Green Chemistry最新文献

New and enhanced processes will not be the only drivers toward a sustainable chemical industry. Implementing climate policies will impact all components of the chemical supply chain over the following decades, making improvements in energy generation, material extraction, or transportation contribute to reducing the overall impacts of chemical technologies. Including this synergistic effect when comparing technologies offers a clearer vision of their future potential and may allow researchers to support their sustainability propositions more strongly. Ammonia and methanol production account for more than fifty percent of the CO₂ emissions in this industry and are, therefore, excellent case studies. This work performs a prospective life cycle assessment until 2050 for fossil, blue, wind, and solar-based technologies under climate policies aiming to limit the global temperature rise to 1.5 °C, 2 °C, or 3.5 °C. The first finding is the inability of fossil-based routes to reduce their CO₂ emissions beyond 10% by 2050 without tailored decarbonisation strategies, regardless of the chemical and climate policy considered. In contrast, green routes may produce chemicals with around 90% fewer emissions than today and even with net negative emissions (on a cradle-to-gate basis), as in the case of methanol (up to −1.4 kg CO₂-eq per kg), mainly due to the contributions of technology development and increasing penetration of renewable energies. Overall, the combined production of these chemicals could be net-zero by 2050 despite their predicted two to fivefold increase in demand. Lastly, we propose a roadmap for progressive implementation by 2050 of green routes in 26 regions worldwide, applying the criterion of at least 80% reduction in climate change impacts when compared to their fossil alternatives. Furthermore, an exploratory prospective techno-economic assessment showed that by 2050, green routes could become more economically attractive. This work offers quantitative arguments to reinforce research, development, and policymaking efforts on green chemical routes reliant on renewable energies.

We demonstrate that the catalytic metal centre for ammonia production can be selectively activated with only a slight alteration in ligand isomerization (α and β isomers), making it practical and effective even for agricultural effluents. With almost 90% faradaic efficiency, the β isomer generates approximately 0.64 mg h⁻¹ cm⁻² of ammonia. Energy-efficient ammonia recovery is made possible by the interfacial proton charge assembly that β-isomerization creates, which attracts the reacting nitrate and repels the competing hydronium ions. With minimal energy consumption, this isomerization approach can interconvert agricultural effluents into ammonia fuel, reaching up to 84% of its theoretical yield and maintaining stability over 100 hours of continuous electrolysis.

Electrochemical conversion of CO₂ and NO₃⁻ waste (EC-CO₂/NO₃⁻) into valuable urea is a promising method for fertilizer production and environmental remediation, but its practical application is currently limited by the low efficiency of electrocatalytic processes. Here, we report a novel In₂O₃ nanotube (In₂O₃-NT) material derived from a metal–organic framework (MOF) which functions as an electrocatalyst for durable and efficient urea synthesis via EC-CO₂/NO₃⁻. The obtained In₂O₃-NT-500 with a porous structure and rich oxygen vacancies (Vo) is more conducive to the target reaction system, reaching a urea formation rate of 1441 μg mg_cat⁻¹ h⁻¹ with a high faradaic efficiency of 60.3%, exhibiting the top-level performance toward urea synthesis via the current route. In situ attenuated total reflection Fourier transform infrared spectroscopy verified that In₂O₃-NT with enriched Vo could stabilize the *CO₂NH₂ intermediate, thus accelerating the rate-determining step (RDS). The DFT simulation demonstrated that the transformation of *COOHNH₂ to *CONH₂ is the RDS for urea formation. The defect-engineered In₂O₃-NT catalyst significantly lowers the energy barrier for this step, thus boosting the overall efficiency of urea synthesis. This work provides an example showing that the defect engineering of In₂O₃-NT is highly capable of activating CO₂ and NO₃⁻ waste molecules for urea synthesis, and is conceptually versatile for other value-added chemical production methods.

Aqueous zinc-ion batteries (ZIBs) offer numerous advantages, such as high energy density, enhanced safety, and low cost, making them an ideal choice for energy storage and conversion applications in the “post-lithium” era. Hydrogel electrolytes, as the key component of flexible ZIBs, combine the ionic conductivity of traditional water electrolytes with the dimensional stability of solid polymer electrolytes. However, it remains a challenge to design comprehensive and appropriate hydrogel electrolytes to provide flexible ZIBs with good reversibility and versatility. This review discusses the engineering design of hydrogel electrolytes required for flexible ZIBs from the viewpoint of an electrolyte designer. The basic properties of the hydrogel electrolytes, zinc anodes, cathodes and electrolyte stabilization effects are described in detail. Furthermore, we explore the various challenges faced by hydrogel electrolytes and propose corresponding strategies. Finally, the review offers insights into the future development of hydrogel-stabilized ZIBs.

Hard carbon (HC) exhibits promising potential as an anode material for sodium-ion batteries; however, it is confronted with challenges such as low initial coulombic efficiency (ICE) and poor rate performance. Developing biomass-based binders is a significant strategy to promote electrochemical performance and improve the stability of the solid electrolyte interface (SEI). In this work, green biomass of carboxymethyl cellulose (CMC) and sodium lignosulfonate (LS) with excellent adhesion and dispersibility is demonstrated as an efficient binder for hard carbon anodes. The semi-rigid skeleton of LS effectively wraps the hard carbon particles, surface modifies HC, and fills defects. The polar functional groups of the binder facilitate the adsorption of Na⁺ and reduce irreversible Na⁺ insertion. Furthermore, the functional groups induce the formation of a unique SEI layer. The SEI layer consists of an organic outer layer and an inorganic inner layer, promoting ion transport and mechanical integrity. Therefore, the HC anode with the CMC/LS binder demonstrates a high reversible capacity of 348 mA h g⁻¹ at 0.05 A g⁻¹, a high ICE of 87%, and an outstanding rate performance with 243 mA h g⁻¹ at 5 A g⁻¹.

In this work, we present a sustainable and environmentally benign electrochemical method for the synthesis of β-keto spirolactones. The reaction is carried out using green solvents such as acetone and water, and simple electrons as oxidants, instead of the stoichiometric oxidants used in classical approaches. The robustness of the method allows the functionalization of cyclic β-keto esters and a β-keto amide, the latter affording α-spiroiminolactone. The method also gives good results with double bonds bearing substituents of different electronic natures. Furthermore, this methodology can be easily scalable through a continuous flow electrochemical approach that improves the productivity of the reaction. Mechanistic investigations support the radicalic nature of the transformation, and the generation of a carbocation intermediate that is further trapped with the water employed as co-solvent in the reaction.

Furfural (mainly furfural and 5-hydroxymethylfurfural) and its derivatives stand out as an important platform for C5 and C6 compounds from lignocellulosic biomass. Catalytic valorization of these renewable carbohydrates not only enables the manufacture of various high-valued chemicals but also enriches routes and theories for the direct use of crude biomass. Photocatalytic conversion of furfural and its derivatives using solar energy has recently received great attention. Such an environmentally friendly and energy-saving approach enables activation and transformation of the target chemical bonds under very mild reaction conditions using photoexcited charge carriers or photogenerated reactive species. However, highly selective photocatalysts are somewhat lacking and the reaction mechanisms usually remain obscure. Herein, this review article aims to systematically summarize the recent advances in sunlight-driven photocatalytic conversion of furfural and 5-hydroxymethylfurfural to sustainable building-block chemicals. In particular, the strategies of catalyst design and the unique roles of reactive species (i.e., photogenerated electrons and holes, hydroxyl and superoxide radicals, and singlet oxygen) are discussed. This allows insights into the catalytic mechanisms. In addition, the latest progress in the combination of such photooxidation with H₂ evolution or CO₂ reduction, as well as photo(electro)chemical conversion, is also reviewed. In addition to the common oxidation and reduction reactions, some nontraditional reaction paths (i.e., reductive coupling, oxidative decarboxylation and ring-opening) and promising products are introduced. Finally, challenges and future opportunities from the perspective of green chemistry are also analyzed. Therefore, a bright prospect can be foreseen in the near future for many more photocatalytic valorizations of furfural-like molecules.

A highly reversible Zn metal anode is the prerequisite for realizing the practical applications of aqueous Zn ion batteries (ZIBs), which are limited by severe zinc dendrites and corrosion. Herein, bio-inspired hydroxyl-rich l-ascorbic acid (vitamin C, l-Aa) was employed to regulate coordination chemistry via the strong interaction between –OH and H₂O with dual remodeling functions and further improve the reversibility of Zn anodes. Specifically, l-Aa not only reconstructs the Zn²⁺ solvation shell, thus reducing Zn²⁺ desolvation energy, but also forms a molecular adsorption interface via excellent zincophilicity to improve zinc redox kinetics and suppress Zn anode corrosion. Meanwhile, the molecular adsorption interface facilitates the homogenization of the interfacial electric field, thereby promoting the predominant deposition of Zn(002). Consequently, the Zn//Cu asymmetric cell presents a low overpotential for zinc nucleation and exceptional average coulombic efficiency (CE) of 99.6% over 1200 cycles at a high current density of 20 mA cm⁻². The Zn//Zn cell also delivers excellent cycling stability for over 1400 h at 5 mA cm⁻². In addition, the Zn//MnO₂ full cell exhibits a robust long-term cycling performance of 1000 cycles at 1 A g⁻¹. This strategy of simultaneously regulating coordination chemistry and further constructing molecular interfaces may boost the applications of highly reversible ZIBs.

The development of an efficient and environmentally sustainable chemical hydrolysis process for recycling waste plastics, based on green chemistry principles, is a key challenge. In this work, we investigated the role of subcritical CO₂ on the hydrolysis of polyethylene terephthalate (PET) into terephthalic acid (TPA) at 180–200 °C for 10–100 min. The addition of CO₂ into the reaction mixture led to the in situ formation of carbonic acid that helps to catalyze PET hydrolysis relative to hot compressed H₂O (i.e. N₂–H₂O). The highest TPA yield of 85.0 ± 1.3% was obtained at 200 °C, PET loading of 2.5 g PET in 20 mL H₂O for 100 min, and 208 psi of initial CO₂ pressure. In addition, the subcritical CO₂–H₂O system demonstrated high selectivity toward hydrolyzing PET in a mixture with polyethylene (PE) at 200 °C for 100 min, thus providing “molecular sorting” capabilities to the recycling process. The robustness of the process was also demonstrated by the ability to hydrolyze both colored Canada Dry and transparent Pure Life® waste PET bottles into high yields of TPA (>86%) at 200 °C. In addition, subcritical CO₂–H₂O hydrolysis of colored PET bottles resulted in a white TPA product similar to that generated from transparent PET bottles. Overall, this work shows that, under optimized reaction conditions, subcritical CO₂ can provide acid tunability to the reaction medium to favor waste PET hydrolysis for subsequent recycling.