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Volumn 129, Issue 41, 2007, Pages 12521-12530

Hydrogen generation from weak acids: Electrochemical and computational studies of a diiron hydrogenase mimic

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; COMPUTATIONAL METHODS; ELECTROCHEMISTRY; ENZYME KINETICS; HYDROGEN PRODUCTION;

EID: 35349012651     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja073886g     Document Type: Article
Times cited : (334)

References (77)
  • 1
  • 27
    • 30744464865 scopus 로고    scopus 로고
    • See also mononuclear Ni catalysts: Wilson, A. D.; Newell, R. H.; McNevin, M. J.; Muckerman, J. T.; Rakowski DuBois, M.; DuBois, D. L. J. Am. Chem. Soc. 2006, 128, 358-366.
    • See also mononuclear Ni catalysts: Wilson, A. D.; Newell, R. H.; McNevin, M. J.; Muckerman, J. T.; Rakowski DuBois, M.; DuBois, D. L. J. Am. Chem. Soc. 2006, 128, 358-366.
  • 31
    • 35348999955 scopus 로고    scopus 로고
    • See ref 5 for further discussion of the diiron structure in the enzyme
    • See ref 5 for further discussion of the diiron structure in the enzyme.
  • 42
    • 35348962459 scopus 로고    scopus 로고
    • 24 The structural change must be reversible to account for the overall electrochemical reversibility that is observed.
    • 24 The structural change must be reversible to account for the overall electrochemical reversibility that is observed.
  • 47
    • 35349016203 scopus 로고    scopus 로고
    • For very large distortions of the positive ion away from the vibrational amplitudes of the neutral molecule, adiabatic ionization intensity may not be observed and the onset of ionization intensity represents an upper bound to the true adiabatic ionization energy
    • For very large distortions of the positive ion away from the vibrational amplitudes of the neutral molecule, adiabatic ionization intensity may not be observed and the onset of ionization intensity represents an upper bound to the true adiabatic ionization energy.
  • 53
    • 28044448515 scopus 로고    scopus 로고
    • Although calculations show that reaction of 6H2- with AcOH is facile, it has been reported that a μ-H in a Fe-only hydrogenase model with two Fe(II) centers is experimentally unreactive to HOTf or H(OEt 2)2BArF4 in contrast to its terminal hydride isomer: van der Vlugt, J. I, Rauchfuss, T. B, Whaley, C. M, Wilson, S. R. J. Am. Chem. Soc. 2005, 127, 16012-16013
    • 4 in contrast to its terminal hydride isomer: van der Vlugt, J. I.; Rauchfuss, T. B.; Whaley, C. M.; Wilson, S. R. J. Am. Chem. Soc. 2005, 127, 16012-16013.
  • 59
    • 35349011486 scopus 로고    scopus 로고
    • Compound 6 is not stable in the presence of acetate alone with decomposition occurring over a period of a few minutes. The presence of acid slows the decomposition. The data shown in Figure 4 were obtained by adding 10 mM acetic acid to the solution containing 0.100 M acetate. Then the catalyst was added, and the voltammogram was recorded. The acetic acid concentration was then increased to 50 mM. We suspect that the smaller peak height for catalyst reduction seen with 50 mM is due to some decomposition that occurred between recording the 10 and 50 mM voltammograms
    • Compound 6 is not stable in the presence of acetate alone with decomposition occurring over a period of a few minutes. The presence of acid slows the decomposition. The data shown in Figure 4 were obtained by adding 10 mM acetic acid to the solution containing 0.100 M acetate. Then the catalyst was added, and the voltammogram was recorded. The acetic acid concentration was then increased to 50 mM. We suspect that the smaller peak height for catalyst reduction seen with 50 mM is due to some decomposition that occurred between recording the 10 and 50 mM voltammograms.
  • 61
    • 35348975950 scopus 로고    scopus 로고
    • The results of simulations reported in Figure 5 are for the catalytic peak current only. As seen in Figure 6, another feature of the data is that the peak potential moves in the positive direction as the acid strength increases. The simulated peak potentials, however, are almost independent of acid strength, based on reactions 3 through 8. There are various other reactions that will cause a potential shift similar to that seen in Figure 6. For example, formation of a hydrogen-bonded complex between 6H- and A, 6H-·A, or between 6H2- and HA (6H2--HA) will have the effect of shifting the peak if one assumes that the formation constants correlate with acid strength. As there are many such possible reactions, and perhaps other types as well, we have refrained from attempting to fit this potential shift
    • 2--HA) will have the effect of shifting the peak if one assumes that the formation constants correlate with acid strength. As there are many such possible reactions, and perhaps other types as well, we have refrained from attempting to fit this potential shift.
  • 68
    • 33845883717 scopus 로고    scopus 로고
    • Vrije Universiteit, Amsterdam, The Netherlands
    • ADF2006.01b, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, 2006, http://www.scm.com.
    • (2006) 01b, SCM, Theoretical Chemistry
    • ADF1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.