FTIR spectroscopic investigation of pyruvate electroreduction on copper in alkaline medium — On the mechanistic aspects

Martin, Cedric; Hahn, F.; Servat, Karine; Huser, Hervé; Tito, Duarte Novaes; Kalaji, M.; Kokoh, K. Boniface

doi:10.1139/v08-137

Cited by 1 publication

(2 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A recent report by Calvo et al also demonstrated that the Orito reaction can be successfully performed electrocatalytically using an aqueous solvent . In situ FTIR studies of pyruvic acid reduction at copper electrodes have also indicated that pyruvate can be reduced to lactate via a surface-adsorbed intermediate . We recently reported an in situ SERS study of the racemic hydrogenation of several α-ketoesters at Pt surfaces under gas-phase and electrochemical conditions .…”

Section: Introductionmentioning

confidence: 80%

“…48 In situ FTIR studies of pyruvic acid reduction at copper electrodes have also indicated that pyruvate can be reduced to lactate via a surface-adsorbed intermediate. 49 We recently reported an in situ SERS study of the racemic hydrogenation of several α-ketoesters at Pt surfaces under gasphase and electrochemical conditions. 50 In that study, we confirmed that under hydrogenation conditions dimeric and polymeric derivatives of the substrate (in that case EP) appeared to play no part in the surface reaction.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Enantioselective Hydrogenation of α-Ketoesters: An in Situ Surface-Enhanced Raman Spectroscopy (SERS) Study

et al. 2011

View full text Add to dashboard Cite

Adsorption of ethyl pyruvate (EP) and methyl pyruvate (MP) has been studied on a SERS-active platinum electrode. Gas-phase experiments under a hydrogen atmosphere show that decarbonylation to form adsorbed CO together with formation of a half-hydrogenated state of MP/EP are the dominant surface reaction pathways occurring under these conditions. Similar findings were obtained using a hydrogen-evolving platinum electrode under potentiostatic control in 0.1 M aqueous sulfuric acid containing EP or MP. DFT calculations have been used to support the assignment of vibrational bands in the SERS obtained from the half-hydrogenated state intermediate. At hydrogen evolution potentials and using concentrations of MP and EP < 0.02M, adsorbed hydrogen adatoms were detected. At higher EP concentrations, hydrogen-atom formation was inhibited by the greater surface coverages of the half-hydrogenated state of EP/MP and to a lesser extent adsorbed CO derived from decarbonylation side reactions. Addition of the chiral modifier cinchonidine (CD) to the acidic electrolyte under conditions of hydrogen evolution resulted in significantly less CO production and a reduction in the intensity of all SERS peaks associated with the half-hydrogenated state. Most importantly, however, the presence of surface hydrogen, previously absent on the unmodified surface, was always observed irrespective of the EP concentration. The significance of this result in relation to the question of the origin of rate enhancement during heterogeneously catalyzed enantioselective hydrogenation of α-ketoesters is discussed.

show abstract

Section: Introductionmentioning

confidence: 80%