Green Chemistry最新文献

A green and efficient synthetic route to novel tetrahydropyrimidine-fused coumarins has been established via a visible-light-induced multicomponent reaction. This additive- and exogenous photocatalyst-free strategy employs 4-aminocoumarins, N-arylglycines, and formaldehyde as readily available feedstocks, proceeding under mild conditions with high atom economy. The protocol features broad substrate scope, excellent functional group compatibility, high yields and facile scalability. Furthermore, the synthesized compounds exhibit promising biological activities in preliminary assays.

Methanol oxidation reaction (MOR) has garnered extensive attention as a pivotal technology for the synthesis of high-value-added products. However, the high selectivity of methanol oxidation products into high-value formic acid requires precise control of the reaction pathway and the reconstruction of Ni. Herein, a microbial corrosion strategy was employed to construct Ni(Fe)(OH)₂–FeS nanosheets. The constructed Ni(Fe)(OH)₂–FeS electrode exhibits superior MOR performance, achieving 1.378 V vs. RHE at 10 mA cm⁻² with a Tafel slope of 21 mV dec⁻¹. Density functional theory calculations indicate that the introduced S²⁻ enables modulation of the d-band center and the coordination environment of Ni sites. Furthermore, this effect can promote the buildup of *OH at the active site, thus increasing the local *OH concentration around the electrode surface. Moreover, the anion S²⁻ promotes the surface reconstruction of Ni(Fe)(OH)₂ and enhances the Ni–O bond in Ni(Fe)OOH–FeS, thereby optimizing the adsorption and binding energy of the intermediate, which significantly enhances the MOR performance. This innovative design facilitates the controlled conversion of the *CHO intermediate to HCOOH by enhancing the CO-free pathway, demonstrating significant potential in fostering the sustainable advancement of the interdisciplinary fusion between biology and clean energy technologies.

Conventional thermosets cannot self-repair at room temperature due to their immobilized networks and chain segments in the glassy state and are unrecyclable due to permanent cross-links. Herein, we design a new class of room-temperature self-healing thermosets with chemical upcyclability. The incorporation of amine-terminated dangling chains into the cross-linked networks provides two complementary advantages: (i) the terminal amines readily form hydrogen bonds with hydroxyl and ester groups, and due to their high mobility, these hydrogen bonds can reorganize in the glassy state; (ii) the hydrogen-bond network mediated by terminal amines effectively weakens the bond energy of disulfide bonds, thereby facilitating their dynamic exchange under mild pressure at room temperature. ¹³C NMR of the soluble network fraction together with gel-fraction analysis indicates that tertiary-amine-assisted transesterification may occur to a limited extent under mild pressure at room temperature. Consequently, the cross-linked networks exhibit exceptional room-temperature self-healing capability. Remarkably, the damaged material autonomously restores 86.8% of its tensile strength at room temperature without external intervention and achieves 100% recovery within 30 min under mild pressure. Moreover, end-of-life ETs can be mildly degraded and efficiently chemically upcycled into high-performance poly(urethane-urea) elastomers. This work presents a practical molecular strategy for sustainable thermosets that couple glassy-state self-repair with mechanical robustness and circular-economy compatibility.

The electrocatalytic upgrading of biomass-derived furanics offers a sustainable route to high-value monomers for polymer manufacturing. Herein, we report a bromine-mediated electrochemical platform that converts 2-furoic acid and CO₂ into 2,5-furandicarboxylic acid (FDCA) and its dimethyl ester, dimethyl furan-2,5-carboxylate (FDME), under ambient conditions with faradaic efficiency exceeding 80% for the critical debromocarboxylation step. Specifically, our process involves sequential esterification and bromination of 2-furoic acid to yield methyl 5-bromofuran-2-carboxylate (MBFC), followed by electrochemical debromo-carboxylation on Ag to afford 5-(methoxycarbonyl)-2-furoic acid (MFCA). Subsequent hydrolysis or esterification would furnish the synthesis of FDCA and FDME, respectively. Comprehensive mechanistic studies, including in situ infrared spectroscopy, single-crystal facet analysis, and computational investigation, reveal that the key debromocarboxylation reaction proceeds through a two-electron transfer pathway, with Ag (100) and Ag (311) facets exhibiting the lowest activation barriers. Importantly, coupling cathodic debromocarboxylation with anodic bromide oxidation enables a paired electrolysis configuration in which the generated Br₂ can be recycled for substrate bromination, eliminating the need for a sacrificial anode and enhancing electron economy. Such an integrated, redox-balanced system establishes a scalable and environmentally benign route for converting renewable furanics and CO₂ into polymer precursors, highlighting the potential of bromine-mediated paired electrolysis for sustainable electrosynthetic manufacturing.

The selective recovery of lithium-ion battery (LIB) cathodes with high leaching efficiency and low-energy consumption using water-containing green solvents is challenging. However, to date, there have been limited reports on using water as a green solvent for the selective recovery of LIB cathodes. Here, we propose for the first time a dual-stage skeleton-disruption (DSSD) strategy for the selective recycling of LIB cathodes at room temperature using water-containing green solvents. In the first stage, under temperature conditions of 60 °C for 24 h, the leaching efficiencies of Li, Co, Ni, and Mn from NCM using low-melting mixture solvents reach 91.4%, 1.0%, 30.9%, and 28.7%, and the leaching selectivity ratios of metals are calculated to be 91.4, 30.9, and 28.7, respectively. In the second stage, all the remaining metals in the residue after the first stage can be rapidly and completely dissolved in water at room temperature. The DSSD strategy shows a high level of applicability for common cathodes, such as NCM, LCO and LFP. This work provides a novel and general strategy for the selective recycling of LIB cathode materials with high sustainability and low-energy consumption.

This article discusses the challenges to a resilient energy transition. The power shortage in the Iberian Peninsula in 2025 illustrates the limitations of a resilient energy sector. To the best of our knowledge, the reason for the collapse of the Spanish electric grid has not been identified as a single system failure but was likely caused by a cascade of events that led to the instability of the grid (frequency) and the shutdown. Fortunately, the grid was restored within a day. A prolonged shortage could have had a massive impact, compromising the food supply, fresh-water supply and critical infrastructure (i.e. hospitals) for 60 million citizens since off-grid energy storage only covers short periods. Broader implementation of large energy storage could have been the key to stabilising the electric grids and preventing a shutdown. Hydrogen is promising for large energy storage to improve the safe operation/implementation of renewable energies/UNSDG7 (PV/solar/wind/hydropower) and may prevent a variation in power supply and grid stability. Considering the required scale-up for the infrastructure (UNSDG9 + 12) along with the essential role of academia/education (UNSDG4) as the fundamental keys for sustainability, these factors are limiting, and the requirements to enable a fast energy transition are alarming. Data on energy consumption and GHG emissions discussed here are exemplary for selected European countries (France/Germany/Portugal/Spain/Sweden/UK) and neighbouring Morocco/Africa. The countries’ strategies for the energy transition take into account different geographical/topological/natural/climatic limitations and opportunities. We have learnt from this blackout and previous events that the number and capacities/connectivity to neighbouring countries are crucial for blackout prevention and that implemented energy storage is important to stabilise the electric grid but remains insufficient for net-zero based on renewable energies. Islands, countries with large coastal regions or isolated countries (mountains) with limited connectivity to neighbouring grids are more sensitive to blackouts. National strategies need to consider the societal/industrial requirements to enable a net-zero transition. The assessment targets defossilisation for energy supply/transport, the requirements for the energy sector and large energy storage facilities (i.e. H₂ storage) and national infrastructures for its realisation. The goal of net-zero-by-2050 is challenged by natural resources, and delays are due to the limited infrastructure/workforce in the STEM field provided by the respective national education and academic sectors.

This review explores the advancements made toward sustainable practices in the field of additive manufacturing for electroanalysis. The adoption of Fused Filament Fabrication within the field of electroanalysis has allowed the development of unique sensing platforms, but reliance on commercially available conductive filament has limited the field. Through the development of bespoke filament researchers have progressed both the performance and sustainability of the produced filaments, moving towards using recycled polymers and bio-based additives. Key advancements have been made utilising base polymers with improved chemical and electrochemical stability, facilitating the transition away from single-use electrodes. Despite these advancements, critical challenges remain, especially considering the end-of-life processing of these items and the implementation of closed-loop recycling systems. Continued efforts are essential to realise a true circular economy electroanalytical device fabrication.

We describe an efficient and feasible visible-light-driven photocatalytic protocol for the synthesis of γ,γ-difluoroallylic ketones from α-trifluoromethyl alkenes. A recyclable and photostable heterogeneous CdS photocatalyst is employed for the first time to promote this transformation via a radical–polar crossover pathway using readily available aliphatic and aromatic aldehydes as acyl radical precursors. The method proceeds under mild conditions, exhibits a broad substrate scope, and demonstrates excellent tolerance to various functional groups. Notably, the protocol enables the late-stage functionalization of biologically active molecules, offering a sustainable and metal-free approach to access valuable difluoroalkylated carbonyl compounds.

Meeting surging lithium-carbonate demand requires routes that are efficient, low-impact, and economically viable. We compare the conventional sulfuric-acid process from β-spodumene with a patented direct lithium extraction (DLE) process from α-spodumene based on low-temperature NaOH roasting, room-temperature water leaching, and CO₂ precipitation, and a newly developed electrochemical direct leaching (EDL) method, which bypasses thermal conversion by operating at room temperature in dilute acid under applied potential. A cradle-to-gate life cycle and technoeconomic analysis shows that DLE reduces global warming potential by 59% (2.76 × 10³vs. 6.72 × 10³ kg CO₂-eq) and lowers acidification and smog through reduced heat demand (325 °C vs. 1100 °C) and elimination of sulfuric acid. EDL shows further reductions in fossil fuel depletion, global warming, and respiratory effects. Economically, at 1 t per day, DLE delivers 41% ROROI and $18.9M NPV, outperforming the conventional route (35% and $16.0M), while EDL remains profitable (24% ROROI; $12.5M NPV) though burdened by higher CAPEX. Annual OPEX is lowest for DLE ($1.6M vs. $1.9M conventional; $2.0M EDL). Monte Carlo simulations confirm DLE's superior profitability (+$652k per year mean profit vs. −$120k per year conventional) at a small-scale process, while EDL provides intermediate returns (+$416k per year) and the lowest downside risk. Together, these results show that integrated TEA–LCA assessments capture trade-offs among emerging processes and support responsible innovation toward greener, more resilient critical-mineral extraction.

The electrocatalytic hydrogen evolution reaction (HER) in alkaline media is hindered by sluggish water dissociation kinetics and suboptimal hydrogen adsorption/desorption. Herein, we present a crystal-phase-tailored metal heterojunction, composed of hexagonal close-packed (hcp) Ni and face-centered cubic (fcc) Rh (hcp Ni/fcc Rh), synthesized through a galvanic replacement strategy. Impressively, hcp Ni/fcc Rh exhibits exceptional HER performance, achieving an ultralow overpotential of 20 mV at 10 mA cm⁻², which is 2.25 times lower than that of fcc Ni/fcc Rh. Additionally, this catalyst demonstrates long-term stability with a current density of 500 mA cm⁻² at 1.73 V for over 150 h in an anion exchange membrane water electrolyzer. Mechanistic investigations reveal that the hcp Ni scaffold plays a critical role in enhancing water dissociation by promoting efficient hydrogen generation and facilitating the desorption of *OH to regenerate the Ni sites. Simultaneously, the fcc Rh sites effectively optimize hydrogen adsorption due to the directional interfacial electron transfer from hcp Ni to fcc Rh. This work highlights the potential of crystal phase engineering in advancing heterostructure electrocatalysts for efficient HER.