ❣r♦✉♣s ♦❢ ❝♦❛❞s♦r❜❛t❡s✱ ❜✉t ✉♥❧✐❦❡ ❖✷ ✱ t❤✐s r❡❛❝t✐♦♥ ✐s ✐♥tr✐♥s✐❝❛❧❧② ❡①♦t❤❡r♠✐❝✳
❲❡ ✜♥❞ t❤❛t ❖ ♣r✐♠❛r✐❧② r❡❛❝ts ✇✐t❤ ❛❞s♦r❜❡❞ ♠❡t❤❛♥♦❧ t♦ ❢♦r♠ ❖❍ ❛♥❞
♠❡t❤♦①②✳
✸✳✷✳✺ ❚❤❡ r♦❧❡ ♦❢ ❜❛s❡ ❚❤❡ ✐♠♣❛❝t ♦❢ ❜❛s❡ ✐♥ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ✐s ❛❧s♦ ❝♦♠♣❧❡①✳ ❯❧t✐✲ ♠❛t❡❧②✱ ✇❡ ✜♥❞ t❤❛t ❜❛s❡ ❢❛❝✐❧✐t❛t❡s r❡♠♦✈❛❧ ♦❢ ❍ ❛t♦♠s ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✱ ❜✉t t❤❛t ✐ts ❛❜✐❧✐t② t♦ ❞♦ s♦ ✐s ❧✐♠✐t❡❞ ❜② r❡♠♦✈❛❧ ♦❢ ❡①❝❡ss ♥❡❣❛t✐✈❡ ❝❤❛r❣❡ ❢r♦♠ t❤❡ ❝❛t❛❧②st ✈✐❛ ❖❍
✕
❞❡s♦r♣t✐♦♥✳ ❇❛s❡❞ ♦♥ t❤❡ r❡s✉❧ts ♦❢ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ✭s❡❡ ❋✐❣✉r❡ ✶✵✮✱ ✇❡ ✜♥❞ t❤❛t ❢♦r ❡❛❝❤ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ♣r♦❞✉❝❡❞✱ ❛♣♣r♦①✐♠❛t❡❧② ✶✳✻✹ ❖❍
✕
❛♥✐♦♥s ❛♥❞ ✵✳✵✽ ♣r♦♣♦①✐❞❡ ❛♥✐♦♥s
❞❡s♦r❜ ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳ ❚♦ ♠❛✐♥t❛✐♥ ❝❤❛r❣❡ ❜❛❧❛♥❝❡✱ ✶✳✶✾ ♠❡t❤♦①✐❞❡ ❛♥✐♦♥s ❛♥❞ ✵✳✺✸ ❞❡♣r♦t♦♥❛t❡❞ ❤❡♠✐❛❝❡t❛❧ ❛♥✐♦♥s ❛❞s♦r❜ t♦ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳
❇♦t❤ ♠❡t❤♦①✐❞❡ ❛♥❞
t❤❡ ❞❡♣r♦t♦♥❛t❡❞ ❤❡♠✐❛❝❡t❛❧ ❛♥✐♦♥s ❛r❡ ❞✐r❡❝t❧② ✐♥✈♦❧✈❡❞ ✐♥ t❤❡ ❢♦r♠❛t✐♦♥ ♦❢ ♠❡t❤②❧ ♣r♦✲ ♣✐♦♥❛t❡✱ ❜✉t ✇❡ ✜♥❞ t❤❛t ❛❞s♦r♣t✐♦♥ ♦❢ ♠❡t❤♦①✐❞❡ ✐s ✐♥ ❡①❝❡ss ♦❢ ✇❤❛t ✐s r❡q✉✐r❡❞ t♦ r❡❛❝t ✇✐t❤ ♣r♦♣❛♥♦②❧ ♦♥ t❤❡ s✉r❢❛❝❡ t♦ ❢♦r♠ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡✳ ❚❤✐s ❡①❝❡ss ♠❡t❤♦①✐❞❡ ❡✈❡♥t✉❛❧❧② ❞❡s♦r❜s ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ❛s ♠❡t❤❛♥♦❧✱ t❤❡r❡❜② ❢❛❝✐❧✐t❛t✐♥❣ t❤❡ r❡♠♦✈❛❧ ♦❢ ❍ ❛t♦♠s✳ ■♥ ❢❛❝t✱ t❤❡ ❡✛❡❝t ♦❢ ❜❛s❡ ❝❛♥ ❜❡ ❜r♦❛❞❧② ❝❤❛r❛❝t❡r✐③❡❞ ❛s ❧♦✇❡r✐♥❣ t❤❡ st❡❛❞② st❛t❡ ❍ ❛t♦♠ ❝♦♥❝❡♥tr❛t✐♦♥ ♦♥ t❤❡ s✉r❢❛❝❡✱ ❡✐t❤❡r ❜② ❞✐r❡❝t ❍ ❛t♦♠ r❡♠♦✈❛❧ ✭s❡❡ ❡q✉❛t✐♦♥ ✺✮ ♦r ❜② ❡❧✐♠✐✲
✷✹
ACS Paragon Plus Environment
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ACS Paragon Plus Environment
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✕
♦❢ ❖❍ ✱ ✇❤✐❝❤ ✐s ❢♦r♠❡❞ ❢♦❧❧♦✇✐♥❣ r❡❞✉❝t✐♦♥ ♦❢ ❖✷ t♦ ❖❖❍✳ ❚❤❡r❡❢♦r❡✱ ✇❡ ❛r❣✉❡ t❤❛t t❤❡ ❛❜✐❧✐t② ♦❢ ❝❛t❛❧②t✐❝ ❜❛s❡ t♦ r❡♠♦✈❡ ❡①❝❡ss ❍ ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ✐s ❧✐♠✐t❡❞ ❜② t❤❡ r❛t❡ ❛t ✇❤✐❝❤ ❖✷ ✐s r❡❞✉❝❡❞ t♦ ❖❖❍✳ ❲❡ ♦❜s❡r✈❡ t❤❛t t❤❡ ♠❛❥♦r✐t② ♦❢ ❖❍ ❢♦r♠❡❞ ♦♥ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ✐♠♠❡❞✐❛t❡❧② ❛❝❝❡♣ts
✕
❛♥ ❡❧❡❝tr♦♥ ❢r♦♠ t❤❡ ❝❛t❛❧②st ❛♥❞ ❞❡s♦r❜s ❛s ❖❍ ✳ ■♥ t❤❡ ❛❜s❡♥❝❡ ♦❢ ❜❛s❡✱ ❖❍ ✇♦✉❧❞ ♥❡❡❞ t♦ ❜❡ ❢✉rt❤❡r r❡❞✉❝❡❞ t♦ ❍✷ ❖ ❜❡❢♦r❡ ❞❡s♦r❜✐♥❣✳ ❲❤✐❧❡ t❤✐s r❡❛❝t✐♦♥ ✐s str♦♥❣❧② ❡①♦t❤❡r♠✐❝✱ ✐t ❤❛s ❛ ❢❛✐r❧② ❤✐❣❤ ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡r ♦❢
0.59 eV
✐♥ t❤❡ st❡❛❞② st❛t❡ ✉♥❞❡r ❜❛s✐❝ ❝♦♥❞✐t✐♦♥s✳
❈♦♥s❡q✉❡♥t❧②✱ t❤✐s r❡❛❝t✐♦♥ ✇♦✉❧❞ ❝♦♠♣❡t❡ ✇✐t❤ ❖ ❛♥❞ ❖✷ ❢♦r t❤❡ ❧✐♠✐t❡❞ ♥✉♠❜❡r ♦❢ ❖−❍ ❣r♦✉♣ ❝♦♥t❛✐♥✐♥❣ ❝♦❛❞s♦r❜❛t❡s✳ ■♥ s✉♠♠❛r②✱ ❝❛t❛❧②t✐❝ ❜❛s❡ ♣❧❛②s t❤r❡❡ ❦❡② r♦❧❡s ✐♥ t❤❡ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ ♦♥ P❞✭✶✶✶✮✿
✶✮ s❝❛✈❡♥❣✐♥❣ ♦❢ ❍ ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✱ ✷✮ ❞❡♣r♦t♦♥❛t✐♦♥ ♦❢ ❛❧❝♦❤♦❧s ✐♥
s♦❧✉t✐♦♥ t♦ t❤❡ ❝♦rr❡s♣♦♥❞✐♥❣ ❛❧❦♦①✐❞❡ ✭t❤❡r❡❜② r❡♠♦✈✐♥❣ t❤❡ ♥❡❡❞ ❢♦r ♦♥✲s✉r❢❛❝❡ ❛❧❝♦❤♦❧ ❞❡♣r♦t♦♥❛t✐♦♥✮✱ ❛♥❞ ✸✮ ❞r✐✈✐♥❣ s✉r❢❛❝❡✲❜♦✉♥❞ ❖❍ t♦ ❞❡s♦r❜ ❛s ❖❍
✕
r❛t❤❡r t❤❛♥ r❡q✉✐r✐♥❣ ✐t
❜❡ ❢✉❧❧② ❤②❞r♦❣❡♥❛t❡❞ t♦ ❍✷ ❖ ♦♥ t❤❡ ❝❛t❛❧②st✳
✹
❈♦♥❝❧✉❞✐♥❣ r❡♠❛r❦s
❖✉r ✜rst✲♣r✐♥❝✐♣❧❡s ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ♦❢ t❤❡ s♦❧✉t✐♦♥✲♣❤❛s❡ ❜❛s❡✲❝❛t❛❧②③❡❞ ♦①✐❞❛t✐✈❡ ❡st❡r✲ ✐✜❝❛t✐♦♥ ♦❢ ♣r♦♣❛♥♦❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ♣r❡❞✐❝ts ❛ ❚❖❋ ♦❢
88.4 h−1 ✱
♠♦❞❡st ❡①♣❡r✐♠❡♥t❛❧❧② ♦❜s❡r✈❡❞ ❛❝t✐✈✐t② ♦❢ t❤❡ ✉♥♣r♦♠♦t❡❞ ❝❛t❛❧②st✳
❝♦♥s✐st❡♥t ✇✐t❤ t❤❡ ❙❡♥s✐t✐✈✐t② ❛♥❛❧②s✐s
❞❡♠♦♥str❛t❡s t❤❛t ❛❝t✐✈✐t② ✐s ❧✐♠✐t❡❞ ❜② t❤❡ s❧♦✇ r❡♠♦✈❛❧ ♦❢ ❍ ❢r♦♠ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡✳ ◆♦♥❡t❤❡❧❡ss✱ ❛♣♣r♦①✐♠❛t❡❧②
7%
♦❢ t❤❡ ❝❛t❛❧②st s✉r❢❛❝❡ ✐s ✉♥♦❝❝✉♣✐❡❞ ✐♥ t❤❡ st❡❛❞② st❛t❡✱
s✉❣❣❡st✐♥❣ t❤❡ s✉r❢❛❝❡ ✐s ♥♦t ♥❡❝❡ss❛r✐❧② ♣♦✐s♦♥❡❞ ✈✐❛ s✐t❡ ❜❧♦❝❦✐♥❣✳
❘❛t❤❡r✱ ✇❡ ✜♥❞ t❤❛t
t❤❡ ♣r❡s❡♥❝❡ ♦❢ ❛❞s♦r❜❡❞ ❍ ❞❡st❛❜✐❧✐③❡s ♦t❤❡r r❡❛❝t✐♦♥ ✐♥t❡r♠❡❞✐❛t❡s ✈✐❛ str♦♥❣ ❧❛t❡r❛❧ ✐♥t❡r✲ ❛❝t✐♦♥s✳ ❆❞❞✐t✐♦♥❛❧❧②✱ t❤❡ ❛❝t✐✈✐t② ♦❢ t❤❡ ❝❛t❛❧②st ✐s ❤✐♥❞❡r❡❞ ❜② ❛ ❤✐❣❤ ❦✐♥❡t✐❝ ❜❛rr✐❡r ❢♦r ✐♥✐t✐❛❧ ❈−❍ ❜♦♥❞ s❝✐ss✐♦♥ ✐♥ ♣r♦♣❛♥♦❧ ❛♥❞ t❤❡ ✉♥❢❛✈♦r❛❜❧❡ t❤❡r♠♦❞②♥❛♠✐❝s ♦❢ r❡❞✉❝t✐♦♥ ♦❢ ❖✷ t♦ ❖❖❍✳
✷✻
ACS Paragon Plus Environment
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ACS Catalysis
❚❤❡r❡ ❤❛✈❡ ❜❡❡♥ ❛ ♥✉♠❜❡r ♦❢ ❤②♣♦t❤❡s❡s ❢♦r t❤❡ ♠❡❝❤❛♥✐s♠ ❜② ✇❤✐❝❤ ♠❛✐♥ ❣r♦✉♣ ♣r♦✲ ♠♦t❡r ❡❧❡♠❡♥ts ✐♠♣r♦✈❡ ❝❛t❛❧②st ❛❝t✐✈✐t② ❛♥❞ s❡❧❡❝t✐✈✐t② ❢♦r ♦①✐❞❛t✐✈❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ❛♥❞ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ❛❧❝♦❤♦❧s✳
❚❤❡s❡ ❤②♣♦t❤❡s❡s ❢❛❧❧ ✐♥t♦ ♦♥❡ ♦❢ t❤r❡❡ ❜r♦❛❞ ❝❧❛ss❡s✿
✶✮ t❤❡
♣r♦♠♦t❡r ❜❧♦❝❦s s✐t❡s✱ t❤❡r❡❜② ♣r❡✈❡♥t✐♥❣ t❤❡ ❢♦r♠❛t✐♦♥ ♦❢ str♦♥❣❧②✲❜♦✉♥❞ ✉♥❞❡s✐r❡❞ s✐❞❡✲ ♣r♦❞✉❝ts ✭t❤❡ s♦✲❝❛❧❧❡❞ ❡♥s❡♠❜❧❡ ❡✛❡❝t✮❀
✶✺✱✶✻
✷✮ t❤❡ ♣r♦♠♦t❡r ✐♥❞✐r❡❝t❧② ♠♦❞✉❧❛t❡s t❤❡ ❛❝t✐✈✲
✐t② ♦❢ t❤❡ ❝❛t❛❧②st✱ ✇❤✐❝❤ ❝❛♥✱ ❢♦r ❡①❛♠♣❧❡✱ ♣r❡✈❡♥t ❝♦rr♦s✐♦♥
✶✹
♦r s✉♣♣r❡ss ❛ ❜✉✐❧❞✉♣ ♦❢ ❍❀
♦r ✸✮ t❤❡ ♣r♦♠♦t❡r ❞✐r❡❝t❧② ✐♥t❡r❛❝ts ✇✐t❤ s✉r❢❛❝❡ ❛❞s♦r❜❛t❡s✱ ❡✐t❤❡r ❛❝t✐♥❣ ❛s ❛ ❝♦✲❝❛t❛❧②st✱ ♦r ❜② s✐♠♣❧② ❝♦♦r❞✐♥❛t✐♥❣ ❛❞s♦r❜❛t❡s t♦ ❝r❡❛t❡ ♠♦r❡ st❛❜❧❡ ❝♦♥✜❣✉r❛t✐♦♥s✳
✶✸ ✶✶
✶✷
❚❤❡ r❡s✉❧ts ♦❢ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧ ❛♥❞ s♦♠❡ ♣r❡❧✐♠✐♥❛r② ❝❛❧❝✉❧❛t✐♦♥s ♦♥ ♠♦❞❡❧ ♠❛✐♥✲ ❣r♦✉♣ ♣r♦♠♦t❡❞ s✉r❢❛❝❡s s✉❣❣❡st t❤❛t ❜♦t❤ t❤❡ ✐♥❞✐r❡❝t ♠♦❞✉❧❛t✐♦♥ ♦❢ ✐♥tr✐♥s✐❝ P❞ ♠❡t❛❧ ❜✐♥❞✐♥❣ ❡♥❡r❣❡t✐❝s ❛♥❞ ❞✐r❡❝t ♣❛rt✐❝✐♣❛t✐♦♥ ♦❢ ♠❛✐♥ ❣r♦✉♣ ♣r♦♠♦t❡r ❡❧❡♠❡♥ts ♠❛② ♣❧❛② ❛ r♦❧❡ ✐♥ t❤❡ ♦①✐❞❛t✐✈❡ ❞❡❤②❞r♦❣❡♥❛t✐♦♥ ❛♥❞ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ❛❧❝♦❤♦❧s ♦♥ P❞✳ ■♥ ♦✉r ♠✐❝r♦❦✐♥❡t✐❝ ♠♦❞❡❧✱ t❤❡ s✉r❢❛❝❡ ✐s ❤❡❛✈✐❧② ❍✲❝♦✈❡r❡❞✱ ❛♥❞ t❤✐s r❡s✉❧ts ✐♥ t❤❡ ❞❡st❛❜✐❧✐③❛t✐♦♥ ♦❢ ♠❛♥② r❡❛❝t✐♦♥ ✐♥t❡r♠❡❞✐❛t❡s ❞✉❡ t♦ r❡♣✉❧s✐✈❡ ❧❛t❡r❛❧ ✐♥t❡r❛❝t✐♦♥s✳
Pr❡❧✐♠✐♥❛r② ❝❛❧❝✉❧❛t✐♦♥s ♦❢ ❛
❚❡✲♣r♦♠♦t❡❞ P❞✭✶✶✶✮ s✉r❢❛❝❡ ✐♥❞✐❝❛t❡ t❤❛t ♠♦st s♣❡❝✐❡s✱ ✐♥❝❧✉❞✐♥❣ ❍✱ ❜✐♥❞ ♠♦r❡ ✇❡❛❦❧② t♦ t❤✐s s✉r❢❛❝❡ t❤❛♥ t♦ t❤❡ ✉♥♣r♦♠♦t❡❞ s✉r❢❛❝❡✳ ❲❡ ❛❧s♦ ✜♥❞ t❤❛t st❛❜❧❡ ♠♦❧❡❝✉❧❡s ❛♥❞ ❍ ❞♦ ♥♦t ❜✐♥❞ t♦ ❚❡ ❛t♦♠s ❛t ❛❧❧✱ ✇❤❡r❡❛s ♦t❤❡r r❡❛❝t✐♦♥ ✐♥t❡r♠❡❞✐❛t❡s ❞♦ ✭❛❧❜❡✐t ♠♦r❡ ✇❡❛❦❧② t❤❛♥ t♦ P❞✮✳ ❲❤✐❧❡ ✐♥ ♦✉r ♠♦❞❡❧ t❤❡ s✉r❢❛❝❡ ✐s ♥♦t ♣♦✐s♦♥❡❞ ❜② ❍✱ ✐t ✐s ❛♣♣r♦①✐♠❛t❡❧②
74 %
❝♦✈❡r❡❞ ❜② ❍✱ ❛♥❞ t❤✐s ②✐❡❧❞s ❛ str♦♥❣ ❞❡st❛❜✐❧✐③✐♥❣ ❡✛❡❝t ♦♥ ♦t❤❡r ❛❞s♦r❜❛t❡s✳ ❈♦♥s❡q✉❡♥t❧②✱ ✇❡ ❜❡❧✐❡✈❡ t❤❛t t❤❡ ❚❡✲♣r♦♠♦t❡❞ ❝❛t❛❧②st s✉r❢❛❝❡ ✇✐❧❧ ❤❛✈❡ ❛ s✉❜st❛♥t✐❛❧❧② ❧♦✇❡r st❡❛❞② st❛t❡ ❍ ❝♦✈❡r❛❣❡ t❤❛♥ t❤❡ ✉♥♣r♦♠♦t❡❞ ❝❛t❛❧②st✳
▼✐❝r♦❦✐♥❡t✐❝ ❛♥❛❧②s✐s ♦❢ t❤❡ ❡st❡r✐✜❝❛t✐♦♥ ♦❢
♣r♦♣❛♥♦❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡ ♦♥ t❤❡ ❚❡✲ ❛♥❞ ❇✐✲♣r♦♠♦t❡❞ P❞✭✶✶✶✮ s✉r❢❛❝❡s ✇✐❧❧ ❜❡ t❤❡ s✉❜❥❡❝t ♦❢ ❛ ❢✉t✉r❡ ❝♦♠♠✉♥✐❝❛t✐♦♥✳
✷✼
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
✺
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❙✉♣♣♦rt✐♥❣ ✐♥❢♦r♠❛t✐♦♥
❆ ❢r❡❡ ❡♥❡r❣② ♣r♦✜❧❡ ♦❢ t✇♦ r❡♣r❡s❡♥t❛t✐✈❡ ♠❡❝❤❛♥✐s♠s ❢♦r t❤❡ ♦✈❡r❛❧❧ ❡st❡r✐✜❝❛t✐♦♥ ♦❢ ✶✲ ♣r♦♣❛♥♦❧ t♦ ♠❡t❤②❧ ♣r♦♣✐♦♥❛t❡❀ ❢r❡❡ ❡♥❡r❣② ♣r♦✜❧❡s ❢♦r t❤❡② ♣r♦♣♦①② ❛♥❞ ❤②❞r♦①②♣r♦♣②❧ ♣❛t❤✇❛②s ❢♦r ♣r♦♣❛♥❛❧ ❢♦r♠❛t✐♦♥ ♦♥ t❤❡ ♣r✐st✐♥❡ s✉r❢❛❝❡❀ ❛ t❛❜❧❡ ♦❢ ❛❧❧ r❡❛❝t✐♦♥ ❢r❡❡ ❡♥❡r❣✐❡s ❛♥❞ ❢r❡❡ ❡♥❡r❣② ❜❛rr✐❡rs ❢♦r ❛❧❧ r❡❛❝t✐♦♥s ❝♦♥s✐❞❡r❡❞ ✐♥ t❤✐s ♠♦❞❡❧ ♦♥ t❤❡ ♣r✐st✐♥❡ s✉r❢❛❝❡ ❛♥❞ ✉♥❞❡r st❡❛❞② st❛t❡ ❝♦♥❞✐t✐♦♥s❀ ❛ t❛❜❧❡ ❝♦♠♣❛r✐♥❣ ♦✉r r❡s✉❧ts t♦ t❤♦s❡ ♦❢ ❍✐❜❜✐tts ❛♥❞ ◆❡✉r♦❝❦❀ st❡❛❞② st❛t❡ r❛t❡ ❛♥❞ ❞❡❣r❡❡ ♦❢ r❛t❡ ❝♦♥tr♦❧ ❢♦r ❛❧❧ r❡❛❝t✐♦♥s ❝♦♥s✐❞❡r❡❞ ✐♥ t❤✐s ♠♦❞❡❧❀ ❢✉rt❤❡r ❞❡t❛✐❧s ♦♥ ♦✉r ❞♦✉❜❧❡ ❧❛②❡r ❝❛♣❛❝✐t♦r ♠♦❞❡❧❀ ❞❡t❛✐❧s ♦♥ t❤❡ ❝❛❧❝✉❧❛t✐♦♥ ♦❢ ❢r❡❡ ❡♥❡r❣✐❡s ♦❢ s♣❡❝✐❡s ✐♥ t❤❡ ♠♦❞❡❧❀ ❞❡t❛✐❧s ♦♥ t❤❡ ❝❛❧❝✉❧❛t✐♦♥ ♦❢ r❛t❡ ❝♦♥st❛♥ts❀ ❛ ❜r✐❡❢ ❡①♣❧❛♥❛t✐♦♥ ♦♥ t❤❡ ❞✐✛❡r❡♥❝❡s ❜❡t✇❡❡♥ ♦✉r s❡♥s✐t✐✈✐t② ❛♥❛❧②s✐s ❛♥❞ t❤❡ ♠❡t❤♦❞ ❞❡s❝r✐❜❡❞ ❜② ❈❛♠♣❜❡❧❧❀ ❱❆❙P P❖❙❈❆❘ ✜❧❡s ❢♦r ❡❛❝❤ s♣❡❝✐❡s ❝♦♥s✐❞❡r❡❞ ✐♥ t❤✐s ✇♦r❦❀ ✐♥♣✉t ✜❧❡s t♦ ❜❡ ✉s❡❞ ✇✐t❤ ▼✐❝❦✐ ✭❛✈❛✐❧❛❜❧❡ ♦♥ ♦✉r ✇❡❜s✐t❡✮✳
✻
❆❝❦♥♦✇❧❡❞❣♠❡♥ts
❚❤✐s ♠❛t❡r✐❛❧ ✐s ❜❛s❡❞ ✉♣♦♥ ✇♦r❦ s✉♣♣♦rt❡❞ ❜② t❤❡ ◆❛t✐♦♥❛❧ ❙❝✐❡♥❝❡ ❋♦✉♥❞❛t✐♦♥ ✉♥❞❡r ●r❛♥t ◆♦✳ ❈❍❊✲✶✸✻✷✶✸✻✳ ❚❤✐s ✇♦r❦ ✉s❡❞ t❤❡ ❊①tr❡♠❡ ❙❝✐❡♥❝❡ ❛♥❞ ❊♥❣✐♥❡❡r✐♥❣ ❉✐s❝♦✈❡r② ❊♥✈✐r♦♥♠❡♥t ✭❳❙❊❉❊✮✱ ✇❤✐❝❤ ✐s s✉♣♣♦rt❡❞ ❜② ◆❛t✐♦♥❛❧ ❙❝✐❡♥❝❡ ❋♦✉♥❞❛t✐♦♥ ❣r❛♥t ♥✉♠❜❡r ❚●✲❈❍❊✶✷✵✵✽✽✳ ❏✳❘✳❙ ✐s ❛ ❈❛♠✐❧❧❡ ❉r❡②❢✉s ❚❡❛❝❤❡r✲❙❝❤♦❧❛r✳
❘❡❢❡r❡♥❝❡s ✭✶✮ ❙❤❡❧❞♦♥✱ ❘✳
▼❡t❛❧✲❈❛t❛❧②③❡❞ ❖①✐❞❛t✐♦♥s ♦❢ ❖r❣❛♥✐❝ ❈♦♠♣♦✉♥❞s✿ ▼❡❝❤❛♥✐st✐❝ Pr✐♥❝✐♣❧❡s
❛♥❞ ❙②♥t❤❡t✐❝ ▼❡t❤♦❞♦❧♦❣② ■♥❝❧✉❞✐♥❣ ❇✐♦❝❤❡♠✐❝❛❧ Pr♦❝❡ss❡s ❀ ✭✷✮ ❱✐♥♦❞✱ ❈✳ P✳❀ ❲✐❧s♦♥✱ ❑✳❀ ▲❡❡✱ ❆✳ ❋✳
✭✸✮ P❛r♠❡❣❣✐❛♥✐✱ ❈✳❀ ❈❛r❞♦♥❛✱ ❋✳
❊❧s❡✈✐❡r ❙❝✐❡♥❝❡✱ ✷✵✶✷✳
❏✳ ❈❤❡♠✳ ❚❡❝❤♥♦❧✳ ❇✐♦t❡❝❤♥♦❧✳ ✷✵✶✶✱ ✽✻✱
●r❡❡♥ ❈❤❡♠✳
✷✽
✷✵✶✷✱ ✶✹✱ ✺✹✼✳
ACS Paragon Plus Environment
✶✻✶✕✶✼✶✳
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ACS Catalysis
✭✹✮ ▼❛❧❧❛t✱ ❚✳❀ ❇❛✐❦❡r✱ ❆✳
❈❤❡♠✳ ❘❡✈✳
✷✵✵✹✱ ✶✵✹✱ ✸✵✸✼✕✸✵✺✽✳
✭✺✮ ❙❤❡❧❞♦♥✱ ❘✳ ❆✳❀ ❆r❡♥❞s✱ ■✳❀ ❉✐❥❦s♠❛♥✱ ❆✳
✭✻✮ ❋✐❡❣❡✱ ❍✳❀ ❲❡❞❡♠❡②❡r✱ ❑✳
❈❛t❛❧✳ ❚♦❞❛②
❆♥❣❡✇✳ ❈❤❡♠✳
✭✼✮ ▼❛❧❧❛t✱ ❚✳❀ ❇♦❞♥❛r✱ ❩✳❀ ❇❛✐❦❡r✱ ❆✳
✷✵✵✵✱ ✺✼✱ ✶✺✼✕✶✻✻✳
✶✾✽✶✱ ✾✸✱ ✽✶✷✕✽✶✸✳
❙t✉❞✳ ❙✉r❢✳ ❙❝✐✳ ❈❛t❛❧✳
✶✾✾✸✱ ✼✽✱ ✸✼✼✕✸✽✹✳
✭✽✮ ▼❛❧❧❛t✱ ❚✳❀ ❇♦❞♥❛r✱ ❩✳❀ ❇❛✐❦❡r✱ ❆✳❀ ●r❡✐s✱ ❖✳❀ ❙trü❜✐❣✱ ❍✳❀ ❘❡❧❧❡r✱ ❆✳
✶✹✷✱
❏✳ ❈❛t❛❧✳
✶✾✾✸✱
✷✸✼✕✷✺✸✳
✭✾✮ ▼❛♥♥❡❧✱ ❉✳ ❙✳❀ ❆❤♠❡❞✱ ▼✳ ❙✳❀ ❘♦♦t✱ ❚✳ ❲✳❀ ❙t❛❤❧✱ ❙✳ ❙✳
❏✳ ❆♠✳ ❈❤❡♠✳ ❙♦❝✳
✷✵✶✼✱ ✶✸✾✱
✶✻✾✵✕✶✻✾✽✳
✶✾✾✹✱ ✶✾✱ ✷✹✼✕✷✽✹✳
✭✶✵✮ ▼❛❧❧❛t✱ ❚✳❀ ❇❛✐❦❡r✱ ❆✳
❈❛t❛❧✳ ❚♦❞❛②
✭✶✶✮ ❋✉r✉②❛✱ ◆✳❀ ▼♦t♦♦✱ ❙✳
❏✳ ❊❧❡❝tr♦❛♥❛❧✳ ❈❤❡♠✳
✶✾✼✾✱ ✾✽✱ ✶✾✺✕✷✵✷✳
✭✶✷✮ ❙♠✐ts✱ P✳ ❈✳ ❈✳❀ ❑✉st❡r✱ ❇✳ ❋✳ ▼✳❀ ✈❛♥ ❞❡r ❲✐❡❧❡✱ ❑✳❀ ✈❛♥ ❞❡r ❇❛❛♥✱ ❙✳
❆♣♣❧✳ ❈❛t❛❧✳
✶✾✽✼✱ ✸✸✱ ✽✸✕✾✻✳ ✭✶✸✮ P❛rs♦♥s✱ ❘✳❀ ❱❛♥❞❡r◆♦♦t✱ ❚✳
❏✳ ❊❧❡❝tr♦❛♥❛❧✳ ❈❤❡♠✳ ■♥t❡r❢❛❝✐❛❧ ❊❧❡❝tr♦❝❤❡♠✳ ✶✾✽✽✱ ✷✺✼✱
✾✕✹✺✳
✭✶✹✮ ❚s✉❥✐♥♦✱ ❚✳❀ ❖❤✐❣❛s❤✐✱ ❙✳❀ ❙✉❣✐②❛♠❛✱ ❙✳❀ ❑❛✇❛s❤✐r♦✱ ❑✳❀ ❍❛②❛s❤✐✱ ❍✳
❏✳ ▼♦❧✳ ❈❛t❛❧✳
✶✾✾✷✱ ✼✶✱ ✷✺✕✸✺✳ ✭✶✺✮ ❑✐♠✉r❛✱ ❍✳❀ ❚s✉t♦✱ ❑✳❀ ❲❛❦✐s❛❦❛✱ ❚✳❀ ❑❛③✉♠✐✱ ❨✳❀ ■♥❛②❛✱ ❨✳
❆♣♣❧✳ ❈❛t❛❧✳✱ ❆
✶✾✾✸✱ ✾✻✱
✷✶✼✕✷✷✽✳
✶✾✾✸✱ ✺✷✸✱ ✸✵✽✕✸✶✼✳
✭✶✻✮ ▼❛❧❧❛t✱ ❚✳❀ ❇♦❞♥❛r✱ ❩✳❀ ❇❛✐❦❡r✱ ❆✳
❆❈❙ ❙②♠♣✳ ❙❡r✳
✭✶✼✮ ❍♦rá♥②✐✱ ●✳❀ ❱ért❡s✱ ●✳❀ ❑ö♥✐❣✱ P✳
❆❝t❛ ❈❤✐♠✳ ❆❝❛❞✳ ❙❝✐✳ ❍✉♥❣✳
✶✾✼✷✱ ✼✷✱ ✶✼✾✕✶✽✼✳
✭✶✽✮ ❉✐r❦①✱ ❏✳ ▼✳ ❍✳❀ ✈❛♥ ❞❡r ❇❛❛♥✱ ❍✳ ❙✳❀ ✈❛♥ ❞❡♥ ❇r♦❡❦✱ ❏✳ ▼✳ ❆✳ ❏✳ ❏✳
✶✾✼✼✱ ✺✾✱ ✻✸✕✼✷✳ ✷✾
ACS Paragon Plus Environment
❈❛r❜♦❤②❞r✳ ❘❡s✳
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
✭✶✾✮ ❉✐r❦①✱ ❏✳ ▼✳ ❍✳❀ ✈❛♥ ❞❡r ❇❛❛♥✱ ❍✳ ❙✳
❏✳ ❈❛t❛❧✳
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✶✾✽✶✱ ✻✼✱ ✶✹✕✷✵✳
✭✷✵✮ ❉✐❥❦❣r❛❛❢✱ P✳ ❏✳ ▼✳❀ ❉✉✐st❡rs✱ ❍✳ ❆✳ ▼✳❀ ❑✉st❡r✱ ❇✳ ❋✳ ▼✳❀ ✈❛♥ ❞❡r ❲✐❡❧❡✱ ❑✳
❏✳ ❈❛t❛❧✳
✶✾✽✽✱ ✶✶✷✱ ✸✸✼✕✸✹✹✳ ✭✷✶✮ ◆✐❝♦❧❡tt✐✱ ❏✳ ❲✳❀ ❲❤✐t❡s✐❞❡s✱ ●✳ ▼✳
❏✳ P❤②s✳ ❈❤❡♠✳
✭✷✷✮ ●r✉♥✇❛❧❞t✱ ❏✳✲❉✳❀ ❈❛r❛✈❛t✐✱ ▼✳❀ ❇❛✐❦❡r✱ ❆✳
✭✷✸✮ ❍♦✛♠❛♥✱ ❆✳❀ ❑✉❤♥✱ ❆✳ ❚✳
✶✾✽✾✱ ✾✸✱ ✼✺✾✕✼✻✼✳
❏✳ P❤②s✳ ❈❤❡♠✳ ❇
❊❧❡❝tr♦❝❤✐♠✳ ❆❝t❛
✷✵✵✻✱ ✶✶✵✱ ✷✺✺✽✻✕✷✺✺✽✾✳
✶✾✻✹✱ ✾✱ ✽✸✺✕✽✸✾✳
✭✷✹✮ ❉✐❥❦❣r❛❛❢✱ P✳ ❏✳ ▼✳❀ ❘✐❥❦✱ ▼✳ ❏✳ ▼✳❀ ▼❡✉❧❞✐❥❦✱ ❏✳❀ ✈❛♥ ❞❡r ❲✐❡❧❡✱ ❑✳
✶✶✷✱
❏✳ ❈❛t❛❧✳
✶✾✽✽✱
✸✷✾✕✸✸✻✳
✭✷✺✮ ❉✐❥❦❣r❛❛❢✱ P✳ ❏✳ ▼✳ ❖①✐❞❛t✐♦♥ ♦❢ ●❧✉❝♦s❡ t♦ ●❧✉❝❛r✐❝ ❆❝✐❞ ❜② Pt✴❈ ❈❛t❛❧②sts✳ P❤✳❉✳ t❤❡s✐s✱ ❚❡❝❤♥✐s❝❤❡ ❯♥✐✈❡rs✐t❡✐t ❊✐♥❞❤♦✈❡♥✱ ✶✾✽✾✳
✭✷✻✮ ❱✐♥❦❡✱ P✳❀ ❞❡ ❲✐t✱ ❉✳❀ ❞❡ ●♦❡❞❡✱ ❆✳ ❚✳ ❏✳ ❲✳❀ ✈❛♥ ❇❡❦❦✉♠✱ ❍✳
❙t✉❞✳ ❙✉r❢✳ ❙❝✐✳ ❈❛t❛❧✳
✶✾✾✷✱ ✼✷✱ ✶✕✷✵✳ ✭✷✼✮ ❉✐❈♦s✐♠♦✱ ❘✳❀ ❲❤✐t❡s✐❞❡s✱ ●✳
❏✳ P❤②s✳ ❈❤❡♠✳
✶✾✽✾✱ ✾✸✱ ✼✻✽✕✼✼✺✳
✭✷✽✮ ❙❝❤✉✉r♠❛♥✱ ❨✳❀ ❑✉st❡r✱ ❇✳❀ ✈❛♥ ❞❡r ❲✐❡❧❡✱ ❑✳❀ ▼❛r✐♥✱ ●✳
✼✷✱
❙t✉❞✳ ❙✉r❢✳ ❙❝✐✳ ❈❛t❛❧✳
✶✾✾✷✱
✹✸✕✺✺✳
✭✷✾✮ ❱❛ss✐❧②❡✈✱ ❨✳ ❇✳❀ ❑❤❛③♦✈❛✱ ❖✳ ❆✳❀ ◆✐❦♦❧❛❡✈❛✱ ◆✳ ◆✳
❏✳ ❊❧❡❝tr♦❛♥❛❧✳ ❈❤❡♠✳
✶✾✽✺✱ ✶✾✻✱
✶✷✼✕✶✹✹✳
✭✸✵✮ P♦♣♦✈✐➣✱ ❑✳ ❉✳❀ ▼❛r❦♦✈✐➣✱ ◆✳ ▼✳❀ ❚r✐♣❦♦✈✐➣✱ ❆✳ ❱✳❀ ❆❞➸✐➣✱ ❘✳ ❘✳
❏✳ ❊❧❡❝tr♦❛♥❛❧✳ ❈❤❡♠✳
✶✾✾✶✱ ✸✶✸✱ ✶✽✶✕✶✾✾✳ ✭✸✶✮ ❆❞❦✐♥s✱ ❍✳❀ ❇r♦❞❡r✐❝❦✱ ❆✳ ❊✳
✭✸✷✮ ▲❛✉❞❡r✱ ■✳
❏✳ ❆♠✳ ❈❤❡♠✳ ❙♦❝✳
❚r❛♥s✳ ❋❛r❛❞❛② ❙♦❝✳
✶✾✷✽✱ ✺✵✱ ✹✾✾✕✺✵✸✳
✶✾✹✽✱ ✹✹✱ ✼✷✾✕✼✸✺✳
✭✸✸✮ ▼❝❑❡♥♥❛✱ ❋✳ ❊✳❀ ❚❛rt❛r✱ ❍✳ ❱✳❀ ▲✐♥❣❛❢❡❧t❡r✱ ❊✳ ❈✳
✸✵
❏✳ ❆♠✳ ❈❤❡♠✳ ❙♦❝✳ ✶✾✺✸✱ ✼✺✱ ✻✵✹✕✻✵✼✳
ACS Paragon Plus Environment
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ACS Catalysis
✭✸✹✮ P♦✇❡❧❧✱ ❆✳ ❇✳❀ ❙t❛❤❧✱ ❙✳ ❙✳
❖r❣✳ ▲❡tt✳
✭✸✺✮ ❍✐❜❜✐tts✱ ❉✳ ❉✳❀ ◆❡✉r♦❝❦✱ ▼✳
✷✵✶✸✱ ✶✺✱ ✺✵✼✷✕✺✵✼✺✳
❏✳ ❈❛t❛❧✳
✷✵✶✸✱ ✷✾✾✱ ✷✻✶✕✷✼✶✳
✭✸✻✮ ❑r❡ss❡✱ ●✳❀ ❍❛❢♥❡r✱ ❏✳
P❤②s✳ ❘❡✈✳ ❇
✶✾✾✸✱ ✹✼✱ ✺✺✽✕✺✻✶✳
✭✸✼✮ ❑r❡ss❡✱ ●✳❀ ❍❛❢♥❡r✱ ❏✳
P❤②s✳ ❘❡✈✳ ❇
✶✾✾✹✱ ✹✾✱ ✶✹✷✺✶✕✶✹✷✻✾✳ ✶✾✾✻✱ ✺✹✱ ✶✶✶✻✾✕✶✶✶✽✻✳
✭✸✽✮ ❑r❡ss❡✱ ●✳❀ ❋✉rt❤♠ü❧❧❡r✱ ❏✳
P❤②s✳ ❘❡✈✳ ❇
✭✸✾✮ ❑r❡ss❡✱ ●✳❀ ❋✉rt❤♠ü❧❧❡r✱ ❏✳
❈♦♠♣✉t✳ ▼❛t❡r✳ ❙❝✐
✭✹✵✮ ▲❛rs❡♥✱ ❆✳ ❍✳❀
▼♦rt❡♥s❡♥✱ ❏✳ ❏✳❀
✶✾✾✻✱ ✻✱ ✶✺✕✺✵✳
❇❧♦♠q✈✐st✱ ❏✳❀
❈❛st❡❧❧✐✱ ■✳ ❊✳❀
❈❤r✐st❡♥s❡♥✱ ❘✳❀
❉✉➟❛❦✱ ▼✳❀ ❋r✐✐s✱ ❏✳❀ ●r♦✈❡s✱ ▼✳ ◆✳❀ ❍❛♠♠❡r✱ ❇✳❀ ❍❛r❣✉s✱ ❈✳❀ ❍❡r♠❡s✱ ❊✳ ❉✳❀ ❏❡♥✲ ♥✐♥❣s✱ P✳ ❈✳❀ ❏❡♥s❡♥✱ P✳ ❇✳❀ ❑❡r♠♦❞❡✱ ❏✳❀ ❑✐t❝❤✐♥✱ ❏✳ ❘✳❀ ❑♦❧s❜❥❡r❣✱ ❊✳ ▲✳❀ ❑✉❜❛❧✱ ❏✳❀ ❑❛❛s❜❥❡r❣✱ ❑✳❀ ▲②s❣❛❛r❞✱ ❙✳❀ ▼❛r♦♥ss♦♥✱ ❏✳ ❇✳❀ ▼❛①s♦♥✱ ❚✳❀ ❖❧s❡♥✱ ❚✳❀ P❛st❡✇❦❛✱ ▲✳❀ P❡✲ t❡rs♦♥✱ ❆✳❀ ❘♦st❣❛❛r❞✱ ❈✳❀ ❙❝❤✐øt③✱ ❏✳❀ ❙❝❤ütt✱ ❖✳❀ ❙tr❛♥❣❡✱ ▼✳❀ ❚❤②❣❡s❡♥✱ ❑✳❀ ❱❡❣❣❡✱ ❚✳❀ ❱✐❧❤❡❧♠s❡♥✱ ▲✳❀ ❲❛❧t❡r✱ ▼✳❀ ❩❡♥❣✱ ❩✳❀ ❏❛❝♦❜s❡♥✱ ❑✳ ❲✳
✷✾✱
❏✳ P❤②s✳✿ ❈♦♥❞❡♥s✳ ▼❛tt❡r
✷✵✶✼✱
✷✼✸✵✵✷✳
✭✹✶✮ P❡r❞❡✇✱ ❏✳ P✳❀ ❇✉r❦❡✱ ❑✳❀ ❊r♥③❡r❤♦❢✱ ▼✳
P❤②s✳ ❘❡✈✳ ▲❡tt✳
✶✾✾✻✱ ✼✼✱ ✸✽✻✺✕✸✽✻✽✳
✭✹✷✮ P❡r❞❡✇✱ ❏✳ P✳❀ ❇✉r❦❡✱ ❑✳❀ ❊r♥③❡r❤♦❢✱ ▼✳
P❤②s✳ ❘❡✈✳ ▲❡tt✳
✶✾✾✼✱ ✼✽✱ ✶✸✾✻✳
✭✹✸✮ ❍❡②❞✱ ❏✳❀ ❙❝✉s❡r✐❛✱ ●✳ ❊✳
❏✳ ❈❤❡♠✳ P❤②s✳
✷✵✵✹✱ ✶✷✶✱ ✶✶✽✼✕✶✶✾✷✳
✭✹✹✮ ❍❡②❞✱ ❏✳❀ P❡r❛❧t❛✱ ❏✳ ❊✳❀ ❙❝✉s❡r✐❛✱ ●✳ ❊✳❀ ▼❛rt✐♥✱ ❘✳ ▲✳
❏✳ ❈❤❡♠✳ P❤②s✳
✷✵✵✺✱ ✶✷✸✱
✶✼✹✶✵✶✳
✭✹✺✮ ❍❡②❞❡♥✱ ❆✳❀ ❇❡❧❧✱ ❆✳ ❚✳❀ ❑❡✐❧✱ ❋✳ ❏✳
❏✳ ❈❤❡♠✳ P❤②s✳
✭✹✻✮ ■③♠❛②❧♦✈✱ ❆✳ ❋✳❀ ❙❝✉s❡r✐❛✱ ●✳ ❊✳❀ ❋r✐s❝❤✱ ▼✳ ❏✳
✭✹✼✮ ❍❡②❞✱ ❏✳❀ ❙❝✉s❡r✐❛✱ ●✳ ❊✳❀ ❊r♥③❡r❤♦❢✱ ▼✳
✷✵✵✺✱ ✶✷✸✱ ✷✷✹✶✵✶✳
❏✳ ❈❤❡♠✳ P❤②s✳
❏✳ ❈❤❡♠✳ P❤②s✳
✸✶
ACS Paragon Plus Environment
✷✵✵✻✱ ✶✷✺✱ ✵✕✽✳
✷✵✵✻✱ ✶✷✹✱ ✷✶✾✾✵✻✳
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Page 32 of 35
✭✹✽✮ ❑r✉❦❛✉✱ ❆✳ ❱✳❀ ❱②❞r♦✈✱ ❖✳ ❆✳❀ ■③♠❛②❧♦✈✱ ❆✳ ❋✳❀ ❙❝✉s❡r✐❛✱ ●✳ ❊✳
✶✷✺✱
❏✳ ❈❤❡♠✳ P❤②s✳
✷✵✵✻✱
✷✷✹✶✵✻✳
✭✹✾✮ ●r✐♠♠❡✱ ❙✳❀ ❆♥t♦♥②✱ ❏✳❀ ❊❤r❧✐❝❤✱ ❙✳❀ ❑r✐❡❣✱ ❍✳
✭✺✵✮ ●r✐♠♠❡✱ ❙✳❀ ❊❤r❧✐❝❤✱ ❙✳❀ ●♦❡r✐❣❦✱ ▲✳
✭✺✶✮ ▼♦❡❧❧♠❛♥♥✱ ❏✳❀ ●r✐♠♠❡✱ ❙✳
❏✳ ❈❤❡♠✳ P❤②s✳
❏✳ ❈♦♠♣✉t✳ ❈❤❡♠✳
❏✳ P❤②s✳ ❈❤❡♠✳ ❈
✷✵✶✵✱ ✶✸✷✱ ✶✺✹✶✵✹✳
✷✵✶✶✱ ✶✹✺✻✕✶✹✻✺✳
✷✵✶✹✱ ✶✶✽✱ ✼✻✶✺✕✼✻✷✶✳
✭✺✷✮ ●✐❧✱ ❆✳❀ ❈❧♦t❡t✱ ❆✳❀ ❘✐❝❛rt✱ ❏✳ ▼✳❀ ❑r❡ss❡✱ ●✳❀ ●❛r❝í❛✲❍❡r♥á♥❞❡③✱ ▼✳❀ ❘ös❝❤✱ ◆✳❀ ❙❛✉t❡t✱ P✳
❙✉r❢✳ ❙❝✐✳
✭✺✸✮ ❩❡♥❣✱ ❩✳❀ ●r❡❡❧❡②✱ ❏✳
✷✵✵✸✱ ✺✸✵✱ ✼✶✕✽✻✳ ❈❛t❛❧✳ ❈♦♠♠✉♥✳
✷✵✶✹✱ ✺✷✱ ✼✽✕✽✸✳
✭✺✹✮ ❩❤❛♦✱ ❩✳ ❏✳❀ ▲✐✱ ❩✳❀ ❈✉✐✱ ❨✳❀ ❩❤✉✱ ❍✳❀ ❙❝❤♥❡✐❞❡r✱ ❲✳ ❋✳❀ ❉❡❧❣❛ss✱ ❲✳ ◆✳❀ ❘✐❜❡✐r♦✱ ❋✳❀ ●r❡❡❧❡②✱ ❏✳
❏✳ ❈❛t❛❧✳
✷✵✶✼✱ ✸✹✺✱ ✶✺✼✕✶✻✾✳
✭✺✺✮ ●❛❧❡✱ ❲✳❀ ❚♦t❡♠❡✐❡r✱ ❚✳
❙♠✐t❤❡❧❧s ▼❡t❛❧s ❘❡❢❡r❡♥❝❡ ❇♦♦❦ ❀
✭✺✻✮ ▼♦♥❦❤♦rst✱ ❍✳ ❏✳❀ P❛❝❦✱ ❏✳ ❉✳
❊❧s❡✈✐❡r ❙❝✐❡♥❝❡✱ ✷✵✵✸✳
✶✾✼✻✱ ✶✸✱ ✺✶✽✽✕✺✶✾✷✳
P❤②s✳ ❘❡✈✳ ❇
✭✺✼✮ ●✉♥❝❡❧❡r✱ ❉✳❀ ▲❡t❝❤✇♦rt❤✲❲❡❛✈❡r✱ ❑✳❀ ❙✉♥❞❛r❛r❛♠❛♥✱ ❘✳❀ ❙❝❤✇❛r③✱ ❑✳ ❆✳❀ ❆r✐❛s✱ ❚✳ ❆✳
▼♦❞❡❧❧✳ ❙✐♠✉❧✳ ▼❛t❡r✳ ❙❝✐✳ ❊♥❣✳
✷✵✶✸✱ ✷✶✱ ✵✼✹✵✵✺✳
✭✺✽✮ ▼❛t❤❡✇✱ ❑✳❀ ❙✉♥❞❛r❛r❛♠❛♥✱ ❘✳❀ ▲❡t❝❤✇♦rt❤✲❲❡❛✈❡r✱ ❑✳❀ ❆r✐❛s✱ ❚✳ ❆✳❀ ❍❡♥♥✐❣✱ ❘✳ ●✳
❏✳ ❈❤❡♠✳ P❤②s✳ ✭✺✾✮ ▼❛t❤❡✇✱ ❑✳❀ ♣❧❛♥❡✲✇❛✈❡
✷✵✶✹✱ ✶✹✵ ✳
❍❡♥♥✐❣✱ ❘✳ ●✳ ■♠♣❧✐❝✐t s❡❧❢✲❝♦♥s✐st❡♥t ❞❡s❝r✐♣t✐♦♥ ♦❢ ❡❧❡❝tr♦❧②t❡ ✐♥
❞❡♥s✐t②✲❢✉♥❝t✐♦♥❛❧
t❤❡♦r②✳
✷✵✶✻❀
❤tt♣✿✴✴❛r①✐✈✳♦r❣✴❛❜s✴✶✻✵✶✳✵✸✸✹✻ ✱
❛r❳✐✈✿✶✻✵✶✳✵✸✸✹✻✳ ❛r❳✐✈✳♦r❣ ❡✲Pr✐♥t ❛r❝❤✐✈❡✳
✭✻✵✮ ❏ó♥ss♦♥✱ ❍✳❀ ▼✐❧❧s✱ ●✳❀ ❏❛❝♦❜s❡♥✱ ❑✳ ❲✳ ■♥
❞❡♥s❡❞ P❤❛s❡ ❙✐♠✉❧❛t✐♦♥s ❀
❈❧❛ss✐❝❛❧ ❛♥❞ ◗✉❛♥t✉♠ ❉②♥❛♠✐❝s ✐♥ ❈♦♥✲
❇❡r♥❡✱ ❇✳ ❏✳✱ ❈✐❝❝♦tt✐✱ ●✳✱ ❈♦❦❡r✱ ❉✳ ❋✳✱ ❊❞s✳❀ ❲♦r❧❞ ❙❝✐❡♥✲
t✐✜❝✱ ✶✾✾✽❀ ❈❤❛♣t❡r ✶✻✱ ♣♣ ✸✽✺✕✹✵✹✳
✸✷
ACS Paragon Plus Environment
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ACS Catalysis
✭✻✶✮ ❍❡♥❦❡❧♠❛♥✱ ●✳❀ ❏ó♥ss♦♥✱ ❍✳
❏✳ ❈❤❡♠✳ P❤②s✳
✭✻✷✮ ❙❤❡♣♣❛r❞✱ ❉✳❀ ❚❡rr❡❧❧✱ ❘✳❀ ❍❡♥❦❡❧♠❛♥✱ ●✳
✭✻✸✮ ❍❡♥❦❡❧♠❛♥✱ ●✳❀ ❏ó♥ss♦♥✱ ❍✳
✭✻✹✮ ❑äst♥❡r✱ ❏✳❀ ❙❤❡r✇♦♦❞✱ P✳
❏✳ ❈❤❡♠✳ P❤②s✳
❏✳ ❈❤❡♠✳ P❤②s✳
❏✳ ❈❤❡♠✳ P❤②s✳
✷✵✵✵✱ ✶✶✸✱ ✾✾✼✽✕✾✾✽✺✳ ✷✵✵✽✱ ✶✷✽✱ ✶✸✹✶✵✻✳
✶✾✾✾✱ ✶✶✶✱ ✼✵✶✵✳
✷✵✵✽✱ ✶✷✽✱ ✵✶✹✶✵✻✳
✭✻✺✮ ❋r✐s❝❤✱ ▼✳ ❏✳❀ ❚r✉❝❦s✱ ●✳ ❲✳❀ ❙❝❤❧❡❣❡❧✱ ❍✳ ❇✳❀ ❙❝✉s❡r✐❛✱ ●✳ ❊✳❀ ❘♦❜❜✱ ▼✳ ❆✳❀ ❈❤❡❡s❡✲ ♠❛♥✱ ❏✳ ❘✳❀ ❙❝❛❧♠❛♥✐✱ ●✳❀ ❇❛r♦♥❡✱ ❱✳❀ ▼❡♥♥✉❝❝✐✱ ❇✳❀ P❡t❡rss♦♥✱ ●✳ ❆✳❀ ◆❛❦❛ts✉❥✐✱ ❍✳❀ ❈❛r✐❝❛t♦✱ ▼✳❀ ▲✐✱ ❳✳❀ ❍r❛t❝❤✐❛♥✱ ❍✳ P✳❀ ■③♠❛②❧♦✈✱ ❆✳ ❋✳❀ ❇❧♦✐♥♦✱ ❏✳❀ ❩❤❡♥❣✱ ●✳❀ ❙♦♥♥❡♥✲ ❜❡r❣✱ ❏✳ ▲✳❀ ❍❛❞❛✱ ▼✳❀ ❊❤❛r❛✱ ▼✳❀ ❚♦②♦t❛✱ ❑✳❀ ❋✉❦✉❞❛✱ ❘✳❀ ❍❛s❡❣❛✇❛✱ ❏✳❀ ■s❤✐❞❛✱ ▼✳❀ ◆❛❦❛❥✐♠❛✱ ❚✳❀ ❍♦♥❞❛✱ ❨✳❀ ❑✐t❛♦✱ ❖✳❀ ◆❛❦❛✐✱ ❍✳❀ ❱r❡✈❡♥✱ ❚✳❀ ▼♦♥t❣♦♠❡r② ❏r✳✱ ❏✳ ❆✳❀ P❡r❛❧t❛✱ ❏✳ ❊✳❀ ❖❣❧✐❛r♦✱ ❋✳❀ ❇❡❛r♣❛r❦✱ ▼✳❀ ❍❡②❞✱ ❏✳ ❏✳❀ ❇r♦t❤❡rs✱ ❊✳❀ ❑✉❞✐♥✱ ❑✳ ◆✳❀ ❙t❛r♦✈❡r♦✈✱ ❱✳ ◆✳❀ ❑❡✐t❤✱ ❚✳❀ ❑♦❜❛②❛s❤✐✱ ❘✳❀ ◆♦r♠❛♥❞✱ ❏✳❀ ❘❛❣❤❛✈❛❝❤❛r✐✱ ❑✳❀ ❘❡♥✲ ❞❡❧❧✱ ❆✳❀ ❇✉r❛♥t✱ ❏✳ ❈✳❀ ■②❡♥❣❛r✱ ❙✳ ❙✳❀ ❚♦♠❛s✐✱ ❏✳❀ ❈♦ss✐✱ ▼✳❀ ❘❡❣❛✱ ◆✳❀ ▼✐❧❧❛♠✱ ❏✳ ▼✳❀ ❑❧❡♥❡✱ ▼✳❀ ❑♥♦①✱ ❏✳ ❊✳❀ ❈r♦ss✱ ❏✳ ❇✳❀ ❇❛❦❦❡♥✱ ❱✳❀ ❆❞❛♠♦✱ ❈✳❀ ❏❛r❛♠✐❧❧♦✱ ❏✳❀ ●♦♠✲ ♣❡rts✱ ❘✳❀ ❙tr❛t♠❛♥♥✱ ❘✳ ❊✳❀ ❨❛③②❡✈✱ ❖✳❀ ❆✉st✐♥✱ ❆✳ ❏✳❀ ❈❛♠♠✐✱ ❘✳❀ P♦♠❡❧❧✐✱ ❈✳❀ ❖❝❤t❡r✲ s❦✐✱ ❏✳ ❲✳❀ ▼❛rt✐♥✱ ❘✳ ▲✳❀ ▼♦r♦❦✉♠❛✱ ❑✳❀ ❩❛❦r③❡✇s❦✐✱ ❱✳ ●✳❀ ❱♦t❤✱ ●✳ ❆✳❀ ❙❛❧✈❛❞♦r✱ P✳❀ ❉❛♥♥❡♥❜❡r❣✱ ❏✳ ❏✳❀ ❉❛♣♣r✐❝❤✱ ❙✳❀ ❉❛♥✐❡❧s✱ ❆✳ ❉✳❀ ❋❛r❦❛s✱ ❖✳❀ ❋♦r❡s♠❛♥✱ ❏✳ ❇✳❀ ❖r✲ t✐③✱ ❏✳ ❱✳❀ ❈✐♦s❧♦✇s❦✐✱ ❏✳❀ ❋♦①✱ ❉✳ ❏✳ ●❛✉ss✐❛♥⑦✵✾ ❘❡✈✐s✐♦♥ ❉✳✵✶✳ ●❛✉ss✐❛♥ ■♥❝✳ ❲❛❧❧✐♥❣✲ ❢♦r❞ ❈❚ ✷✵✶✻✳
✭✻✻✮ ❉✉♥♥✐♥❣ ❏r✱ ❚✳ ❍✳
❏✳ ❈❤❡♠✳ P❤②s✳
✶✾✽✾✱ ✾✵✱ ✶✵✵✼✳
✭✻✼✮ ▼❛r❡♥✐❝❤✱ ❆✳ ❱✳❀ ❈r❛♠❡r✱ ❈✳ ❏✳❀ ❚r✉❤❧❛r✱ ❉✳ ●✳
❏✳ P❤②s✳ ❈❤❡♠✳ ❇
✷✵✵✾✱ ✶✶✸✱ ✻✸✼✽✕✻✸✾✻✳
✭✻✽✮ ❍❡r♠❡s✱ ❊✳ ❉✳❀ ❏❛♥❡s✱ ❆✳ ◆✳❀ ❙❝❤♠✐❞t✱ ❏✳ ❘✳ ✉♥♣✉❜❧✐s❤❡❞ ✇♦r❦✳
✭✻✾✮ ❍❛♥s❡♥✱ ❍✳ ❆✳❀ ❱✐s✇❛♥❛t❤❛♥✱ ❱✳❀ ◆ørs❦♦✈✱ ❏✳ ❑✳
❏✳ P❤②s✳ ❈❤❡♠✳ ❈
✷✵✶✹✱ ✶✶✽✱ ✻✼✵✻✕
✻✼✶✽✳
✭✼✵✮ ❙✐❧❜❛✉❣❤✱ ❚✳ ▲✳❀ ❈❛♠♣❜❡❧❧✱ ❈✳ ❚✳
❏✳ P❤②s✳ ❈❤❡♠✳ ❈ ✸✸
✷✵✶✻✱ ✷✺✶✻✶✕✷✺✶✼✷✳
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
✭✼✶✮ ❈❛♠♣❜❡❧❧✱ ❈✳ ❚✳
❚♦♣✳ ❈❛t❛❧✳
Page 34 of 35
✶✾✾✹✱ ✶✱ ✸✺✸✕✸✻✻✳
✭✼✷✮ ❙t❡❣❡❧♠❛♥♥✱ ❈✳❀ ❆♥❞r❡❛s❡♥✱ ❆✳❀ ❈❛♠♣❜❡❧❧✱ ❈✳ ❚✳
❏✳ ❆♠✳ ❈❤❡♠✳ ❙♦❝✳
✽✵✽✷✳
✭✼✸✮ ❈❛♠♣❜❡❧❧✱ ❈✳ ❚✳
❆❈❙ ❈❛t❛❧✳
✷✵✶✼✱ ✼✱ ✷✼✼✵✕✷✼✼✾✳
✸✹
ACS Paragon Plus Environment
✷✵✵✾✱ ✶✸✶✱ ✽✵✼✼✕
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ACS Catalysis
RCH2 OH + O2 + 2CH3 O – −−→ RCHOOCH3 + CH3 OH + 2 OH –
✸✺
ACS Paragon Plus Environment
