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Despite the growing use of organic or mixed solvents in zeolite processing, most studies focus only on aqueous suspension systems. We investigated the colloidal characteristics of submicron-sized zeolite NaA in mixed ethanol–water solvents. The effects of the mixing ratio of solvents and various additives on the dispersion of the zeolite powders were studied. The zeolite NaA particles were destabilized in solvent mixtures at a high ethanol-to-water ratio, a reduction in the zeta potential was observed, and the destabilization was rationalized by the Derjaguin, Landau, Verwey, Overbeek (DLVO) theory. An improved stabilization of the zeolite NaA suspensions was achieved in ethanol-rich solvent mixtures using nonionic low molecular weight organic additives, but not with their ionic counterparts such as anionic, cationic surfactants or inorganic acids or bases. Polyethylene glycol (PEG)-400 was found to be a good dispersant for the submicron-sized zeolite NaA particles in the ethanol–water mixtures, which was attributed to its interaction with the zeolite surface, leading to an increased zeta potential. The PEG-stabilized zeolite suspensions led to low suspension viscosities as well as uniform and consistent spin-coated films.

Microporous polyureas can be highly stable, but isocyanates or phosgene are normally used for the synthesis. Here, it was postulated and demonstrated that 1,1′-carbonyl diimidazole (CDI) could be used for the synthesis. By reacting tetrakis(4-aminophenyl)methane with CDI, a series of new polyureas with ultramicropores (pores <0.7 nm) were synthesized. To tailor thermal properties and porosity, the ratio of tetraamine-to-CDI and the reaction temperature were varied. The CO2 adsorption capacities (with values up to 0.74 mmol/g at 0.15 bar/273 K and 1.91 mmol/g at 1 bar/273 K) were ascribed to the ultramicroporosity. The CO2-based Dubinin-Radushkevich surface areas reached 395 m2/g (at 273 K), while the N2-based BET surface areas (at 77 K) were small. The apparent CO2-over-N2 selectivity was also high for the polymers at 273 K with estimated values of 31–92 for 15/85 v/v mixtures of CO2 and N2. This high selectivity was ascribed to the kinetic hindrance of N2 diffusion. It was noted that one of the polymers changed color irreversibly upon heating. In conclusion, it was shown that CDI and amines could be used to synthesize ultramicroporous polyureas, and that these polymers can exhibit irreversible thermochromism. This thermal effect was attributed to the electron-rich urea moieties, aromatic units, and conjugation.

The agro-sector generates organic waste of various kinds, which potentially could be used to prepare functional materials, lessen environmental problems, and enhance circularity. In this context, the hypothesis that was put forward in this work is that prickly pear seed waste from the Tunisian agro-food industry could be used to prepare activated carbons. The prickly pear seed waste was first hydrothermally carbonized and the resulting hydrochar was activated in CO2 at 800 °C. The yield of the hydrothermal carbonization process is of importance, and it was the highest at intermediate dwell times and temperatures, which was ascribed to the re-precipitation of hydrochar particles on the heat-treated biomass. The hydrochars and activated carbons were characterized with scanning electron microscopy, thermogravimetry, Raman spectroscopy, and N2 and CO2 adsorption/desorption analyses. The activated carbons had micro- (<2 nm) and mesopores (2–50 nm), and specific surface areas and total pore volumes of about 400 m2 −1 and 0.21 cm3 g−1. The study showed that the prickly pear seed waste could be effectively transformed into both hydrochars and activated carbons and that is advisable to optimize the hydrothermal process for the mass yield. A life cycle analysis was performed to assess the environmental impact of the production of typical activated carbons using the approach of this study. Further studies could be focused on enhancing the properties of the activated carbons by further optimization of the activation process.

Patterns of assembled colloidal particles can form on substrates due to solvent evaporation, and here we studied such phenomena in the drying of monodispersed colloidal hydrochar dispersions prepared by the hydrothermal carbonization of glucose and purified by dialysis. During the evaporation of water, line patterns or, in some cases, mud-like patterns formed. The line formation was investigated as a function of the pH of the dispersion, substrate shape, particle concentration, and concentration of sodium dodecylsulfate (SDS). The lines comprised dense assemblies of hydrochar particles. The line width increased with the successive evaporation of water. Sharper lines formed with the addition of SDS, which was ascribed to the effects of solubilization or moderated interactions. At greater particle concentrations, we also observed a continuous layer of colloidal particles between the lines. A mechanism for the line pattern formation derived from the literature on other colloids was proposed. Mud-like patterns formed on the substrate in concentrated samples without SDS addition and were put in the context of the formation of cracks in the drying of colloidal coatings. Hydrochars belong to carbon-rich colloids, which are of fundamental and technological importance. This research could be useful for in situ line printing within microfluidic devices, for example.

Piezoelectric semiconductors have emerged as redox catalysts, and challenges include effective conversion of mechanical energy to piezoelectric polarization and achieving high catalytic activity. The catalytic activity can be enhanced by simultaneous irradiation of ultrasound and light, but the existing piezoelectric semiconductors have trouble absorbing visible light. A piezoelectric catalyst is designed and tested for the generation of hydrogen peroxide (H2O2). It is based on Nb-doped tetragonal BaTiO3 (BaTiO3:Nb) and is sensitized by carbon quantum dots (CDs). The photosensitizer injects electrons into the conduction band of the semiconductor, while the piezoelectric polarization directed electrons to the semiconductor surface, allowing for a high-rate generation of H2O2. The piezoelectric polarization field restricts the recombination of photoinduced electron–hole pairs. A production rate of 1360 µmol gcatalyst−1 h−1 of H2O2 is achieved under visible light and ultrasound co-irradiation. Individual piezo- and photocatalysis yielded lower production rates. Furthermore, the CDs enhance the piezocatalytic activity of the BaTiO3:Nb. It is noted that moderating the piezoelectricity of BaTiO3:Nb via microstructure modulation influences the piezophotocatalytic activity. This work shows a new methodology for synthesizing H2O2 by using visible light and mechanical energy.

Thermosetting polymeric materials have advantageous properties and are therefore used in numerous applications. In this study, it was hypothesized and ultimately shown that thermosets could be derived from comparably sustainable sub-components. A two-step procedure to produce a thermoset comprising of Kraft lignin (KL) and the cross-linker adipic acid (AdA) was developed. The cross-linking was activated by means of an acetylating agent comprising isopropenyl acetate (IPA) to form a cross-linking mixture (CLM). The cross-linking was confirmed by FTIR and solid-state NMR spectroscopy, and the esterification reactions were further studied using model compounds. When the KL lignin was mixed with the CLM, partial esterification occurred to yield a homogeneous viscous liquid that could easily be poured into a mold, as the first step in the procedure. Without any additions, the mold was heated and the material transformed into a thermoset by reaction of the two carboxylic acid-derivatives of AdA and KL in the second step.

Electronic structure calculations are fundamentally important for the interpretation of nuclear magnetic resonance (NMR) spectra from paramagnetic systems that include organometallic and inorganic compounds, catalysts, or metal-binding sites in proteins. Prediction of induced paramagnetic NMR shifts requires knowledge of electron paramagnetic resonance (EPR) parameters: the electronic g tensor, zero-field splitting D tensor, and hyperfine A tensor. The isotropic part of A, called the hyperfine coupling constant (HFCC), is one of the most troublesome properties for quantum chemistry calculations. Yet, even relatively small errors in calculations of HFCC tend to propagate into large errors in the predicted NMR shifts. The poor quality of A tensors that are currently calculated using density functional theory (DFT) constitutes a bottleneck in improving the reliability of interpretation of the NMR spectra from paramagnetic systems. In this work, electron correlation effects in calculations of HFCCs with a hierarchy of ab initio methods were assessed, and the applicability of different levels of DFT approximations and the coupled cluster singles and doubles (CCSD) method was tested. These assessments were performed for the set of selected test systems comprising an organic radical, and complexes with transition metal and rare-earth ions, for which experimental data are available. Severe deficiencies of DFT were revealed but the CCSD method was able to deliver good agreement with experimental data for all systems considered, however, at substantial computational costs. We proposed a more computationally tractable alternative, where the A was computed with the coupled cluster theory exploiting locality of electron correlation. This alternative is based on the domain-based local pair natural orbital coupled cluster singles and doubles (DLPNO-CCSD) method. In this way the robustness and reliability of the coupled cluster theory were incorporated into the modern formalism for

Piezoelectric semiconductors can be polarized and used in mechanoredox systems and photoredox catalysis. Conventional non-piezoelectric semiconductors have limitations when it comes to charge carrier recombination and slow transport rates in catalytic reactions, which can be overcome by piezoelectric polarization processes in piezoelectric semiconductors. Heterostructures based on semiconducting piezoelectrics often offer enhanced catalytic reactivities that are related to their mechanical, piezoelectric, optical, and electronic characteristics. We review how to use such heterostructures to convert mechanical energy into chemical energy, and how the related piezoelectric polarization tunes the band structures and provides advantages in piezophotocatalysis over regular photocatalysis. We discuss fundamental concepts of piezoelectricity, piezoelectric potential, and examine different piezoelectric heterostructures for piezo- and piezophotocatalysis. A review of dynamic investigations of piezo- and piezophotocatalytic processes is presented. The complementary developments in the understanding of the piezotronic and piezophototronic effects are described, which include the induced charge-transfer mechanisms for piezo- and piezophotocatalytic reactions that can occur with piezoelectric heterostructures. Finally, we derive design principles and suggest future research directions in the emerging field of piezo- and piezophotocatalysis employing semiconductive heterostructures.

Sulfur-containing compounds are undesirable in fossil fuels, thus stringent regulations are in place to curb their atmospheric emissions. In this context, we hypothesized and showed that acid catalysis promoted by metal particles could be used to oxidize dibenzothiophene (DBT) and benzothiophene (BT) into sulfones that, in principle, can be subsequently removed. In specific, we studied the oxidative step of catalytic oxidative desulfurization (CODS) processes using a new bifunctional catalyst based on Pd-promoted molybdovanadophosphoric acid (Pd-PMV) supported on mesoporous zirconia (Pd-PMV/mZrO2). The PMV was supported on zirconia using a one-pot sol–gel method, and the Pd nanoparticles were deposited in a subsequent step. The activity of catalyst was excellent, with high conversions >99% and a turnover frequency (TOF) value of 384 h−1 for DBT, using catalyst Pd-15PMV/mZrO2, which had 15-wt% loading of PMV. tert-butyl hydrogen peroxide (tBHP) was used as an oxidant under relatively mild reaction conditions. The catalyst had both Brønsted and Lewis acid sites, and the Pd nanoparticles enhanced its synergistic catalytic performance. Up to a threshold level loading of PMV, the thermal stability of the catalysts was higher than the underlying mZrO2 support. A high catalytic activity was maintained with only a minor loss over 10 cycles, making the catalyst promising for oxidative deep-desulfurization of liquid hydrocarbon fuels.

Despite the growing use of organic or mixed solvents in zeolite processing, most studies focus only on aqueous suspension systems. We investigated the colloidal characteristics of submicron-sized zeolite NaA in mixed ethanol-water solvents. The effects of the mixing ratio of solvents and various additives on the dispersion of the zeolite powders were studied. The zeolite NaA particles were destabilized in solvent mixtures at a high ethanol-to-water ratio, a reduction in the zeta potential was observed, and the destabilization was rationalized by the Derjaguin, Landau, Verwey, Overbeek (DLVO) theory. An improved stabilization of the zeolite NaA suspensions was achieved in ethanol-rich solvent mixtures using nonionic low molecular weight organic additives, but not with their ionic counterparts such as anionic, cationic surfactants or inorganic acids or bases. Polyethylene glycol (PEG)-400 was found to be a good dispersant for the submicron-sized zeolite NaA particles in the ethanol-water mixtures, which was attributed to its interaction with the zeolite surface, leading to an increased zeta potential. The PEG-stabilized zeolite suspensions led to low suspension viscosities as well as uniform and consistent spin-coated films.

Methane has been successfully encapsulated within cages of C-60 fullerene, which is an appropriate model system to study confinement effects. Its chemistry and physics are also relevant for theoretical model descriptions. Here we provide insights into intermolecular interactions and predicted spectroscopic responses of the CH4@C-60 complex and compared them with results from other methods and with data from the literature. Local energy decomposition analysis (LED) within the domain-based local pair natural orbital coupled cluster singles, doubles, and perturbative triples (DLPNO-CCSD(T)) framework was used, and an efficient protocol for studies of endohedral complexes of fullerenes is proposed. This approach allowed us to assess energies in relation to electronic and geometric preparation, electrostatics, exchange, and London dispersion for the CH4@C-60 endohedral complex. The calculated stabilization energy of CH4 inside the C-60 fullerene was -13.5 kcal mol(-1) and its magnitude was significantly larger than the latent heat of evaporation of CH4. Evaluation of vibrational frequencies and polarizabilities of the CH4@C-60 complex revealed that the infrared (IR) and Raman bands of the endohedral CH4 were essentially silent due to the dielectric screening effect of C-60, which acted as a molecular Faraday cage. Absorption spectra in the UV-vis domain and ionization potentials of C-60 and CH4@C-60 were predicted. They were almost identical. The calculated H-1/C-13 NMR shifts and spin-spin coupling constants were in very good agreement with experimental data. In addition, reference DLPNO-CCSD(T) interaction energies for complexes with noble gases (Ng@C-60; Ng = He, Ne, Ar, Kr) were calculated. The values were compared with those derived from supramolecular MP2/SCS-MP2 calculations and estimates with London-type formulas by Pyykko and coworkers [Phys. Chem. Chem. Phys., 2010, 12, 6187-6203], and with values derived from DFT-based symmetry-adapted perturbation theory (DFT

Metal-free nitrogen-doped carbon is considered as a green functional material, but the structural determination of the atomic positions of nitrogen remains challenging. We recently demonstrated that directly-excited solid state N-15 NMR (ssNMR) spectroscopy is a powerful tool for the determination of such positions in N-doped carbon at natural N-15 isotope abundance. Here we report a green chemistry approach for the synthesis of N-doped carbon using cellulose as a precursor, and a study of the catalytic properties and atomic structures of the related catalyst. N-doped carbon (NH3) was obtained by the oxidation of cellulose with HNO3 followed by ammonolysis at 800 degrees C. It had a N content of 6.5 wt% and a surface area of 557 m(2) g(-1), and N-15 ssNMR spectroscopy provided evidence for graphitic nitrogen besides regular pyrrolic and pyridinic nitrogen. This structural determination allowed probing the role of graphitic nitrogen in electrocatalytic reactions, such as the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and nitrite reduction reaction. The N-doped carbon catalyst (NH3) showed higher electrocatalytic activities in the OER and HER under alkaline conditions and higher activity for nitrite reduction, as compared with a catalyst prepared by the carbonization of HNO3-treated cellulose in N-2. The electrocatalytic selectivity for nitrite reduction of the N-doped carbon catalyst (NH3) was directly related to the graphitic nitrogen functions. Complementary structural analyses by means of C-13 and H-1 ssNMR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and low-temperature N-2 adsorption were performed and provided support to the findings. The results show that directly-excited N-15 ssNMR spectroscopy at natural N-15 abundance is generally capable of providing information on N-doped carbon materials if relaxation properties ar

Biomethane is a renewable fuel with a small environmental footprint. In its production, the removal of CO2 from the fermentation gas is critical. Pressure and vacuum swing adsorption (PSA and VSA) processes have certain advantages over other processes for the removal. Silicoaluminophosphate-56 (SAPO-56) has promising properties as an adsorbent for PSA- or VSA-based upgrading of raw biogas. It is typically synthesized by using N,N,N', N'-tetramethyl-1,6-hexanediamine (TMHD) as a structure directing agent (SDA). In this study, TMHD was partly replaced with three different low-cost templates: isopropylamine (IPA), dibutylamine, and tripropylamine. SAPO-56 was co-crystallized with mixtures of templating amines with up to a ratio of 30%:70% of TMHD:IPA. With using TMHD and IPA, small and defined crystals of SAPO-56 plus SAPO-47 formed instead of the large aggregates of SAPO-56 that formed when only TMHD was used. Solid-state 13C NMR spectroscopy was used to show that the IPA and TMHD had not been decomposed and that both molecules were included within the assynthesized crystals of SAPO-56. Synthetic composition diagrams were drawn with respect to the P2O5, SiO2, and Al2O3 compositions of the reaction mixtures and the formed crystalline SAPOs. In relation to these diagrams, the domains for stability of SAPO-56 were contrasted with those of SAPO-11, -17, -20, and -47. In particular, it was observed that SAPO-47 co-crystallized with SAPO-56 when a very large fraction of IPA was used under otherwise optimized conditions. As consistent with other studies, the SAPO-56 synthesized with dual SDAs had a very high uptake of CO2 at conditions relevant for PSA- or VSA-driven upgrading of raw biogas into methane.

A femtosecond laser process is presented increasing the surface area of copper electrocatalysts for an electrochemical CO2 reduction reaction (CO2RR). The laser treatment allows us to tune the surface morphology and the chemical composition of the copper electrocatalysts. This tunability is used to correlate the role of the surface area and catalyst dopants with the selectivity of the CO2RR. The liquid products of the CO2RR are monitored through ex situ nuclear magnetic resonance spectroscopy. The products’ distribution shows that the electrode surface area plays a key role in the electrochemical conversion of CO2 into multicarbon liquid products. We show that sulfur dopants boost the production of formate. Remarkably, by co-doping sulfur and fluoride, we show that the chalcogenide dopant counteracts the known boosting effect of fluoride to convert CO2 into multicarbon products. Oxygen doping in the range of 2–19 atom % does not significantly affect the distribution of liquid products from CO2 electroreduction. In a broad perspective, this work highlights the potential of the femtosecond laser process to fine-tune surfaces to produce photo- and electrocatalyst materials.

Methanol is a liquid hydrogen carrier and potential platform molecule, and significant efforts are currently devoted to hydrogenate CO2 to methanol. In this work, hydrogenations of CO2 and captured CO2 (as dimethyl-carbamic acid, DMCA, and methylcarbamic acid, MCA) to methanol over Ru-MACHO (pre)catalysts were studied with a Ru-II-catalyst model by Density Functional Theory (DFT) calculations. For the hydrogenation of CO2, the concerted reaction was the rate-determining step involving a synchronous hydride transfer and proton transfer from the Ru-II-catalyst to coordinatively saturated intermediate methanediol. In the hydrogenation cycles of DMCA and MCA, the first hydride transfer reactions were more difficult than the concerted hydride and proton transfer from the Ru-II-catalyst to the aldehyde group of intermediate formaldehyde. These first hydride transfer reactions were identified as the rate-determining steps. The hydrogenations of DMCA and MCA were found much more favourable in methanol production than the direct CO2 hydrogenation, however, formamides could be main intermediate products due to the easier C-O breakage than C-N breakage in gem diols, and during the further hydrogenation of formamides, formaldehyde could be the main intermediate due to the easier C-N breakage than C-O breakage in alkanolamines. In all three hydrogenation cases, the amino (NH) ligand of the Ru-II-catalyst initially remained chemically innocent, and intermediates were stabilized by N-H center dot O hydrogenbonding interactions (HBIs) facilitating the continuation of catalytic hydrogenation cycles, but the NH ligand took part in multi-bond concerted reactions to produce eventually methanol.

The chemisorption of CO2 on aminated silica has a rich chemistry, and its details are important to research in relation to CO2 capture and catalytic chemistry. In this study, such chemisorption was investigated on aminated and diaminated silica with H-1 and C-13 solid state nuclear magnetic resonance (NMR) spectroscopy under dry and wet conditions. Fast magic-angle spinning (MAS) allowed us to obtain high resolution spectra. Porous silica was modified into a monoaminated version using (3-aminopropyl)triethoxysilane (APTS) and a diaminated one by using 3-(2-aminoethylamino)propyltriethoxysilane (AEAPTS). From the corresponding NMR spectra we could conclude that, under dry conditions, CO2 chemisorbed as carbamic acid and carbamate ammonium ion pairs and gave similar spectra for both directly-excited C-13 and under cross-polarization (CP) {H-1}C-13 MAS NMR. Under wet conditions, direct excitation and {H-1}C-13 CPMAS NMR showed that carbamate ammonium ion pairs formed along with bicarbonates (HCO3-). For the wet conditions, the C-13 and H-1 NMR spectra were especially well resolved, and we could detect two different types of carbamate ammonium ion pairs forming on the diaminated silica. We conclude that carbamate ammonium ion pairs and HCO3- moieties can be detected by {H-1}C-13 MAS NMR, at least qualitatively, in addition to the more time consuming direct excitation.

Zeolites with appropriately narrow pore apertures can kinetically enhance the selective adsorption of CO2 over N-2. Here, we showed that the exchangeable cations (e.g., Na' or K) on zeolite ZK-4 play, an important role in the CO2 selectivity. Zeolites NaK ZK-4 with Si/Al = 1.8-2.8 had very high CO2 selectivity when an intermediate number of the exchangeable cations were K+ (the rest being Na+) Zeolites NaK ZK-4 with Si/Al = 1.8 had high CO, uptake capacity and very high CO2-over-N-2 selectivity (1190). Zeolite NaK ZK-4 with Si/A1 = 2.3 and 2.8 also had enhanced CO2 selectivity with an intermediate number of K cations. The high CO, selectivity was related to the I(' cation in the 8 -rings of the alpha-cage, together with Na+ cations in the 6 -ring, obstructing the diffusion of N2 throughout the zeolite. The positions of the K+ cation in the 8 -ring moved slightly (max 0.2 angstrom) toward the center of the a-cage upon the adsorption of CO2, as revealed by in situ X-ray diffraction. The CO2-over-N-2 selectivity was somewhat reduced when the number of K+ cations approached 100%. This was possibly due to the shift in the IC' cation positions in the 8 -ring when the number of Na+ was going toward 0%, glowing N, diffusion through the 8 -ring. According to 'm situ infrared spectroscopy, the amount of chemisorbed CO2 was reduced on zeolite ZK-4s with increasing Si/Al ratio. In the context of potential applications, a kinetically enhanced selection of CO2 could be relevant for applications in carbon capture and bio- and natural gas upgrading.

Microporous organic polymers (MOPs) with internal pores less than 2 nm have potential use in gas separation, sensing, and storage, in the form of membranes, monoliths, fibers, or adsorbent granules. These covalently bonded polymers are being formed by reacting with rigid organic monomers, and MOPs have lately been studied for capturing CO2 from gas mixtures in the form of membranes and adsorbents. Especially, the potential of MOPs in the processes of carbon capture and storage has been in the focus and small pore MOPs are preferred for regular separation processes but larger pores could be suitable if cryogenic processes would be used. Recent studies (2014 – mid 2019) on the potential use of MOPs as CO2 adsorbents and, to some degree, CO2-selective membranes are reviewed.