Chemistry of Materials for Energy and Environmental Sustainability

We modified C₃-symmetric benzene-1,3,5-tris-amide (BTA) by introducing flexible linkers in order to generate an N-centered BTA (N-BTA) molecule. The N-BTA compound formed gels in alcohols and aqueous mixtures of high-polar solvents. Rheological studies showed that the DMSO/water (1:1, v/v) gels were mechanically stronger compared to other gels, and a similar trend was observed for thermal stability. Powder X-ray analysis of the xerogel obtained from various aqueous gels revealed that the packing modes of the gelators in these systems were similar. The stimuli-responsive properties of the N-BTA towards sodium/potassium salts indicated that the gel network collapsed in the presence of more nucleophilic anions such as cyanide, fluoride, and chloride salts at the MGC, but the gel network was intact when in contact with nitrate, sulphate, acetate, bromide, and iodide salts, indicating the anion-responsive properties of N-BTA gels. Anion-induced gel formation was observed for less nucleophilic anions below the MGC of N-BTA. The ability of N-BTA gels to act as an adsorbent for hazardous anionic and cationic dyes in water was evaluated. The results indicated that the ethanolic gels of N-BTA successfully absorbed methylene blue and methyl orange dyes from water. This work demonstrates the potential of the N-BTA gelator to act as a stimuli-responsive material and a promising candidate for water purification. Full article

Manganese molybdate has garnered considerable interest in supercapacitor research owing to its outstanding electrochemical properties and nanostructural stability but still suffers from the common problems of transition metal oxides not being able to reach the theoretical specific capacitance and lower electrical conductivity. Doping phosphorus elements is an effective approach to further enhance the electrochemical characteristics of transition metal oxides. In this study, MnMoO₄·H₂O nanosheets were synthesized on nickel foam via a hydrothermal route, and the MnMoO₄·H₂O nanosheet structure was successfully doped with a phosphorus element using a gas–solid reaction method. Phosphorus element doping forms phosphorus–metal bonds and oxygen vacancies, thereby increasing the charge storage and conductivity of the electrode material. The specific capacitance value is as high as 2.112 F cm⁻² (1760 F g⁻¹) at 1 mA cm⁻², which is 3.2 times higher than that of the MnMoO₄·H₂O electrode (0.657 F cm⁻²). The P–MnMoO₄//AC ASC device provides a high energy density of 41.9 Wh kg⁻¹ at 666.8 W kg⁻¹, with an 84.5% capacity retention after 10,000 charge/discharge cycles. The outstanding performance suggests that P–MnMoO₄ holds promise as an electrode material for supercapacitors. Full article

In this study, pyrazole tartrate (Pya·DL) and tartaric acid (DL) complexed with cobalt–iron bimetallic modified hydrogen-type mordenite (HMOR) were prepared using the ion exchange method. The results demonstrate that the stability of the dimethyl ether (DME) carbonylation reaction to methyl acetate (MA) was significantly improved after the introduction of Pya·DL to HMOR. The Co∙Fe∙DL-Pya·DL-HMOR (0.8) sample exhibited sustainable stability within 400 h DME carbonylation, exhibiting a DME conversion rate of about 70% and MA selectivity of above 99%. Through modification with the DL-complexed cobalt–iron bimetal, the dispersion of cobalt–iron was greatly enhanced, leading to the formation of new metal Lewis acidic sites (LAS) and thus a significant improvement in catalysis activity. Pya·DL effectively eliminated non-framework aluminum in HMOR, enlarged its pore size, and created channels for carbon deposition diffusion, thereby preventing carbon accumulation and pore blockage. Additionally, Pya·DL shielded the Bronsted acid sites (BAS) in the 12 MR channel, effectively suppressing the side reactions of carbon deposition and reducing the formation of hard carbon deposits. These improvements collectively contribute to the enhanced stability of the DME carbonylation reaction. Full article

With the rapid progress in a power conversion efficiency reaching up to 26.1%, which is among the highest efficiency for single-junction solar cells, organic–inorganic hybrid perovskite solar cells have become a research focus in photovoltaic technology all over the world, while the instability of these perovskite solar cells, due to the decomposition of its unstable organic components, has restricted the development of all-inorganic perovskite solar cells. In recent years, Br-mixed halogen all-inorganic perovskites (CsPbI3−xBrx) have aroused great interests due to their ability to balance the band gap and phase stability of pure CsPbX3. However, the photoinduced phase segregation in lead mixed halide perovskites is still a big burden on their practical industrial production and commercialization. Here, we demonstrate inhibited photoinduced phase segregation all-inorganic CsPbI1.2Br1.8 films and their corresponding perovskite solar cells by incorporating a 1-butyl-1-methylpiperidinium tetrafluoroborate ([BMP]+[BF4]−) compound into the CsPbI1.2Br1.8 films. Then, its effect on the perovskite films and the corresponding hole transport layer-free CsPbI1.2Br1.8 solar cells with carbon electrodes under light is investigated. With a prolonged time added to the reduced phase segregation terminal, this additive shows an inhibitory effect on the photoinduced phase segregation phenomenon for perovskite films and devices with enhanced cell efficiency. Our study reveals an efficient and simple route that suppresses photoinduced phase segregation in cesium lead mixed halide perovskite solar cells with enhanced efficiency. Full article

The fouling of separation membranes has consistently been a primary factor contributing to the decline in membrane performance. Enhancing the surface hydrophilicity of the membrane proves to be an effective strategy in mitigating membrane fouling in water treatment processes. Zwitterionic polymers (containing an equimolar number of homogeneously distributed anionic and cationic groups on the polymer chains) have been used extensively as one of the best antifouling materials for surface modification. The conventional application of zwitterionic compounds as surface modifiers is intricate and inefficient, adding complexity and length to the membrane preparation process, particularly on an industrial scale. To overcome these limitations, zwitterionic polymer, directly used as a main material, is an effective method. In this work, a novel zwitterionic polymer (TB)—zwitterionic Tröger’s base (ZTB)—was synthesized by quaternizing Tröger’s base (TB) with 1,3-propane sultone. The obtained ZTB is blended with TB to fabricate microfiltration (MF) membranes via the vapor-induced phase separation (VIPS) process, offering a strategic solution for separating emulsified oily wastewater. Atomic force microscopy (AFM), scanning electron microscopy (SEM), water contact angle, and zeta potential measurements were employed to characterize the surface of ZTB/TB blended membranes, assessing surface morphology, charge, and hydrophilic/hydrophobic properties. The impact of varying ZTB levels on membrane surface morphology, hydrophilicity, water flux, and rejection were investigated. The results showed that an increase in ZTB content improved hydrophilicity and surface roughness, consequently enhancing water permeability. Due to the attraction of water vapor, the enrichment of zwitterionic segments was enriched, and a stable hydration layer was formed on the membrane surface. The hydration layer formed by zwitterions endowed the membrane with good antifouling properties. The proposed mechanism elucidates the membrane’s proficiency in demulsification and the reduction in irreversible fouling through the synergistic regulation of surface charge and hydrophilicity, facilitated by electrostatic repulsion and the formation of a hydration layer. The ZTB/TB blended membranes demonstrated superior efficiency in oil–water separation, achieving a maximum flux of 1897.63 LMH bar⁻¹ and an oil rejection rate as high as 99% in the oil–water emulsion separation process. This study reveals the migration behavior of the zwitterionic polymer in the membrane during the VIPS process. It enhances our comprehension of the antifouling mechanism of zwitterionic membranes and provides guidance for designing novel materials for antifouling membranes. Full article

Herein, activated red mud particles are used as adsorbents for phosphorus adsorption. HCl solutions with different concentrations and deionized water are employed for desorption tests, and the desorption mechanism under the following optimal conditions is investigated: HCl concentration = 0.2 mol/L, desorbent dosage = 0.15 L/g, desorption temperature = 35 °C, and desorption time = 12 h. Under these conditions, the phosphate desorption rate and amount reach 99.11% and 11.29 mg/g, respectively. Notably, the Langmuir isothermal and pseudo-second-order kinetic linear models exhibit consistent results: monomolecular-layer surface desorption is dominant, and chemical desorption limits the rate of surface desorption. Thermodynamic analysis indicates that phosphorus desorption by the desorbents is spontaneous and that high temperatures promote such desorption. Moreover, an intraparticle diffusion model demonstrates that the removal of phosphorus in the form of precipitation from the surface of an activated hematite particle adsorbent primarily occurs via a chemical reaction, and surface micromorphological analysis indicates that desorption is primarily accompanied by Ca dissolution, followed by Al and Fe dissolutions. The desorbents react with the active elements in red mud, and the vibrations of the [SiO₄]⁴⁻ functional groups of calcium–iron garnet and calcite or aragonite disappear. Further, in Fourier-transform infrared spectra, the intensities of the peaks corresponding to the PO₄³⁻ group considerably decrease. Thus, desorption primarily involves monomolecular-layer chemical desorption. Full article

Dual-ion batteries (DIBs) are a new kind of energy storage device that store energy involving the intercalation of both anions and cations on the cathode and anode simultaneously. They feature high output voltage, low cost, and good safety. Graphite was usually used as the cathode electrode because it could accommodate the intercalation of anions (i.e., PF₆⁻, BF₄⁻, ClO₄⁻) at high cut-off voltages (up to 5.2 V vs. Li⁺/Li). The alloying-type anode of Si can react with cations and boost an extreme theoretic storage capacity of 4200 mAh g⁻¹. Therefore, it is an efficient method to improve the energy density of DIBs by combining graphite cathodes with high-capacity silicon anodes. However, the huge volume expansion and poor electrical conductivity of Si hinders its practical application. Up to now, there have been only a few reports about exploring Si as an anode in DIBs. Herein, we prepared a strongly coupled silicon and graphene composite (Si@G) anode through in-situ electrostatic self-assembly and a post-annealing reduction process and investigated it as an anode in full DIBs together with home-made expanded graphite (EG) as a fast kinetic cathode. Half-cell tests showed that the as-prepared Si@G anode could retain a maximum specific capacity of 1182.4 mAh g⁻¹ after 100 cycles, whereas the bare Si anode only maintained 435.8 mAh g⁻¹. Moreover, the full Si@G//EG DIBs achieved a high energy density of 367.84 Wh kg⁻¹ at a power density of 855.43 W kg⁻¹. The impressed electrochemical performances could be ascribed to the controlled volume expansion and improved conductivity as well as matched kinetics between the anode and cathode. Thus, this work offers a promising exploration for high energy DIBs. Full article