The role of Zn in the sustainable one-pot synthesis of dimethyl carbonate from carbon dioxide, methanol and propylene oxide

Dimethyl carbonate (DMC) can be applied as a greener alternative to more hazardous materials, e.g. phosgene or dimethyl sulfate. Herein, one-pot synthesis of DMC from propylene oxide, methanol and CO2 using alkali halide catalysts under mild conditions was studied. Addition of Zn powder to the K2CO3-NaBr-ZnO catalyst system was seen to increase DMC selectivity from 19.8% (TOF = 39.0 h-1) to 40.2% (TOF = 78.1 h-1) at 20 bar and 160 °C for 5 h. Catalyst characterisation showed that Zn powder increases the stability of the catalyst, preventing the active ingredients on the catalyst surface from leaching. An increase in propylene oxide conversion to DMC is attributed to the increase of Zn2+ ions in the reaction solution. Elevated pressure was not found to be a necessary reaction condition for transesterification. This study shows that increased selectivity to DMC can be achieved at mild conditions with the addition of Zn powder

The role of Zn in the sustainable one-pot synthesis of dimethyl carbonate from carbon dioxide, methanol and propylene oxide

Dimethyl carbonate (DMC) can be applied as a greener alternative to more hazardous materials, e.g. phosgene or dimethyl sulfate. Herein, one-pot synthesis of DMC from propylene oxide, methanol and CO2 using alkali halide catalysts under mild conditions was studied. Addition of Zn powder to the K2CO3-NaBr-ZnO catalyst system was seen to increase DMC selectivity from 19.8% (TOF = 39.0 h-1) to 40.2% (TOF = 78.1 h-1) at 20 bar and 160 °C for 5 h. Catalyst characterisation showed that Zn powder increases the stability of the catalyst, preventing the active ingredients on the catalyst surface from leaching. An increase in propylene oxide conversion to DMC is attributed to the increase of Zn2+ ions in the reaction solution. Elevated pressure was not found to be a necessary reaction condition for transesterification. This study shows that increased selectivity to DMC can be achieved at mild conditions with the addition of Zn powder

Operando Studies of Aerosol-Assisted Sol–Gel Catalyst Synthesis via Combined Optical Trapping and Raman Spectroscopy

New insights have been gained into chemical transformations occurring in the initial stages of aerosol-assisted sol–gel (AASG) synthesis of catalysts. This has been achieved through the combined application of optical trapping and Raman spectroscopy. AASG is an emerging technology in catalyst manufacturing that presents numerous advantages over conventional approaches, including the ability to access unique catalyst morphologies. However, the processes occurring during synthesis are largely inferred from bulk-phase analyses due to challenges in conducting in situ or operando measurements on moving aerosols within a flow tube. Herein, these obstacles are overcome through Raman spectroscopic interrogation of a single aerosol droplet constrained within an optical trap, which acts as a direct analogue for a particle moving along a flow tube. These studies represent the first operando investigations of AASG synthesis. The synthesis of Ni/Al2O3 catalysts has been studied, with spectroscopic interrogation conducted on each component of the precursor synthesis solution, where possible, up to and including a mixture containing all components necessary for catalyst synthesis. Raman spectroscopy confirms the formation of stable self-assembled macrostructures within the aerosol and provides direct insights into the reaction mechanisms. Crucially, evidence was obtained allowing alternative reaction pathways to be postulated within the confined environment of an aerosol droplet in comparison to bulk-phase syntheses. In aerosols where nickel was not present, but contained all other components, isothermal room-temperature studies showed the formation of stable but unreactive droplets of ∼1 μm, which were proposed to contain micelle-type structures. Upon heating, initial gelation transformations were seen to be achieved at temperatures higher than ∼56 °C. Notably, little loss of spectral intensity corresponding to the C–H stretch (ethanol) was observed from the heated aerosol, implying that evaporation is not a prerequisite for the reaction. When nickel is present in the synthesis solution reactive transformations occur at room temperature, proposed to result in a continuous Al–O–Ni–NO3 structure; a more rapid transformation takes place at elevated temperatures. These results provide the first direct evidence of the processes occurring within aerosols during AASG and shed new light on the mechanistic understanding of this technology. This therefore facilitates the design of new synthetic approaches and hence the production of catalysts and other materials with enhanced properties

CO hydrogenation over K‐Co‐MoSₓ catalyst to mixed alcohols: A kinetic analysis

Higher alcohol synthesis (HAS) from syngas is one of the most promising approaches to produce fuels and chemicals. Our recent investigation on HAS showed that potassium‐promoted cobalt‐molybdenum sulfide is an effective catalyst system. In this study, the intrinsic kinetics of the reaction were studied using this catalyst system under realistic conditions. The study revealed the major oxygenated products are linear alcohols up to butanol and methane is the main hydrocarbon. The higher alcohol products (C3+) followed an Anderson‐Schultz‐Flory distribution while the catalyst suppressed methanol and ethanol formation. The optimum reaction conditions were estimated to be at temperature of 340°C, pressure of 117 bar, gas hourly space velocity of 27 000 mL g–1 h–1 and H2/CO molar feed ratio of 1. A kinetic network has been considered and kinetic parameters were estimated by nonlinear regression of the experimental data. The results indicated an increasing apparent activation energy of alcohols with the length of alcohols except for ethanol. The lower apparent activation energy of alcohols compared with hydrocarbon evidenced the efficiency of this catalyst system to facilitate the formation of higher alcohols

Synthesis of TiO2-x/W18O49 Hollow Double-shell and Core-shell Microspheres for CO2 Photoreduction under Visible Light

TiO2x/W18O49 with core–shell or double-shelled hollow microspheres were synthesized through a facile multi-step solvothermal method. The formation of the hollow microspheres with a doubleshell was a result of the Kirkendall effect during the solvothermal treatment with concentrated NaOH. The advanced architecture significantly enhanced the electronic properties of TiO2x/ W18O49, improving by more than 30 times the CO2 photoreduction efficiency compared to the pristine W18O49. Operando DRIFTS measurements revealed that the yellow TiO2x was a preferable CO2 adsorption and conversion site

Elucidating the Significance of Copper and Nitrate Speciation in Cu-SSZ-13 for N₂O Formation during NH₃-SCR

Unwanted N2O formation is a problem that has been noted in selective catalytic reduction (SCR) where copper zeolite catalysts are utilized. With its immense global warming potential and long-term stability, elevated atmospheric N2O has already been identified as a future challenge in the war on climate change. This paper explores the phenomenon of N2O formation during NH3-SCR over Cu-SSZ-13 catalysts, which are currently commercialized in automotive emissions control systems, and proposes a link between N2O production and the local copper environment found within the zeolite. To achieve this, a comparison is made between two Cu-SSZ-13 samples with different copper co-ordinations produced via different synthesis methods. A combination of synchrotron X-ray absorption near-edge spectroscopy, UV–vis, Raman, and density functional theory (DFT) is used to characterize the nature of copper species present within each sample. Synchrotron IR microspectroscopy is then used to compare their behavior during SCR under operando conditions and monitor the evolution of nitrate intermediates, which, along with further DFT, informs a mechanistic model for nitrate decomposition pathways. Increased N2O production is seen in the Cu-SSZ-13 sample postulated to contain a linear Cu species, providing an important correlation between the catalytic behavior of Cu-zeolites and the nature of their metal ion loading and speciation

Efficient low-loaded ternary Pd-In2O3-Al2O3 catalysts for methanol production

Pd-In2O3 catalysts are among the most promising alternatives to Cu-ZnO-Al2O3 for synthesis of CH3OH from CO2. However, the intrinsic activity and stability of In2O3 per unit mass should be increased to reduce the content of this scarcely available element and to enhance the catalyst lifetime. Herein, we pro -pose and demonstrate a strategy for obtaining highly dispersed Pd and In2O3 nanoparticles onto an Al2O3 matrix by a one-step coprecipitation followed by calcination and activation. The activity of this catalyst is comparable with that of a Pd-In2O3 catalyst (0.52 vs 0.55 gMeOH h-1 gcat-1 at 300 & DEG;C, 30 bar, 40,800 mL h-1 gcat-1 ) but the In2O3 loading decreases from 98 to 12 wt% while improving the long-term stability by three-fold at 30 bar. In the new Pd-In2O3-Al2O3 system, the intrinsic activity of In2O3 is highly increased both in terms of STY normalized to In specific surface area and In2O3 mass (4.32 vs 0.56 g gMeOH h-1 gIn2O3-1 of a Pd-In2O3 catalyst operating at 300 & DEG;C, 30 bar, 40,800 mL h-1 gcat-1).The combination of ex situ and in situ catalyst characterizations during reduction provides insights into the interaction between Pd and In and with the support. The enhanced activity is likely related to the close proximity of Pd and In2O3, wherein the H2 splitting activity of Pd promotes, in combination with CO2 activation over highly dispersed In2O3 particles, facile formation of CH3OH

Efficient low-loaded ternary Pd-In2O3-Al2O3 catalysts for methanol production

Pd-In2O3 catalysts are among the most promising alternatives to Cu-ZnO-Al2O3 for synthesis of CH3OH from CO2. However, the intrinsic activity and stability of In2O3 per unit mass should be increased to reduce the content of this scarcely available element and to enhance the catalyst lifetime. Herein, we propose and demonstrate a strategy for obtaining highly dispersed Pd and In2O3 nanoparticles onto an Al2O3 matrix by a one-step coprecipitation followed by calcination and activation. The activity of this catalyst is comparable with that of a Pd-In2O3 catalyst (0.52 vs 0.55 gMeOH h−1 gcat-1 at 300 °C, 30 bar, 40,800 mL h−1 gcat-1) but the In2O3 loading decreases from 98 to 12 wt% while improving the long-term stability by threefold at 30 bar. In the new Pd-In2O3-Al2O3 system, the intrinsic activity of In2O3 is highly increased both in terms of STY normalized to In specific surface area and In2O3 mass (4.32 vs 0.56 g gMeOH h−1 gIn2O3-1 of a Pd- In2O3 catalyst operating at 300 °C, 30 bar, 40,800 mL h−1 gcat-1).The combination of ex situ and in situ catalyst characterizations during reduction provides insights into the interaction between Pd and In and with the support. The enhanced activity is likely related to the close proximity of Pd and In2O3, wherein the H2 splitting activity of Pd promotes, in combination with CO2 activation over highly dispersed In2O3 particles, facile formation of CH3OH

Efficient low-loaded ternary Pd-In2O3-Al2O3 catalysts for methanol production

Pd-In2O3 catalysts are among the most promising alternatives to Cu-ZnO-Al2O3 for synthesis of CH3OH from CO2. However, the intrinsic activity and stability of In2O3 per unit mass should be increased to reduce the content of this scarcely available element and to enhance the catalyst lifetime. Herein, we propose and demonstrate a strategy for obtaining highly dispersed Pd and In2O3 nanoparticles onto an Al2O3 matrix by a one-step coprecipitation followed by calcination and activation. The activity of this catalyst is comparable with that of a Pd-In2O3 catalyst (0.52 vs 0.55 gMeOH h−1 gcat-1 at 300 \ub0C, 30 bar, 40,800 mL h−1 gcat-1) but the In2O3 loading decreases from 98 to 12 wt% while improving the long-term stability by threefold at 30 bar. In the new Pd-In2O3-Al2O3 system, the intrinsic activity of In2O3 is highly increased both in terms of STY normalized to In specific surface area and In2O3 mass (4.32 vs 0.56 g gMeOH h−1 gIn2O3-1 of a Pd- In2O3 catalyst operating at 300 \ub0C, 30 bar, 40,800 mL h−1 gcat-1).The combination of ex situ and in situ catalyst characterizations during reduction provides insights into the interaction between Pd and In and with the support. The enhanced activity is likely related to the close proximity of Pd and In2O3, wherein the H2 splitting activity of Pd promotes, in combination with CO2 activation over highly dispersed In2O3 particles, facile formation of CH3OH