Effect of gas flow rate and discharge volume on CO2 methanation with plasma catalysis

CO2 methanation can be a key technology for realizing a sustainable society. CH4 is used as an energy carrier and raw material for chemical products, thereby contributing to the reduction of CO2 emissions. Methanation with plasma catalysis lower the process temperature, which can improve the throughput and stability. In this study, we investigated the effect of the gas flow rate and the discharge volume on CO2 methanation, using a low- pressure CCP reactor. Higher gas flow rates can increase the rate of CO2 throughput, but the CH4 selectivity decreases owing to the reduced transportation rate of the reactants to the catalyst surface. Increasing the discharge volume is effective in improving the transportation rate. This study suggested that the structure of the reactor significantly affect the CH4 generation rate.

Realistic Modelling of Dynamics at Nanostructured Interfaces Relevant to Heterogeneous Catalysis

The focus of this short review is directed towards investigations of the dynamics of nanostructured metallic heterogeneous catalysts and the evolution of interfaces during reaction—namely, the metal–gas, metal–liquid, and metal–support interfaces. Indeed, it is of considerable interest to know how a metal catalyst surface responds to gas or liquid adsorption under reaction conditions, and how its structure and catalytic properties evolve as a function of its interaction with the support. This short review aims to offer the reader a birds-eye view of state-of-the-art methods that enable more realistic simulation of dynamical phenomena at nanostructured interfaces by exploiting resource-efficient methods and/or the development of computational hardware and software.

Electrochemical Ruthenium-Catalysed C–H Activation in Water Through Heterogenization of a Molecular Catalyst

Efficient catalytic oxidative C–H activation of organic substrates remains an important challenge in synthetic chemistry. Here, we show that the combination of a transition metal catalyst, surface immobilisation and an...

Characterization of plasma catalytic decomposition of methane: role of atomic O and reaction mechanism

In this work, we investigated atmospheric pressure plasma jet (APPJ)-assisted methane oxidation over a Ni-SiO2/Al2O3 catalyst. We evaluated possible reaction mechanisms by analyzing the correlation of gas phase, surface and plasma-produced species. Plasma feed gas compositions, plasma powers, and catalyst temperatures were varied to expand the experimental parameters. Real-time Fourier-transform infrared spectroscopy (FTIR) was applied to quantify gas phase species from the reactions. The reactive incident fluxes generated by plasma were measured by molecular beam mass spectroscopy (MBMS) using an identical APPJ operating at the same conditions. A strong correlation of the quantified fluxes of plasma-produced atomic oxygen with that of CH4 consumption, and CO and CO2 formation implies that O atoms play an essential role in CH4 oxidation for the investigated conditions. With the integration of APPJ, the apparent activation energy was lowered and a synergistic effect of 30% was observed. We also performed in-situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) to analyze the catalyst surface. The surface analysis showed that surface CO abundance mirrored the surface coverage of CHn at 25 oC. This suggests that CHn adsorbed on the catalyst surface as an intermediate species that was subsequently transformed into surface CO. We observed very little surface CHn absorbance at 500 oC, while a ten-fold increase of surface CO and stronger CO2 absorption were seen. This indicates that for a nickel catalyst at 500 oC, the dissociation of CH4 to CHn may be the rate-determining step in the plasma-assisted CH4 oxidation for our conditions. We also found the CO vibrational frequency changes from 2143 cm-1 for gas phase CO to 2196 cm-1 for CO on a 25 oC catalyst surface, whereas the frequency of CO on a 500 oC catalyst was 2188 cm-1. The change in CO vibrational frequency may be related to the oxidation of the catalyst.

Modified Rate Law for Bimolecular Reactions: Applicable to Surface as well as Non-surface Reactions

The rate equations in kinematics are expressed through basic laws under surface reaction as well as non-surface reaction. Rate law is center theme of non-surface reaction whereas Langmuir adsorption isotherms are basis of surface reaction rate expressions. A modified rate equation for bimolecular reaction is presented which considers both catalyst surface affairs as well as fraction of successful collision of different reactant for cracking and forming bonds. The modified rate law for bimolecular reaction for surface as well as non-surface reaction is stated as “Rate of a reaction is directly proportional to concentration as well as catalyst surface affair of each reactant” as r = k ΩA[A] ΩB[B] where catalyst surface affair of ith species is defined as Ωi = Ki/(1+Ki[i] + Kj[j] + …). Here, Ki is the equilibrium constant of “i” species for adsorption-desorption processes over catalyst. i, j,… indicates the different adsorbed chemical species at uniform catalyst sites and the same [i], [j], … indicates the concentration of different adsorbed chemical species at uniform catalyst sites.

Subsurface Oxygen Defects Electronically Interacting with Active Sites on In2O3 for Enhanced Photothermocatalytic CO2 Reduction

Oxygen defects play an important role in many catalytic reactions. Increasing surface oxygen defects can be done through reduction treatment. However, excessive reduction blocks electron channels and deactivates the catalyst surface due to electron-trapped effects by subsurface oxygen defects. How to effectively extract electrons from subsurface oxygen defects which cannot directly interact with reactants is challenging and remains elusive. Herein, we report a metallic In-embedded In2O3 nanoflake catalyst over which the turnover frequency of CO2 reduction into CO increases by a factor of 866 (7615 h-1) and 376 (2990 h-1) at same light intensity and reaction temperature, respectively, compared to In2O3. Under electron-delocalization effect of O-In-(O)Vo-In-In structural units at the interface, the electrons in the subsurface oxygen defects are extracted and gather at surface active sites. This improves the electronic coupling with CO2 and stabilizes COOH intermediate. The study opens up new insights for exquisite electronic manipulation of oxygen defects.