Theoretical investigation of the carbonyl-ene reaction between encapsulated formaldehyde and propylene over M-Cu-BTC paddlewheels (M= Be, Mg, and Ca): A DFT study.

Formaldehyde is a VOC gas that plays a key role in air pollution. To limit emissions into the environment, the utilization of this waste as a raw material is a promising way. In this work, the M06-L functional calculation was used to investigate the structure, electronic properties, and catalytic activity of group IIA metals (Be, Mg, and Ca) partial substitution on Cu-BTC paddlewheels for formaldehyde encapsulation and carbonyl-ene reaction with propylene. Formaldehyde is absorbed by the metal center of the paddlewheel via its oxygen atom. The adsorption of formaldehyde on the substituted metal sites increased as compared to the parent Cu-BTC which can facilitate formaldehyde to react with propylene. The adsorption free energies are predicted to be -15.1 (Be-Cu-BTC), -14.7 (Mg-Cu-BTC), and -14.5 (Ca-Cu-BTC) kcal mol-1, respectively. The substituted metal has a slight effect on the Lewis acidity of the Cu ion in the paddlewheel. The adsorption free energy of formaldehyde, similar to that found in the pristine Cu-BTC, is observed. For the carbonyl-ene reaction, the reaction is proposed via a single step involving the C-C bond formation between two reactants and one hydrogen of propylene methyl group moves to formaldehyde oxygen, simultaneously. It was found that the substituted metals do not affect the catalytic performance of the Cu center for this reaction. The activation energies for the reaction at the Cu center are in the range of 22.0-23.4 kcal mol-1, which are slightly different from Cu-BTC (21.5 kcal mol-1). Interestingly, the catalytic activity of this reaction on the substituted metal is greater than that on the Cu center. The catalytic activities are in the order Be-Cu-BTC (13.3 kcal mol-1) > Mg-Cu-BTC (15.9 kcal mol-1) > Ca-Cu-BTC (17.8 kcal mol-1). Among them, the Be site of the bimetallic Be-Cu-BTC paddlewheel is predicted as a promising candidate catalyst.

Understanding the effect of the divalent cations (Ni, Cu, and Zn) exchanged FAU zeolite on the kinetic of CO2 cycloaddition with ethylene oxide: A DFT study.

Epoxide ring opening and cycloaddition with CO2 is one of the promising routes to convert CO2 to more valuable industrial chemicals. In this work, density functional theory calculations with the M06-L/6-31G(d,p) level of theory have been employed to study the cycloaddition of ethylene oxide (EO) with CO2 over M(II)-faujasite zeolite (M = Ni, Cu, and Zn) in the absence of a co-catalyst. The influence of the exchanged metals strongly dominates the adsorption of EO. The binding energies of EO on the active site are -39.9 (Ni-FAU), -24.2 (Cu-FAU), and -35.0 (Zn-FAU) kcal/mol, respectively. The reaction mechanism is proposed to occur via the concerted mechanism, in which the metals initiate the EO ring opening and the formation of two new C-O bonds between the adsorbed EO and CO2 proceed in a single step. The activation energy of the reaction catalyzed by Cu-FAU is 24.2 kcal/mol whereas that of Ni and Zn-FAU is found to be 31.1 and 31.4 kcal/mol, respectively. Moderate adsorption of EO and a larger electron transfer at the transition state are the important keys that reduce the activation energy for the Cu-FAU lower than in the other systems.

Moisture-Resistant Electrospun Polymer Membranes for Efficient and Stable Fully Printable Perovskite Solar Cells Prepared in Humid Air.

Fully printable perovskite solar cells (PPSCs) attract attention in the photovoltaic industry and research owing to their controllable and scalable production with reduced material waste during manufacturing. However, the commercialization of PPSCs has been impeded by their inherent vulnerability to ambient moisture, leading to a rapid loss of device efficiency and lifetime. Here, we propose a novel idea to enhance the photovoltaic performance and stability of PPSCs in humid air (relative humidity exceeding 80%) using electrospun hydrophobic polymer membranes, i.e., polylactic acid (PLA), polycaprolactone (PCL), and PLA/PCL blends, as moisture-resistant layers for PPSCs. After optimizing the morphologies, hydrophobicity, and thermal properties of the electrospun membranes by varying the contents of the polymer components in the membranes, the unencapsulated devices with these membranes demonstrated power conversion efficiencies of up to 8.2%, which was significantly higher than for devices without the membranes (6.8%). Moreover, devices with the optimum electrospun membrane retained more than 85% of their original efficiency after being stored in humid air for over 35 days. In comparison, devices without the electrospun membranes lost about 50% of their initial efficiency over the same time. Our work is very useful for the development of highly efficient and stable commercial PPSCs.

Charge storage mechanisms of manganese oxide nanosheets and N-doped reduced graphene oxide aerogel for high-performance asymmetric supercapacitors.

Although manganese oxide- and graphene-based supercapacitors have been widely studied, their charge storage mechanisms are not yet fully investigated. In this work, we have studied the charge storage mechanisms of K-birnassite MnO2 nanosheets and N-doped reduced graphene oxide aerogel (N-rGOae) using an in situ X-ray absorption spectroscopy (XAS) and an electrochemical quart crystal microbalance (EQCM). The oxidation number of Mn at the MnO2 electrode is +3.01 at 0 V vs. SCE for the charging process and gets oxidized to +3.12 at +0.8 V vs. SCE and then reduced back to +3.01 at 0 V vs. SCE for the discharging process. The mass change of solvated ions, inserted to the layers of MnO2 during the charging process is 7.4 µg cm-2. Whilst, the mass change of the solvated ions at the N-rGOae electrode is 8.4 µg cm-2. An asymmetric supercapacitor of MnO2//N-rGOae (CR2016) provides a maximum specific capacitance of ca. 467 F g-1 at 1 A g-1, a maximum specific power of 39 kW kg-1 and a specific energy of 40 Wh kg-1 with a wide working potential of 1.6 V and 93.2% capacity retention after 7,500 cycles. The MnO2//N-rGOae supercapacitor may be practically used in high power and energy applications.

Conversion of CO2 and C2H6 to propanoic acid over a Au-exchanged MCM-22 zeolite.

Finding novel catalysts for the direct conversion of CO2 to fuels and chemicals is a primary goal in energy and environmental research. In this work, density functional theory (DFT) is used to study possible reaction mechanisms for the conversion of CO2 and C2H6 to propanoic acid over a gold-exchanged MCM-22 zeolite catalyst. The reaction begins with the activation of ethane to produce a gold ethyl hydride intermediate. Hydrogen transfers to the framework oxygen leads then to gold ethyl adsorbed on the Brønsted-acid site. The energy barriers for these steps of ethane activation are 9.3 and 16.3 kcal mol(-1), respectively. Two mechanisms of propanoic acid formation are investigated. In the first one, the insertion of CO2 into the Au-H bond of the first intermediate yields gold carboxyl ethyl as subsequent intermediate. This is then converted to propanoic acid by forming the relevant C-C bond. The activation energy of the rate-determining step of this pathway is 48.2 kcal mol(-1). In the second mechanism, CO2 interacts with gold ethyl adsorbed on the Brønsted-acid site. Propanoic acid is formed via protonation of CO2 by the Brønsted acid and the simultaneous formation of a bond between CO2 and the ethyl group. The activation energy there is 44.2 kcal mol(-1), favoring this second pathway at least at low temperatures. Gold-exchanged MCM-22 zeolite can therefore, at least in principle, be used as the catalyst for producing propanoic acid from CO2 and ethane.

Predicting transition pressures for obtaining nanoporous semiconductor polymorphs: oxides and chalcogenides of Zn, Cd and Mg.

The energy versus volume equations of state are calculated for seven known and hypothetical polymorphic forms of ZnX, CdX, and MgX (where X = O, S, Se, Te). From these data the phases of lowest enthalpy are extracted with respect to decreasing pressure starting at the ground state for all compositions. Following these paths of minimum enthalpy, with respect to the polymorphs considered, we predict the transition pressures required to convert the ground-state phase into the novel, as yet hypothetical, nanoporous SOD phase (an analogue of the silicate zeolite sodalite). Our results suggest that the SOD phase would be thermodynamically stable for all compositions considered under suitable negative pressures. Of all the compositions considered CdX and MgX with relatively large anions (i.e. Se and Te) are specifically predicted to be the most amenable materials for the experimental preparation of the SOD phase.

Persistence of magic cluster stability in ultra-thin semiconductor nanorods.

The progression from quasi zero-dimensional (Q0D) nanoclusters to quasi one-dimensional (Q1D) nanorods, and, with increasing length, to nanowires, represents the most conceptually fundamental transition from the nanoscale to bulk-like length scales. This dimensionality crossover is particularly interesting, both scientifically and technologically, for inorganic semiconducting (ISC) materials, where striking concomitant changes in optoelectronic properties occur.(1,2) Such effects are most pronounced for ultra-thin(3) ISC nanorods/nanowires, where the confining and defective nature of the atomic structure become key. Although experiments on ISC materials in this size regime have revealed especially stable (or "magic") non-bulk-like Q0D nanoclusters,(4,5) all ISC Q1D nanostructures have been reported as having structures corresponding to bulk crystalline phases. For two important ISC materials (CdS and CdSe) we track the Q0D-to-Q1D transition employing state-of-the-art electronic structure calculations demonstrating an unexpected persistence of magic cluster stability over the bulk-like structure in ultra-thin nanorods up to >10 nm in length. The transition between the magic-cluster-based and wurtzite nanorods is found to be accompanied by a large change in aspect ratio thus potentially providing a route to nano-mechanical transducer applications.