ChemSusChem最新文献

Gel polymer electrolytes (GPEs) are regarded as a promising alternative to conventional electrolytes, combining the advantages of solid and liquid electrolytes. Leveraging the abundance and eco-friendliness of cellulose-based materials,  GPEs were produced using methyl cellulose and incorporating various doping agents, either an ionic liquid (1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr14][TFSI]), its polymeric ionic liquid analogue (Poly(diallyldimethylammonium bis(trifluoromethylsulfonyl)imide) [PDADMA][TFSI]), or an anionically charged backbone polymeric ionic liquid (lithium poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino) sulfonyl) imide] LiP[STFSI]). The ion dynamics and molecular interactions within the GPEs were thoroughly analyzed using Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy (ATR-FTIR), Heteronuclear Overhauser Enhancement Spectroscopy (HOESY), and Pulsed-Field Gradient Nuclear Magnetic Resonance Diffusion (PFG-NMR). Li+ transference numbers (tLi+) were successfully calculated. Our study found that by combining slow-diffusing polymeric ionic liquids (PILs) with fast-diffusing lithium salt, we were able to achieve transference numbers comparable to those of liquid electrolytes, especially with the anionic PIL, LiP[STFSI]. This research highlights the influence of the polymer's nature on lithium-ion transport within GPEs. Additionally, micro supercapacitor (MSC) devices assembled with these GPEs exhibited capacitive behavior. These findings suggest that further optimization of GPE composition could significantly improve their performance, thereby positioning them for application in sustainable and efficient energy storage systems.

Plastic pollution poses a significant challenge to environmental conservation. Efficient recycling of plastic is a key strategy to address this issue. Polyethylene terephthalate (PET), commonly found in plastic bottles, represents a substantial portion of plastic waste. Consequently, the efficient degradation and recycling of PET is crucial for the sustainable development of society. However, the implementation of methods for PET depolymerization and recycling typically necessitates alkaline/acidic pre-treatment and significant energy input for heating. Here, we propose a gentle, and highly efficient photocatalysis approach for selectively degrading PET plastic waste into terephthalic acid (TPA) in high yield (up to 99%) using cost-effective iron salts. Notably, this method achieved excellent selectivity with high TON and TOF values, applying oxygen or air as environmentally friendly oxidants. In addition, the solvent can be recycled without compromising the TPA yield, and large-scale reactions can be performed smoothly.

In the quest for sustainable hydrogen production, the use of biomass-derived feedstock is gaining importance. Acceptorless Dehydrogenation (AD) in the presence of efficient and selective catalysts has been explored worldwide as a suitable method to produce hydrogen from hydrogen-rich simple organic molecules. Among these, glycerol and sugars have the advantage of being cheap, abundant, and obtainable from fatty acid basic hydrolysis (biodiesel industry) and from biomass by biochemical and thermochemical processing, respectively. Although heterogeneous catalysts are more widely used for hydrogen production from biomass-based feedstock, the harsh reaction conditions applied limit applicability due to deactivation of active sites due to coking  of carbonaceous materials. Moreover, heterogeneous catalyst are more difficult to fine-tune than homogeneous counterparts, and the latter also allow for high process selectivities under milder conditions. The present Concept article summarizes the main features of the most active homogeneous catalysts reported for glycerol and monosaccharides AD. In order to directly compare  hydrogen production efficiencies, the choice of literature works was limited to reports where hydrogen was clearly quantified by yields and turnover numbers (TONs). The types of transition metals and ligands is discussed, together with a perspective view on future challenges of homogeneous AD reactions for practical applications.

In this study, the ultrafast transport dynamics of the valence band hole states in CuBi2O4 (CBO) photocathodes were investigated by varying the atomic composition and manipulating their p-type character. As a comprehensive ultrafast optical transient absorption spectroscopy (TAS) investigation of compositionally manipulated CBO that combines both ex situ and in situ TAS experiments with photoelectrochemical (PEC) performance tests, the study reveals the polaron formation tendencies of the valence band (VB) holes at cationic vacancy sites. Therefore, it draws a complete picture of the ultrafast hole transport dynamics and provides valuable insights into the hindrance of the photocurrent generated in CBO.

Over the past years, enzymatic depolymerization of PET, one of the most widely used plastics worldwide, has become very efficient leading to the end products terephthalic acid (TPA) and ethylene glycol (EG) used for PET re-synthesis. Potent alternatives to these monomers are the intermediates BHET and MHET, the mono- and di-esters of TPA and EG which avoid total hydrolysis and can serve as single starting materials for direct re-polymerization. This study therefore aimed to selectively prepare those intermediates through reaction medium engineering during the biocatalytic hydrolysis of PET. After a comparative pre-screening of 12 PET-hydrolyzing enzymes, two of them (LCC^ICCG, IsPETase^wt) were chosen for detailed investigations. Depending on the reaction conditions, MHET and BHET are predominantly obtainable: (i) MHET was produced in a better ratio and high concentrations at the beginning of the reaction when IsPETase^wt and 10 % EG was used; (ii) BHET was produced as predominant product when LCC^ICCG and 25 % EG was used. TPA itself was nearly the single product at pH 9.0 after 24 h due to the self-hydrolysis of MHET and BHET under basic conditions. Using medium engineering in biocatalytic PET-hydrolysis, the product profile can be adjusted so that TPA, MHET or BHET is predominantly produced.

Hydrogen peroxide (H₂O₂) is a widely used strong oxidant, and its traditional preparation methods, anthraquinone method, and direct synthesis method, have many drawbacks. The method of producing H₂O₂ by two-electron oxygen reduction reaction (2e^- ORR) is considered an alternative strategy for the traditional anthraquinone method due to its high efficiency, energy saving, and environmental friendliness, but it remains a big challenge. In this review, we have described the mechanism of ORR and the principle of electrocatalytic performance testing, and have summarized the standard performance evaluation techniques for electrocatalysts to produce H₂O₂. Secondly, according to the theoretical calculation and experimental results, several kinds of efficient electrocatalysts are introduced. It is concluded that noble metal-based materials, carbon-based materials, non-noble metal composites, and single-atom catalysts are the preferred catalyst materials for the preparation of H₂O₂ by 2e^- ORR. Finally, the advantages and novelty of 2e^- ORR compared with traditional methods for H₂O₂ production, as well as the advantages and disadvantages of the above-mentioned high-efficiency catalysts, are summarized. The application prospect and development direction of high-efficiency catalysts for H₂O₂ production by 2e^- ORR has been prospected, which is of great significance for promoting the electrochemical yield of H₂O₂ and developing green chemical production.

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial processes at the cathode of zinc-air batteries. Developing highly efficient and durable electrocatalysts at the air cathode is significant for the practical application of rechargeable zinc-air batteries. Herein, N-doped layered MX containing Co₂P/Ni₂P nanoparticles is synthesized by growing CoNi-ZIF on the surface and interlayers of the two-dimensional material MXene (Ti₂C₃) followed by phosphating calcination. The growth of CoNi-ZIF on the surface of MXene results in the attenuation of high-temperature structural damage of MXene, which in turn leads to the formation of Co₂P/Ni₂P@MX with a hierarchical configuration, higher electron conductivity, and abundant active sites. The optimized Co₂P/Ni₂P@MX achieves a half-wave potential of 0.85 V for the ORR and an overpotential of 345 mV for the OER. In addition, DFT calculations were adopted to investigate the mechanism at the atomic and molecular levels. The liquid zinc-air battery with Co₂P/Ni₂P@MX as the cathode exhibits a specific capacity of 783.7 mAh g^-1 and exceeds 280 h (840 cycles) cycle stability, superior to zinc-air batteries constructed by the cathode of commercial Pt/C+RuO₂ and other previous works. Furthermore, a solid-state battery synthesized with Co₂P/Ni₂P@MX as the cathode exhibits stable cycle performance (154 h/462 cycles).

In the conversion of furfural using non-noble metal catalysts, preferential cleavage of the C2-O bond followed by hydrogenation of the C=C bond facilitates selective access to valuable 1,5-pentanediol (1,5-PeD). Herein, we developed CeO₂ loaded core-shell CoO@Co nanoparticle catalysts. Adjusting Co loading, Fe doping, and reduction temperature improved reaction efficiency. 7Co-0.2Fe/CeO₂ catalysts reduced at 500 °C demonstrated optimal performance. 1,5-PeD produced at 54.76 mmol/g_Co/h, representing the top activity levels among the reported catalysts. H₂-TPR, XRD, HAADF-STEM, FT-IR, XPS, and XANES were employed to investigate the catalyst structure-activity relationship. Co²⁺ cleaves furan ring C-O bond, Co⁰ promotes double-bond hydrogenation. The CoO@Co structure favors the desired 1,5-PeD production route. Trace Fe species optimize the Co²⁺/Co⁰ ratio, enhance the substrate adsorption, and inhibit the furan ring saturation. These findings emphasize the importance of fine-tuning catalyst structure and composition for selectivity improvement.

The recycling of lithium batteries is essential for a sustainable energy transition. However, impurities in the products obtained from the black mass can lower their market value. In this work, lithium carbonate, which has the highest market share among lithium-based products, is purified using distilled water at controlled temperature, time and stirring speed. The purification process involves dissolving lithium carbonate in distilled water at low temperatures (between 0 and 10 °C), followed by crystallization through water evaporation. Optimal conditions yielded lithium carbonate with a purity of 99.66 % after two stages of purification. The dependence of the variables on the final purity was deeply analyzed and the thermodynamics of the reaction was studied, confirming the exothermic nature of the dissolution reaction.