Kinetics and Thermodynamic Modeling for CO2 Capture Using NiO Supported Activated Carbon by Temperature Swing Adsorption

Solid sorbent from functionalized activated carbon (AC) could enhance the adsorption capacity in CO2 capture. This study emphasizes cyclic CO2 capture using NiO functionalized AC. Different loadings of NiO impregnated on AC were synthesized. This work showed that the most efficient adsorbent of 0.05NiO/AC exhibits an adsorption capacity of 55.464 mg/g at the adsorption temperature of 30 °C by using the temperature swing adsorption method. A slight loss of adsorption capacity at 0.28 % for a five cycles CO2 capture indicated consistency potential for large scales application. The adsorbent exhibited a slightly lower surface area compared to AC, but the presence of NiO improved the adsorption capacity by chemisorption phenomena. The NiO acts as the basic site for CO2 capture. Meanwhile, AC as support could increase the surface area of active sites and reduce the sintering effect of the NiO. It was found that various adsorption temperatures had a good correlation with the pseudo-second-order kinetic model. The magnitude of the sorption process was evaluated by the activation energy of 48.09 kJ/mol, which implies a chemisorption process at various adsorption temperatures. Thermodynamic studies explained the CO2 adsorption process for this study was found to be a spontaneous and endothermic process.

Defect engineering: an effective tool for enhancing the catalytic performance of copper-MOFs for the click reaction and the A3 coupling

A series of Cu(i)-enriched and Lewis basic site-containing defect-engineering MOFs was investigated for significantly enhanced catalytic performance in the click reaction and the A3 coupling.

Turn-on fluorescent probe towards glyphosate and Cr3+ based on Cd(ii)-metal organic framework with Lewis basic sites

Lewis basic site-functionalized porous Cd(ii)-MOF as a bi-functional fluorescent sensor of glyphosate and Cr3+ with exceptional LODs.

Adsorbate-induced Active Site in Zeolite

There has been a long debate on how and where active sites are created for molecular adsorption and catalysis in zeolites which underpin many important industrial applications. For example, Lewis acidic site (LAS) and basic site (LBS) are generally believed to be the extra-framework Al species and residue anion (OH−) species formed at fixed crystallographic positions on the zeolite structures after their synthesis. Here, direct experimental observation of adsorbate-induced active sites in silicoaluminophosphate (SAPO) zeolites is for the first time made, which contradicts the traditional view of the fixed active sites in zeolites. Evidence shows that induced Frustrated Lewis pair (three-coordinated framework Al as LAS and SiO(H) as LBS) can be transiently favored for heterolytic molecular binding/reactions of competitive polar adsorbates due to their ineffective orbitals overlap in the rigid framework. High resolution magic-angle spinning solid-state nuclear magnetic resonance (MAS-SSNMR), synchrotron X-ray diffraction (SXRD), neutron powder diffraction (NPD), in-situ Diffuse Reflectance Infrared Fourier Transform spectroscopy (in-situ DRIFT) and ab initio molecular dynamic (AIMD) demonstrate the presence of only one type of Bronsted acid site (BAS) in the H-SAPO-34, however, when exposed to polar adsorbates such as methanol, the methoxy moiety is shown to be directly coordinated to the framework Al (induced LAS) and the proton to the O(H)-Si (induced LBS) by the induced FLP. Our unprecedented finding opens up a new avenue to understanding of the dynamic establishment of active sites for adsorption or chemical reactions under molecular bombardments to zeolitic structures.

Chemo- and Regioselective Hydroformylation of Alkenes with CO2/H2 over a Bifunctional Catalyst

Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging approach. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield and 93/7 regioselectivity under mild reaction conditions (25 bar, 80 ºC). Key-to-success is the use of bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved feasible with superior regioselectivity than that of CO pathway.

K2O Doped Dolomite as Heterogeneous Catalyst for Fatty Acid Methyl Ester Production from Palm Oil

Biodiesel obtained from palm oil over an environmentally friendly catalyst is highlydesirable. For that matter, dolomite, a natural material was used as a catalyst in this work, and this included potassium oxide (K2O)-doped dolomite, 5 wt% K/D, 10 wt% K/D, 15 wt% K/D, and 20 wt% K/D. X-ray diffraction analysis of dolomite revealed the CaO and MgO phases with high crystallinity, in which intensity reduced after doped with varying concentrations of K2O. When the catalysts were evaluated, the K2O-doped dolomite exhibited a better catalytic activity for palm oil transesterification. In the presence of K2O, the methyl ester reached 98.7%, with the highest being displayed by 15 wt% K/D as compared to 87% over dolomite at reaction temperature of 60 °C, 12:1 methanol to palm oil ratio, 1 wt% catalyst amount and 1 h reaction time. SEM revealed that as more K2O was doped on dolomite, the particles became more agglomerated, with a reduced BET surface area of 1.3 m2/g in 20 wt% K/D as opposed to homogeneously small-sized MgO and CaO particles in dolomite with a high BET surface area of 19.0 m2/g. However, the high activity of the doped catalyst was dictated by the high amount of basic site, as evidenced in TPD-CO2 which showed an increase in the capacity of the basic site with an increased amount of K2O. The catalyst was also reusable up to six times with a negligible decrease in activity due to K+ leaching.