Mechanistic insights into the reduction of carbon dioxide on tin and bismuth electrodes using in situ infrared spectroscopy and differential electrochemical mass spectrometry.

摘要

The factors that govern the electrochemical reduction of CO2 on Sn and Bi electrodes were studied. Chapter 1 discusses the relevant literature, the merits of reducing CO2 electrochemically, the ways in which CO2 reduction systems are characterized, and the outstanding challenges. Chapter 2 describes the design and construction of a differential electrochemical mass spectrometry (DEMS) system that can be used to probe the products of electrochemical reactions in situ and in real time.;In Chapter 3, the role of surface oxides and hydroxides in the reduction of CO2 on Sn electrodes is discussed. in situ attenuated total reflectance infrared (ATR-IR) spectroscopy is the main analytical technique by which the system was studied. Peaks that are attributed to a surface-bound Sn carbonate are present under conditions that are suitable for CO2 reduction. A strong correlation between the presence of these peaks and catalytic activity exists with respect to the applied potential, the pH of the electrolyte, and the surface condition of the electrode. X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and electrochemical analysis were also used characterize the catalysts. Based on these data, a mechanism for the reduction of CO2 on Sn cathodes is proposed.;The roles of morphology and surface oxide presence in the reduction of CO2 on Bi cathodes are discussed in Chapter 4. ATR-IR spectroscopy, XPS, EDX, SEM, cyclic voltammetry, and preparative electrolysis are used to demonstrate that, unlike Sn, Bi electrodes do not possess oxide-dependent catalytic behavior. Instead, it is shown that Bi electrodes are highly sensitive to morphological changes in surface structure, and that surface roughness is detrimental to HCOO-- production from CO2. Finally, it is shown that oxide-derived Bi, formed by the in situ reduction of Bi2O3 nanoparticles at cathodic potentials, can reduce CO2 to HCOO-- at near unit efficiencies at --1.55 V vs. Ag/AgCl.