Formation of hierarchical Bi2MoO6/ln2S3 S-scheme heterojunction with rich oxygen vacancies for boosting photocatalytic CO2 reduction

https://onlinelibrary.wiley.com/doi/pdf/10.1002/sstr.202100058

Defect Engineering on CeO2-Based Catalysts for Heterogeneous Catalytic Applications

For many years, capturing, storing or sequestering CO2 from concentrated emission sources or from air has been a powerful technique for reducing atmospheric CO2. Moreover, the use of CO2 as a C1 building block to mitigate CO2 emissions and, at the same time, produce sustainable chemicals or fuels is a challenging and promising alternative to meet global demand for chemicals and energy. Hence, the chemical incorporation and conversion of CO2 into valuable chemicals has received much attention in the last decade, since CO2 is an abundant, inexpensive, nontoxic, nonflammable, and renewable one-carbon building block. Nevertheless, CO2 is the most oxidized form of carbon, thermodynamically the most stable form and kinetically inert. Consequently, the chemical conversion of CO2 requires highly reactive, rich-energy substrates, highly stable products to be formed or harder reaction conditions. The use of catalysts constitutes an important tool in the development of sustainable chemistry, since catalysts increase the rate of the reaction without modifying the overall standard Gibbs energy in the reaction. Therefore, special attention has been paid to catalysis, and in particular to heterogeneous catalysis because of its environmentally friendly and recyclable nature attributed to simple separation and recovery, as well as its applicability to continuous reactor operations. Focusing on heterogeneous catalysts, we decided to center on zeolite and ordered mesoporous materials due to their high thermal and chemical stability and versatility, which make them good candidates for the design and development of catalysts for CO2 conversion. In the present review, we analyze the state of the art in the last 25 years and the potential opportunities for using zeolite and OMS (ordered mesoporous silica) based materials to convert CO2 into valuable chemicals essential for our daily lives and fuels, and to pave the way towards reducing carbon footprint. In this review, we have compiled, to the best of our knowledge, the different reactions involving catalysts based on zeolites and OMS to convert CO2 into cyclic and dialkyl carbonates, acyclic carbamates, 2-oxazolidones, carboxylic acids, methanol, dimethylether, methane, higher alcohols (C2+OH), C2+ (gasoline, olefins and aromatics), syngas (RWGS, dry reforming of methane and alcohols), olefins (oxidative dehydrogenation of alkanes) and simple fuels by photoreduction. The use of advanced zeolite and OMS-based materials, and the development of new processes and technologies should provide a new impulse to boost the conversion of CO2 into chemicals and fuels.

Advanced zeolite and ordered mesoporous silica-based catalysts for the conversion of CO2 to chemicals and fuels.

CeO2 and CeO2-based nanomaterials for photocatalytic, antioxidant and antimicrobial activities

Effect of Mn and Ce oxides on low-temperature NH3-SCR performance over blast furnace slag-derived zeolite X supported catalysts

Recent developments and challenges in zeolite-based composite photocatalysts for environmental applications

The CO2 gasification reactivity of pine sawdust chars (PS char) obtained from the different high-temperature pyrolysis is studied based on non-isothermal thermogravimetric method. Results show that the order of gasification reactivity is PS char-1073 > PS char-1273 > PS char-1473. Under the effect of high-temperature pyrolysis, the surface structure of biomass char is gradually destroyed and the pore structure parameters of specific surface area, total pore volume and average pore diameter increase. By means of the N2 adsorption-desorption isotherms, it is seen that biomass char has more micro- and mesoporous at higher pyrolysis temperature. Besides, the PS char-1073 mostly has rich closed cylinder pores and parallel plate pores, and the PS char-1273 and PS char-1473 have plentiful open cylinder pores and parallel plate pores. An increase of pyrolysis temperature contributes to the development of porosity and improves diffusion path, which promotes the gasification reactivity. But, its effect on the decline of active site hinders the gasification reactivity. What's more, the kinetic model of distributed activation energy model (DAEM) is applied to calculate activation energy and pre-exponential factor with the integral and differential methods. The calculation results of integral method is more accurate and precise because the differential method is more sensitive than integral method for experimental noise. There is a compensation effect in the CO2 gasification process.

Effect of pore structure on CO2 gasification reactivity of biomass chars under high-temperature pyrolysis

Manganese-containing soil (M-S) is a solid waste generated from the mining and extraction of manganese ore. In this study, the low-temperature denitration performance of Mn-S was investigated via XRF, XRD, XPS, H2-TPR, NH3-TPD and DRIFTS, aiming at exploring its utilization approach as low-temperature NH3-SCR catalyst. The results showed that Mn-S exhibited a relatively high catalytic activity reaching over 75% NO conversion from 150 °C to 200 °C. The physical and chemical properties of Mn-S were studied, indicating that the manganese content of Mn-S reached 8.2% with mainly surface Mn atomic valence state of Mn3+. In situ DRIFTS results revealed the SCR reaction mechanism of Mn-S, suggesting that Mn-S obeyed the E-R reaction mechanism. The Ce/Mn-S catalyst was synthesized by impregnation method. The denitration activity improved and reached 92.4% at 200 °C. A series of characterizations were studied to investigate the strengthening mechanism after doping Ce. It’s found that introducing of Ce could increase the content of Mn4+ and chemisorbed oxygen, NH3 adsorption capacity and reducibility. It was found from in situ DRIFTS experiments that doping of Ce changed the reaction mechanism due to the conversion of inactive substance, which was mainly affected by E-R and L-H.

Application of manganese-containing soil as novel catalyst for low-temperature NH3-SCR of NO

In this work, based on a type of energy band engineering strategy as calcination, TiO2/ZSM-5 hybrids for photodegradation of methyl orange (MO) in water under UV light have been developed via a facile solid state diffusion method. Effects of varied calcination temperatures on TiO2/ZSM-5 hybrids have been systematically characterized including XRD, FT-IR, SEM, TEM, EDX mapping, BET, PL, EIS, UV–vis DRS, active species trapping experiments and Mott-Schottky curves. It was found that the calcination temperature influenced photocatalytic activity, typically on physicochemical properties of materials and adjustment for the energy gap and band position of TiO2. The XRD analysis revealed that hybridization of ZSM-5 kept the crystal phase of TiO2 as anatase unchanged with the high-rising calcined temperature. The optimum sample calcined at 450 °C named as Z-T (450) presented nearly 99% degradation rate for MO, owing to optimal uniform distribution, highest specific surface area and best charge separation/transfer efficiency. The FT-IR comparison result that the functional groups and peak strength of the used catalyst were alike as before, showed the stability of photocatalyst. Adoption of calcination strategy does provide not only a clean, low-cost and highly efficient path to approach the complete degradation of azo dyes, but also a chance for photocatalytic technology to fulfill the implementation in industrial applications.

Optimization of TiO2/ZSM-5 photocatalysts: Energy band engineering by solid state diffusion method with calcination

V2O5-WO3/TiO2 catalyst has been widely used in industry. Alkali metals would cause the deactivation of V2O5-WO3/TiO2 catalyst. In this paper, the poisoning deactivation of NaCl and Na2O on V2O5-WO3/TiO2 catalyst was compared. The properties of the catalysts were characterized by BET, XPS, H2-TPR, NH3-TPD and in situ DRIFTS. It was found the addition of NaCl, Na2O affected the structure, redox properties and acid sites of V2O5-WO3/TiO2 catalyst. Na+ would react with V OH to form V O Na+ destroying the structure of Bronsted sites and affect the adsorption of NH3 on the Lewis acid to restrain the generation of V4+ NH2 to decrease the SCR activity, occupying the oxygen vacancy made a decline in chemisorbed oxygen. The poisoning effect of NaCl was stronger than that of Na2O, even if the property of weak-chemisorption of NaCl is stronger and possessed more V5+ species. There is a reason that NaCl provided HCl and then reacted with VO2 to form Cl V O Cl OH to adsorb NH3. However, Cl V O Cl OH cannot make the catalysis selectively generate nitrogen and water.

Comparative study of the poisoning effect of NaCl and Na2O on selective catalytic reduction of NO with NH3 over V2O5-WO3/TiO2 catalyst

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