Green Chemistry最新文献

Biotin (vitamin B₇/H), a water-soluble member of the B-vitamin family, is widely used in the food additive, cosmetics, feed, and pharmaceutical industries. Current industrial biotin production relies entirely on multi-step chemical synthesis that requires harsh conditions and generates toxic byproducts. Here, we established a sustainable and environmentally friendly biosynthetic route to biotin by systematically engineering Pseudomonas mutabilis. Four strategies were implemented: (1) dual-channel overexpression of recombinant biotin biosynthetic gene clusters through combined chromosomal integration and plasmid expression; (2) introduction of heterologous BioZ, BioW–BioI, and AasS modules to enable de novo synthesis of the precursor pimeloyl–ACP/CoA from supplemented dicarboxylic acids; (3) cofactor engineering to enhance intracellular availability of iron–sulfur clusters and S-adenosyl-L-methionine; and (4) semi-rational redesign of the rate-limiting enzyme BioB, in which the K232R mutant exhibited a 42.3% improvement in catalytic efficiency for converting dethiobiotin to biotin. The resulting engineered strain, PM-XXI, produced 174.3 mg L⁻¹ biotin in shake-flask cultivation, representing a 197.5-fold increase over the parent strain, and achieved a record titer of 993.6 mg L⁻¹ in 10 L fed-batch fermentation using glycerol as the sole carbon source supplemented with 0.5 g L⁻¹ dicarboxylic acid. This work establishes a green, scalable, and resource-efficient microbial platform that replaces energy-intensive chemical synthesis, demonstrating the potential of microbial cell factories for sustainable vitamin manufacturing aligned with the principles of green chemistry.

Guest–host doping is a strongly preferred strategy for organic room-temperature phosphorescence (RTP). Nontoxic, low-cost and versatile hosts are highly desirable for achieving green RTP materials and ultimate practical applications. Herein, edible biomass-derived citric acid (CA) is developed as a novel, green and biorenewable host to activate the persistent RTP of a wide range of aromatic guests, including simple arene, boronic acid, carboxylic acid, aldehyde, phenol, alcohol, halohydrocarbon and alkaloid. In total, 20 representative RTP samples are fabricated by a simple and green process. They show a colorful afterglow, part of which could be directly observed under natural light. The RTP lifetimes range widely from 0.092 to 2.15 s. Experimental and theoretical results reveal that the CA molecules could not only provide a rigid matrix by virtue of the large number of hydrogen bonds but also considerably promote the intersystem crossing of the guest molecule. These RTP materials show promising applications in anticounterfeiting, three-mode latent fingerprint visualization, rewritable luminescent paper preparation and stimuli-responsive sensing. In this study, we develop a powerful biomass-derived host for achieving green and sustainable RTP materials. Based on its excellent versatility, CA could be a promising alternative to traditional fossil fuel-derived hosts.

The reasonable construction of an electrocatalyst with strong corrosion resistance and high catalytic activity for the oxygen evolution reaction (OER) using earth abundant elements is of great significance to realize seawater splitting and hydrogen energy development. In this work, an amorphous/crystalline phase (a–c) heterogeneous interface (FeMoP/Ni₃S₂) is designed, synergizing with in situ dynamically restructured dual Cl⁻-repelling layers to achieve long-term and ultrastable operation in seawater oxidation. The dual Cl⁻-repelling layers (PO₄³⁻/SO₄²⁻) effectively repel Cl⁻ through electrostatic attraction and reduce the adsorption energy of Cl⁻ on the interface, further promoting preeminent corrosion resistance under harsh marine conditions. The built-in electric field formed at the a–c interface modulates the electronic structure and reduces the energy barrier required for the rate-determining step (*O → *OOH), which significantly accelerates the 4e⁻ OER kinetics, endowing it with excellent electrocatalytic OER performance. Benefiting from this ingenious design, FeMoP/Ni₃S₂ needs only a low overpotential of 308 mV to reach a current density of 100 mA cm⁻², achieving excellent long-term durability for 300 hours at 500 mA cm⁻² in alkaline seawater. Thus, a promising strategy is provided for developing high-efficiency and corrosion-resistant seawater electrocatalysts, contributing immensely to the future development of hydrogen energy production.

La₂NiO₄ exhibits a synergistic combination of Lewis acidic and basic sites, enabling efficient carbon–carbon bond formation in water. Its unique surface architecture and sufficient hydrothermal stability redefine the paradigm of metal oxide catalysis, providing a sustainable and non-redox transformation in water.

Ammonia (NH₃) is emerging as a carbon-free energy carrier and chemical feedstock essential for the clean energy transition. Herein, we present an integrated plasma-electrocatalytic tandem system for sustainable ammonia synthesis directly from air and water. In this process, a rotating gliding arc plasma activates atmospheric nitrogen and oxygen to generate NO_x intermediates, which are subsequently electrochemically reduced to ammonia on a Cu₂O-based catalyst. By dynamically balancing plasma-derived NO_x generation (67 mM within 15 min) and electrocatalytic consumption, a pulsed NO_x replenishment strategy is established to maintain stable NO_x concentrations (65–70 mM) during prolonged operation. This approach achieves a high ammonia yield rate of 0.648 mmol h⁻¹ cm⁻² and a faradaic efficiency of 86.97%, sustaining continuous performance without depletion. The study demonstrates a scalable and energy-efficient route for green ammonia synthesis, offering a promising pathway for decentralized, renewable-powered nitrogen fixation.

Polyolefin plastics, though highly resistant to degradation due to their thermodynamic stability and chemical inertness, can be catalytically depolymerized into liquid fuels, offering a promising route to mitigate white pollution and fossil fuel dependency. Here, a sustainable catalytic route for closed-loop polyolefin upcycling is achieved using a bifunctional Sn₁W₉/γ-Al₂O₃ catalyst that integrates redox and acidic functionalities within a self-regenerative hydrogen relay cycle. The optimized interface between Sn and W species promotes simultaneous C–H dehydrogenation and C–C metathesis via dynamic Sn–H ↔ W–OH coupling, enabling quantitative conversion of polypropylene at 250 °C within 1 hour and selective production of C₅–C₂₂ liquid hydrocarbons (95.0%). Structural, spectroscopic, and kinetic analyses identify hydroxylated W⁵⁺–OH sites as the principal active centers, stabilized by Sn-mediated hydrogen spillover. The catalyst achieves exceptional stability and reusability across multiple degradation cycles and diverse commercial plastics. Life cycle and techno-economic assessments reveal 16-fold enhanced thermal efficiency, >85% solvent recyclability, and a carbon footprint of 7.3 kg CO₂ e kg⁻¹—surpassing benchmark catalysts in both sustainability and energy utilization. This self-sustaining redox–hydroxyl loop establishes a scalable, low-carbon paradigm for circular plastic valorization. Under mild conditions, the system delivers excellent degradation performance and stability, demonstrating scalability for kilogram-scale recovery.

Covalent organic frameworks (COFs) hold promise for photocatalytic applications but suffer from suppressed charge separation due to Frenkel exciton formation and detrimental interlayer coupling. To address this issue, we have investigated a thiourea group-mediated interlayer-spacing engineering strategy. The reaction of 1,3,5-triformylphloroglucinol and p-phenylenediamine in the presence of PhNCS gave a thiourea-functionalized COF, TpPa-CS. The in situ formed thiourea groups were distributed within the layers, enlarging interlayer distances via steric defects. The average layer stacking distance of TpPa-CS was 3.30 Å, which is larger than that of TpPa (3.22 Å). The hydrogen evolution rate of Ni²⁺-modified TpPa-CS (TpPa-CS-Ni) was 29.32 mmol g⁻¹ h⁻¹, representing enhancements 75.2 and 5.6 times those of the parent TpPa and TpPa-Ni (i.e. Ni-loaded TpPa), respectively. This design simultaneously suppressed interlayer charge transfer and enhanced intramolecular charge transfer. Photoelectrochemical testing confirmed efficient synergy between the sulfur ligands and metal ions, leading to improved charge carrier separation. Theoretical and experimental analyses confirmed that electron-donating/accepting moieties in TpPa-CS optimized HOMO/LUMO levels, enabling efficient metal coordination at S/N sites to form electron-transfer catalytic centers. This work provides a novel approach to engineering interlayer interactions for high-performance COF photocatalysts.

The efficient capture and conversion of hydrogen sulfide (H₂S) represent a critical challenge in addressing key issues in energy and environmental fields. In this study, we innovatively designed and synthesized a series of carbonyl-functionalized metallic ionic liquids (CMILs), which exhibit dual functionality as both absorbents and catalysts under mild conditions. Experimental results demonstrate that the [Na-15C][LA] system delivers outstanding performance under ambient conditions (30 °C, 1.0 bar), achieving an H₂S absorption capacity of 1.73 mol mol⁻¹, an H₂S/CO₂ selectivity of 101.2, and an exceptionally high H₂S/CH₄ selectivity of 1122.2. NMR, FT-IR, and DFT calculations confirm that the carbonyl group serves as the active site for efficient H₂S capture. Notably, these CMILs function as highly effective catalysts, facilitating the solvent-free conversion of H₂S with α,β-unsaturated carboxylates into thiols and thioethers under mild conditions. Moreover, the system enables spontaneous phase separation between the catalyst and products without requiring additional components, achieving quantitative conversion (>99%) while adhering to green chemistry principles. This integrated design provides a novel technical approach for the efficient capture and resource utilization of H₂S.

Polyvinyl Chloride (PVC) is widely utilized across various industries due to its outstanding comprehensive properties. However, the current reliance on harmful petroleum-based plasticizers, such as phthalates (PAEs), in PVC film processing poses significant environmental and health concerns, limiting its applications. To address this issue, we developed epoxidized isosorbide oleate (EIOA), a non-cytotoxicity, bio-based plasticizer with excellent plasticizing performance, as a sustainable alternative to conventional petroleum-derived plasticizers. EIOA was synthesized via esterification and epoxidation reactions using bio-derived raw materials, including isosorbide and oleic acid. When compared to the commercially available plasticizer di(2-ethylhexyl) terephthalate (DOTP), EIOA-plasticized PVC demonstrated superior performance, including: high optical clarity (87% light transmittance), enhanced thermal stability (T_5% was 100 °C higher than pure PVC), exceptional flexibility (∼636.5% elongation at break), superior migration resistance (only 1.8% migration in n-hexane 24 h), and improved compatibility with PVC. Therefore, EIOA-plasticized PVC is a potential material for medical devices, food packaging, and other applications requiring direct human contact, eliminating safety concerns associated with traditional plasticizers.

The dearomative cycloaddition of non-activated arenes is a powerful strategy for constructing the core structures of biological leads. This process requires losing aromaticity, which remains a challenge due to the inherent stability of arene (benzene) derivatives, therefore limiting their synthetic potential. Herein, we report the development of a green and sustainable dearomative cycloaddition protocol for non-activated arenes enabled by visible-light energy-transfer catalysis under metal-free photocatalytic conditions. The reaction proceeds without expensive metal photocatalysts, oxidants, or additives, delivering complex N-heterocycles in the green solvent 2-methyltetrahydrofuran (2-MeTHF). This method allows the efficient synthesis of fused tricyclic compounds exhibiting multiple quaternary carbon centers from readily accessible precursors at room temperature. Furthermore, the reaction avoids tedious workup, and the organophotocatalyst was reused for five cycles with >86% yield, demonstrating an efficient and environmentally friendly protocol. Moreover, the reaction tolerates diverse functional groups with good yields, enables late-stage functionalization and gram-scale synthesis under green conditions, and offers a general approach to previously underexplored arene dearomatization. Finally, additional experiments and computational studies were conducted to gain mechanistic insights, indicating that the reaction proceeds via a triplet energy transfer pathway rather than a thermal process.