Siwek Hanna, Lukaszewski Mariusz, Czerwiński Andrzej
Industrial Chemistry Research Institute, Rydygiera 8, 01-793, Warsaw, Poland.
Phys Chem Chem Phys. 2008 Jul 7;10(25):3752-65. doi: 10.1039/b718286b. Epub 2008 May 22.
CO(2) reduction and CO adsorption on noble metals (Pt, Rh, Pd) and their alloys (Pt-Rh, Pd-Pt, Pd-Rh, Pd-Pt-Rh) prepared as thin rough deposits have been studied by chronoamperometry (CA), cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). The influence of alloy surface composition on the values of surface coverage, eps (electron per site) and potential of the oxidation of CO(2) reduction and CO adsorption products is shown. The oxidation of the adsorbate on Pt-Rh alloys proceeds more easily (at lower potentials) than on pure metals. On the other hand, in the case of Pd-Pt and Pd-Rh alloys the adsorbate oxidation is more difficult and requires higher potentials than on Pt or Rh. The analysis of the EQCM signal is presented for the case of adsorption and oxidation of carbon oxide adsorption products on the electrodes studied. The comparison of adsorption parameters and the EQCM response obtained for platinum group metals and alloys leads to the conclusion that reduced CO(2) cannot be totally identified with adsorbed CO.
通过计时电流法(CA)、循环伏安法(CV)和电化学石英晶体微天平(EQCM)研究了作为薄粗糙沉积物制备的贵金属(Pt、Rh、Pd)及其合金(Pt-Rh、Pd-Pt、Pd-Rh、Pd-Pt-Rh)上的CO₂还原和CO吸附。展示了合金表面组成对CO₂还原和CO吸附产物的表面覆盖度值、ε(每个位点的电子数)以及氧化电位的影响。Pt-Rh合金上吸附物的氧化比在纯金属上更容易(在更低电位下)进行。另一方面,对于Pd-Pt和Pd-Rh合金,吸附物氧化更困难,并且比在Pt或Rh上需要更高的电位。针对所研究电极上碳氧化物吸附产物的吸附和氧化情况给出了EQCM信号分析。对铂族金属及其合金获得的吸附参数和EQCM响应进行比较得出结论:还原的CO₂不能完全等同于吸附的CO。