Catalytic reduction of CO2 over Cu-based catalysts can produce various carbon-based products such as the critical intermediate CO, yet significant challenges remain in shedding light on the underlying mechanisms. Here, we develop a modified triple-stage quadrupole mass spectrometer to monitor the reduction of CO2 to CO in the gas phase online. Our experimental observations reveal that the coordinated H2O on Cu(I)-based catalysts promotes CO2 adsorption and reduction to CO, and the resulting efficiencies are two orders of magnitude higher than those without H2O. Isotope-labeling studies render compelling evidence that the O atom in produced CO originates from the coordinated H2O on catalysts, rather than CO2 itself. Combining experimental observations and computational calculations with density functional theory, we propose a detailed reaction mechanism of CO2 reduction to CO over Cu(I)-based catalysts with coordinated H2O. This study offers an effective method to reveal the vital roles of H2O in promoting metal catalysts to CO2 reduction.
A plasma-based source named focusing plasma desorption/ionization (FPDI) is described, which applies a high direct current voltage between a metal wire inside a polymeric hollow truncated cone and a piece of a one-sided coated conducting paper substrate. The conducting paper acts as both the counter electrode and the sample carrier. Upon the generation of a visible plasma beam, it would directly ionize the samples spotted on the conducting paper substrate or located around the plasma beam. The signal intensity of target analytes in mass spectrometric analysis is dependent highly on whether the conducting paper substrate is grounded or not, the type of conducting paper substrate, the inside diameter of the polymeric hollow truncated cone tip, the metal wire tip-topolymer tip distance, the polymer tip-to-paper substrate distance, the applied voltage, and the helium flow rate. Based on the experimental observation, a plausible mechanism is proposed for the generation of the plasma beam from FPDI. Compared to the available low-temperature plasma, flowing atmospheric-pressure afterglow, and helium plasma ionization sources, FPDI has demonstrated higher sensitivity and better compatibility with commercial mass spectrometers without any extra power supplies. As a proof of concept, FPDI coupled with a mass spectrometer has also been applied for the discrimination of different brands of gasoline and determination of solid tablets and pesticides with limits of detection in the range of 2.2 to 30.7 ng mL −1 .
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