메뉴 건너뛰기




Volumn 7, Issue 2, 2017, Pages 1330-1339

Elucidating the Key Role of pH on Light-Driven Hydrogen Evolution by a Molecular Cobalt Catalyst

Author keywords

cobaloxime; hydrogen; photocatalysis; time resolved spectroscopy; water splitting

Indexed keywords

ASCORBIC ACID; CATALYSIS; CATALYSTS; HYDROGEN; LASER SPECTROSCOPY; PHOTOCATALYSIS; PHOTOSENSITIZERS; SOLUTIONS;

EID: 85011845590     PISSN: None     EISSN: 21555435     Source Type: Journal    
DOI: 10.1021/acscatal.6b03087     Document Type: Article
Times cited : (80)

References (87)
  • 2
    • 67849128456 scopus 로고    scopus 로고
    • Gray, H. B. Nat. Chem. 2009, 1, 7 10.1038/nchem.141
    • (2009) Nat. Chem. , vol.1 , pp. 7
    • Gray, H.B.1
  • 54
    • 33845556505 scopus 로고
    • Creutz, C. Inorg. Chem. 1981, 20, 4449-4452 10.1021/ic50226a088
    • (1981) Inorg. Chem. , vol.20 , pp. 4449-4452
    • Creutz, C.1
  • 57
    • 85011828395 scopus 로고    scopus 로고
    • note
    • 52
  • 60
    • 85011828400 scopus 로고    scopus 로고
    • note
    • 61 which makes the correlation reasonably acceptable.
  • 62
    • 85011885273 scopus 로고    scopus 로고
    • note
    • 64,65
  • 68
    • 85011877394 scopus 로고    scopus 로고
    • note
    • Subsequent reduction and protonation of the Co(III)-H species are expected to promote hydrogen evolution; see, for example, refs 69 and 70.
  • 75
    • 85011885316 scopus 로고    scopus 로고
    • note
    • obst).
  • 77
    • 85011813592 scopus 로고    scopus 로고
    • note
    • An alternative, stepwise PT-ET mechanism can be clearly ruled out, since it would require protonation of a Co(II) moiety, which is extremely unlikely.
  • 80
    • 85011888543 scopus 로고    scopus 로고
    • note
    • It should be stressed that a straightforward correlation between the hydrogen-evolving activity and the pH is meaningful only in terms of initial rate or maximum TOF, being directly related to the quantum yield of the photoreaction (which is based on the assumption that the kinetic of hydrogen evolution is appreciably dependent on the absorbed photons only), while other parameters, such as the turnover number (TON), are potentially affected by other external variables (rather than absorbed light only).
  • 84
    • 85011928905 scopus 로고    scopus 로고
    • note
    • 56 and Co(III)-H species are likely to make process i rate-determining. Within this hypothesis, the sequence of processes i-iii is thus expected to be overall weakly dependent on pH. The fact that the pH dependence of the photocatalysis at pH >5 is substantially compatible with the pH dependence of the first PCET process (eqs 9 and 10) seems to be consistent with this assumption.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.