Effect of reduction pretreatment on the structure and catalytic performance of Ir-In2O3 catalysts for CO2 hydrogenation to methanol.

In2O3 has been found a promising application in CO2 hydrogenation to methanol, which is beneficial to the utilization of CO2. The oxygen vacancy (Ov) site is identified as the catalytic active center of this reaction. However, there remains a great challenge to understand the relations between the state of oxygen species in In2O3 and the catalytic performance for CO2 hydrogenation to methanol. In the present work, we compare the properties of multiple In2O3 and Ir-promoted In2O3 (Ir-In2O3) catalysts with different Ir loadings and after being pretreated under different reduction temperatures. The CO2 conversion rate of Ir-In2O3 is more promoted than that of pure In2O3. With only a small amount of Ir loading, the highly dispersed Ir species on In2O3 increase the concentration of Ov sites and enhance the activity. By finely tuning the catalyst structure, Ir-In2O3 with an Ir loading of 0.16 wt.% and pre-reduction treatment under 300°C exhibits the highest methanol yield of 146 mgCH3OH/(gcat·hr). Characterizations of Raman, electron paramagnetic resonance, X-ray photoelectron spectroscopy, CO2-temperature programmed desorption and CO2-pulse adsorption for the catalysts confirm that more Ov sites can be generated under higher reduction temperature, which will induce a facile CO2 adsorption and desorption cycle. Higher performance for methanol production requires an adequate dynamic balance among the surface oxygen atoms and vacancies, which guides us to find more suitable conditions for catalyst pretreatment and reaction.

Tailoring Zeolite L-Supported-Cu Catalysts for CO2 Hydrogenation: Insights into the Mechanism of CH3OH and CO Formation.

The utilization of Cu-based catalysts in CO2 conversion into valuable chemicals is of significant interest due to their potential in mitigating greenhouse gas emissions. However, the controllable design of Cu-based catalysts and the regulation of their mechanism remain challenging. In this study, a series of efficient Cu/L catalysts were prepared for this process, and the intrinsic influencing factors on the reaction routes were systematically revealed. Various techniques revealed that Cu particles in L-supported catalysts exhibited higher dispersion and formed Cu-O(OH)-K interfacial sites. However, with increasing Cu loading, the dispersion of Cu particles and the percentage of Cu-O(OH)-K interfaces decreased. Kinetic investigations revealed that the adsorption configuration and electronic structure of Cu species codetermined the reaction pathways and resulting selectivity. Cu/L catalysts possessing Cu-O(OH)-K interfaces and small particles demonstrated the preferential formation of formate species, promoting methanol formation. However, larger Cu particles generated carboxylate intermediates, resulting in higher CO selectivity..

Polyvinyl Chloride-Derived Carbon Spheres for CO2 Adsorption.

Polyvinyl chloride (PVC) is the world's third-most widely produced plastic polymer. Directly transforming PVC to carbonaceous materials for CO2 capture provides an environmentally friendly and attractive strategy to recycle plastics. In this work, a simple and effective method was developed to prepare PVC-derived carbon spheres. In this method, the classical "spheroidization" process shaped the original PVC powders into millimeter spheres, and a special dehalogenation and cross-linking process in the presence of a phase-transfer catalyst transferred the thermoplasticity of the PVC-spheres into thermosetting, which stabilized the shape. Furthermore, by rationally adjusting the activation conditions, the porous structure of the carbon spheres was well optimized. With a specific surface area up to 1738 m2 g-1 and the developed microporous structure, the as-prepared carbon spheres showed not only excellent performance in pure CO2 adsorption (8.93 mmol g-1 , 39.3 wt% at 0 °C and 5.47 mmol g-1 , 24.1 wt% at 25 °C), but also outstanding adsorption capacity and recyclability in low-concentration CO2 capture, even superior to conventional molecular sieves.

Tuning reactivity of Fischer-Tropsch synthesis by regulating TiOx overlayer over Ru/TiO2 nanocatalysts.

The activity of Fischer-Tropsch synthesis (FTS) on metal-based nanocatalysts can be greatly promoted by the support of reducible oxides, while the role of support remains elusive. Herein, by varying the reduction condition to regulate the TiOx overlayer on Ru nanocatalysts, the reactivity of Ru/TiO2 nanocatalysts can be differentially modulated. The activity in FTS shows a volcano-like trend with increasing reduction temperature from 200 to 600 °C. Such a variation of activity is characterized to be related to the activation of CO on the TiOx overlayer at Ru/TiO2 interfaces. Further theoretical calculations suggest that the formation of reduced TiOx occurs facilely on the Ru surface, and it involves in the catalytic mechanism of FTS to facilitate the CO bond cleavage kinetically. This study provides a deep insight on the mechanism of TiOx overlayer in FTS, and offers an effective approach to tuning catalytic reactivity of metal nanocatalysts on reducible oxides.