Electrochemical Mass Spectrometry: Evolution of the Cell Setup for On‐Line Investigation of Products and Screening of Electrocatalysts for Carbon Dioxide Reduction

Abstract

One of the most important current topics in the renewable and sustainable energy scenario is the CO2 electro‐reduction reaction (CO2RR), which is an alternative and important route for its conversion into various high value‐added chemicals, therefore making up a CO2 recycling process. Despite its importance and the works already developed in this field, many challenges still need to be overcome for CO2RR to reach high values of efficiency and selectivity. This is even more challenging considering that this reaction occurs with the transfer of several electrons, making the investigation and elucidation of the reaction mechanism a real need. Thus, several characterization techniques have been employed, and specially, the on‐line Electrochemical Mass Spectrometry (EC‐MS) technique emerges as a powerful tool, thus making possible to improve the understanding of reaction pathways, through the identification of products and intermediaries, and allowing the screening of electrocatalyst potentials for CO2RR. Herein, we present the evolution of adaptations of general electrochemical cell designs for the study of the CO2RR.

In situ characterizations for aqueous rechargeable zinc batteries

“…Different from the other in situ characterizations, DEMS is a mass-resolved technique with high accuracy and sensitivity in investigating the products, intermediates, and reaction pathways from various electrochemical processes. [142][143][144] For regular DEMS experiments set up (Figure 12a), the main chamber is generated by the connection of the first and second chambers, the quadrupole mass spectrometer system is located at the main chamber, the electrochemical cell was connected to the first chamber, operated by the differential pumping mode. MS cyclic voltammograms are obtained by recording the ion current of a specific species of interest and the Faradaic electrode current simultaneously during a potential scan.…”

“…MS cyclic voltammograms are obtained by recording the ion current of a specific species of interest and the Faradaic electrode current simultaneously during a potential scan. [145,147] In most cases of ARZBs, the DEMSbased data is an essential parameter in evaluating the effectiveness of the modification of the zinc anode. [148] DEMS has been applied to quantify the H 2 evolution rates of the zinc anode, which was caused by the side reaction of HER.…”

“…Reproduced with permission: Copyright 2022, John Wiley and Sons. [ 145 ] (b) In situ DEMS profiles displaying released H 2 gas during the first cycle for LMO//Cu@Zn and LMO//MGA@Zn (d) batteries. Reproduced with permission: Copyright 2022, John Wiley and Sons.…”

Perovskite oxides as an opportunity to systematically study the Electrooxidation of alcohols and Polyols on materials based on abundant elements: Learning from the experience using pure metals and metallic oxides in (Electro-)catalysis

“…If it is still not enough, NMR (nuclear magnetic resonance) analysis can render useful information, but always combined with at least one of the techniques mentioned before 217 . Besides, if the reaction generates volatile products, DEMS (Differential electrochemical mass spectrometry) experiments can identify and quantify the products in real time 218,219 . At least to our knowledge, apart from the recent publication of some of us 220 , there is not many articles studying the electrooxidation of organic molecules in perovskites oxides using in situ techniques to unravel the main reaction pathways of the reaction.…”

Perovskite oxides as an opportunity to systematically study the Electrooxidation of alcohols and Polyols on materials based on abundant elements: Learning from the experience using pure metals and metallic oxides in (Electro-)catalysis

“…If it is still not enough, NMR (nuclear magnetic resonance) analysis can render useful information, but always combined with at least one of the techniques mentioned before 218 . Besides, if the reaction generates volatile products, DEMS (Differential electrochemical mass spectrometry) experiments can identify and quantify the products in real time 219,220 . At least to our knowledge, apart from the recent publication of some of us 221 , there is not many articles studying the electrooxidation of organic molecules in perovskites oxides using in situ techniques to unravel the main reaction pathways of the reaction.…”