ACS Sustainable Chemistry & Engineering最新文献

{"title":"In Situ Cross-Linked Solid Polymer Electrolytes with Synergistic Dissociation–Coordination Modulation for Stable Solid-State Lithium Batteries","authors":"Yi Zhang,Caiqian Liang,Yu Cheng,Yu Dou,Jiandong Gong,Yalong Jiang,Ming Yang,Shuguang Bi,Jianhua Ran,Yingkui Yang","doi":"10.1021/acssuschemeng.6c08147","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c08147","url":null,"abstract":"Abstract Solid polymer electrolytes possess excellent flexibility and superior interface compatibility, which can effectively adapt to electrode volume changes and reduce interface resistance. However, they are impeded by the intrinsic incompatibility between lithium salt dissociation and Li+ coordination, along with the unavoidable trade-off between mechanical durability and Li+ conductive kinetics. To address this, an in situ multifunctional cross-linked copolymer electrolyte (TGDODT) is constructed. The crosslinking center promotes the dissociation of lithium salts to deliver more free Li+, while the thioether segment provides weak coordination with Li+ to reduce the transport barrier. Moreover, the cross-linked network ensures excellent mechanical/thermal stability and provides a three-dimensional continuous Li+ diffusion channel. Therefore, this collaborative design provides a Li+ transport highway, induces a stable inorganic SEI to suppress lithium dendrites, and provides flame retardancy. As a result, the TGDODT electrolyte shows high ionic conductivity (1.31 × 10–4 S cm–1), a high Li+ transference number (0.75), and exceptional electrode compatibility. Li||TGDODT||LFP batteries show great cycling stability after 660 cycles at 1 C with 88.2% capacity retention. This study demonstrates a coherent design principle for integrating mechanical stability, rapid ion transport, and interfacial safety, providing a promising avenue for developing high-performance solid-state lithium metal batteries.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"52 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Castor Oil\u0000 as a Renewable Reaction Medium for Sustainable Domino Synthesis of Functionalized Epoxyisoindolyl Ureas","authors":"Ayhan Yıldırım,Mustafa Göker","doi":"10.1021/acssuschemeng.6c06440","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c06440","url":null,"abstract":"Abstract The development of renewable reaction media that can replace conventional organic solvents without affecting reaction performance is highly desirable for the advancement of sustainable chemical processes. In this study, the properties of Castor oil as a bio-based solvent were investigated in the context of a domino multicomponent synthesis of functionalized epoxyisoindolyl ureas. This synthesis involved a tandem condensation/Diels–Alder sequence, with the use of furfurylamine, phenyl isocyanate, and various N-substituted maleimides. In the absence of a catalyst and under mild reaction conditions, the desired products were obtained in satisfactory yields and with generally high diastereoselectivity without the need for chromatographic purification. In the course of the investigation, it was established that among the vegetable oils under consideration, Castor oil demonstrated the highest reaction efficiency. Furthermore, it was ascertained that this oil could be easily recovered and reused. Its superior performance is attributed to its high hydrogen-bonding capability and favorable Hansen solubility parameter profile, which enhance substrate solubilization and facilitate hydrogen bond-assisted organization of the reacting species. The use of Fourier-transform infrared (FTIR) monitoring and DFT calculations has provided support for a proposed mechanism in which the rapid formation of a urea intermediate occurs prior to the intermolecular cycloaddition reaction. In comparison with conventional stepwise protocols, the present methodology integrates multiple bond-forming events into a single operation, thereby reducing purification requirements while employing a renewable and recyclable reaction medium. The findings of this study demonstrate that Castor oil provides an effective platform for sustainable domino synthesis and highlight the potential of vegetable-oil-based solvents for greener multicomponent transformations.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209484","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anchoring the Oxygen Framework: A Cation-Pinning Strategy for Durable High-Voltage Cycling and Strain Suppression of Ni-Rich Layered Cathodes","authors":"Qingling Lu,Yue Zhang,Bing Liu,Wenya Li,Zhongnian Yang,Na Li,Kang Wu","doi":"10.1021/acssuschemeng.6c07242","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c07242","url":null,"abstract":"Abstract Anionic redox reactions (ARRs) in ultrahigh-nickel layered oxides provide additional capacity for high-energy lithium-ion batteries, yet irreversible oxygen charge compensation at high voltage remains a critical challenge. Herein, a tungsten (W)-doping strategy is developed in LiNi0.9Co0.05Mn0.05O2 (NCM90) to regulate defect–oxygen coupling and stabilize reversible oxygen redox chemistry. Neutron diffraction analysis corroborates that the incorporation of W significantly decreases the intrinsic Li/Ni antisite defect concentration, attenuates the oxygen-redox-active Li–O–Li configurations, alleviates irreversible oxygen oxidation, and consequently inhibits the regeneration of Li/Ni antisite defects over extended cycling. Meanwhile, strong W–O interactions increase oxygen vacancy formation energy, inhibit transition-metal migration, and stabilize the lattice oxygen framework. Combined in situ X-ray diffraction, theoretical calculations, and finite element analysis demonstrate that W-induced defect regulation homogenizes Li+ distribution and alleviates lattice strain accumulation during high-voltage cycling. Consequently, W-doped NCM90 achieves over 90% capacity retention after 100 cycles at 4.6 V and 1 C, exhibiting significantly enhanced cycling stability. This work uncovers the intrinsic coupling between Li/Ni antisite defects and oxygen redox evolution and establishes a defect–oxygen coupling regulation strategy that provides a general framework for designing durable cathode materials with reversible anionic redox chemistry.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"292 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Insight into the Acidic/Redox Modulation of Vanadium-Substituted Dawson Polyoxometalates Enabling Overall Conversion of Larch Lignocellulose","authors":"Yuannan Chen,Qiwen Wang,Fukai Yang,Jiahui Si,Fang Luo,Zonghang Li,Luyi Zou,Xiaohong Wang","doi":"10.1021/acssuschemeng.6c06781","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c06781","url":null,"abstract":"Developing structurally well-defined homogeneous catalysts for one-pot lignocellulose depolymerization remains a significant challenge. Herein, V─Mo polyoxometalate (POM) molecules with a Dawson structure have been designed through “metal-to-metal” replacement of addendum MoVI by different amounts of VV to adjust the acidity and redox properties in H6+nP2Mo18–nVnO62 molecules (n = 1–3, H6+nP2Mo18–nVn) via altering the V number, hence studying the activity and mechanism in the aerobic oxidation of the lignin model 2-phenoxy-1-phenylethanol (pp-ol). Experimental and density functional theory results revealed that H9P2Mo15V3 facilitated a unique proton-coupled electron transfer (PCET) mechanism, which was distinct from the electron transfer-oxygen transfer pathway observed in Keggin-type analogues. This PCET process efficiently promoted Cα─OH oxidation to Cα═O and activated β–O–4 bond cleavage by decreasing the C─O bond length in oxidative intermediates. Furthermore, the synergistic effect of protons and redox sites enabled H9P2Mo15V3 to serve as a high-performance homogeneous system for “lignin-first” biorefinery. Through a two-step oxidation–hydrolysis process, raw larch was successfully converted into a suite of value-added products, including aromatic monomers, lignin oligomers, and carbohydrate-derived chemicals (glucose, mannose, glycolic acid, and formic acid), alongside the production of nanosized cellulose. This work provides mechanistic insights into the design of multifunctional POM catalysts for the holistic valorization of native biomass.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aramid Nanofiber and Lithium Acetate Synergistically Regulated Gel Polymer Electrolyte for Stable Zinc-Ion Batteries","authors":"Xun Wang,&nbsp;Ran Liu,&nbsp;Weicheng Sun,&nbsp;Lin Wang,&nbsp;Hua Tian,&nbsp;Yuwen Liu,&nbsp;Zhen Sun,&nbsp;Mingyan Chuai,&nbsp;Yongfu Tang,&nbsp;Fei Wang","doi":"10.1021/acssuschemeng.6c07706","DOIUrl":"10.1021/acssuschemeng.6c07706","url":null,"abstract":"<p>The practical application of aqueous zinc-ion batteries (AZIBs) is hindered by the interfacial parasitic reactions induced by free water and sluggish kinetics arising from the strong solvation effect of Zn²⁺. Herein, we develop a gel polymer electrolyte (GPE) design strategy that synergistically reconstructs the solvation structure and hydrogen bond network by integrating aramid nanofibers (ANF) and lithium acetate (LiOAc) into a polyacrylamide matrix. The carbonyl groups (–C=O) in ANF and polyacrylamide competitively coordinate with Zn²⁺, weakening cation–dipole interactions and providing additional hopping sites for Zn²⁺ transport. Amino groups in ANF anchor anions to enhance the Zn²⁺ transference number, while restricting free water activity by hydrogen bonding. LiOAc shifts OAc^––Zn²⁺ coordination toward a more asymmetric, monodentate-like configuration, in which the exposed –C=O oxygen confines free water. With this GPE, Zn||Cu cells achieve an average Coulombic efficiency of 99.6%, Zn||Zn symmetric cells operate stably for over 2800 h, and Zn||PANI full cells exhibit durable cycling stability. This synergistic regulation of the solvation structure and hydrogen-bond network accelerates Zn²⁺ transport, suppresses parasitic reactions, and stabilizes zinc deposition, thereby significantly advancing the design of high-performance GPEs for zinc-ion batteries.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 41","pages":"18734–18746"},"PeriodicalIF":7.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coupled Electrocatalytic-Enzymatic Tandem Reduction for Selective Nitrate-to-Ammonia Conversion","authors":"Ruoran Song,&nbsp;Zhe Wang,&nbsp;Xuefang Zhu,&nbsp;Shuni Li,&nbsp;Yu Chen,&nbsp;Yucheng Jiang","doi":"10.1021/acssuschemeng.6c08616","DOIUrl":"10.1021/acssuschemeng.6c08616","url":null,"abstract":"<p>As a promising strategy for green synthesis, tandem electroenzymatic catalysis has recently emerged. This work designs a tandem electroenzymatic catalysis platform by directionally immobilizing ionic liquid modified chloroperoxidase (CPO-IL_EMB) onto silver-loaded reduced graphene oxide (Ag/rGO) modified with polyethyleneimine (PEI), thereby constructing the CPO-IL_EMB/Ag/rGO-PEI bioconjugate for NO₃^– reduction reaction (NO₃^–RR). Firstly, Ag/rGO-PEI electrocatalytically reduces NO₃^– to NO₂^–. Subsequently, CPO-IL_EMB converts NO₂^– to NH₄⁺ with high substrate selectivity and catalytic specificity. PEI covalently immobilizes enzyme molecules via glutaraldehyde, enhancing their stability, and its protonated form provides positive charges to enrich NO₃^– and the intermediate NO₂^–. In situ FTIR analysis reveals that the NO₂^– intermediate is rapidly consumed at the CPO-IL_EMB/Ag/rGO-PEI interface, accompanied by the accumulation of NH₄⁺ species, verifying the successful construction of this tandem electroenzymatic system. As a result, the CPO-IL_EMB/Ag/rGO-PEI bioconjugate achieves a Faradaic efficiency of 94.97% and an NH₄⁺ yield rate of 4.94 mg h^–1 mg_cat^–1 at –0.56 V vs. RHE, representing an NH₄⁺ yield rate of 19.8-fold increase over Ag/rGO-PEI, and maintains stable performance during 216 h of continuous operation.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 41","pages":"18841–18851"},"PeriodicalIF":7.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coordinated Interfacial Electron Transfer and Metabolic Coupling Drive Acetate Electrosynthesis in a Synthetic Microbial Consortium","authors":"Jing Zhang,&nbsp;He Liu,&nbsp;Meng-Yao Liu,&nbsp;Jia-Chen Zhu,&nbsp;Min Zhang,&nbsp;Min-Hua Cui,&nbsp;Yan Zhang,&nbsp;Hong-Bo Liu","doi":"10.1021/acssuschemeng.6c09803","DOIUrl":"10.1021/acssuschemeng.6c09803","url":null,"abstract":"<p>Microbial consortia in microbial electrosynthesis (MES) can couple cathodic electron utilization with CO₂ fixation through interspecies electron transfer and metabolite cross-feeding. However, how defined functional members coordinate interfacial electron input with downstream acetogenic metabolism remains insufficiently understood. Here, we constructed a defined three-member consortium comprising the <em>Shewanella oneidensis</em> MR-1 and the acetogens <em>Clostridium aceticum</em> and <em>Acetobacterium woodii</em> to investigate how functional complementarity supports acetate electrosynthesis. The three-member consortium reached a maximum acetate concentration of 2.33 ± 0.17 g L^–1, 2.62-fold that of the <em>A. woodii</em> and <em>C. aceticum</em> binary consortium, accompanied by a higher current density, stronger redox activity, and more pronounced riboflavin-related signals. Phase-resolved <em>fhs</em> abundances, metabolomic profiles, and flavin perturbation experiments further supported spatially differentiated roles within the consortium: <em>S. oneidensis</em> enhanced cathode-associated electron input, while phase-resolved <em>fhs</em> abundances and H₂/formate dynamics indicated that acetogenic functions were maintained across both biofilm and planktonic phases and coupled to soluble-intermediate turnover. Despite varying initial inoculation ratios, the consortium consistently converged on similar acetate production and community functions, indicating that steady-state performance of the consortium was not strongly dependent on the precise initial community composition. These results suggest that the enhanced performance of the three-member consortium was associated with coordinated electron transfer and metabolic handoff among functionally complementary members. This study demonstrates that enhanced CO₂ electrosynthesis arises from the reorganization of electron-metabolic interactions rather than the simple addition of functional members, providing a mechanistic basis for the rational design of electrically driven synthetic microbial communities.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 41","pages":"18886–18897"},"PeriodicalIF":7.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Valorization of Mn-Rich Invasive Alien Species as Janus Ecocatalysts for Sustainable N-Heterocyclic Carbene-Catalyzed Transformations","authors":"Chloé Boisseau,&nbsp;Pierre-Alexandre Deyris,&nbsp;Franck Pelissier,&nbsp;Yves-Marie Legrand,&nbsp;Eddy Petit,&nbsp;Claude Grison,&nbsp;Claire M. Grison","doi":"10.1021/acssuschemeng.6c07675","DOIUrl":"10.1021/acssuschemeng.6c07675","url":null,"abstract":"<p>Water lettuce (<em>Pistia stratiotes</em>), a worldwide invasive alien species (IAS), is presented here for the first time as the source of innovative Janus ecocatalysts. These new ecocatalysts enabled the development of a novel one-pot strategy based on the N-heterocyclic carbene (NHC)-ecocatalyzed oxidative esterification of furfural toward methyl 2-furoate, an increasingly valuable yet challenging platform chemical. Guided by an all-natural approach, the catalytic system relies exclusively on the original combination of ecocatalysts and vitamin B1, as a natural carbene precursor. Careful optimization of the reaction parameters led to high conversion rates and excellent selectivity (yield of 75 ± 11%) in mild conditions with excellent green metrics (e.g., E-factor = 70). Mechanistic investigations and statistical analyses of the ecocatalyst composition associated with their structure highlighted the unique dual oxidative and basic behavior of the ecocatalysts. Remarkably, these catalytic properties remained consistent over seven years of <em>P. stratiotes</em> harvesting, ensuring the reproducibility of the synthetic performances. The scope of the new NHC-ecocatalytic methodology was extended to other aromatic aldehydes, notably enabling the first direct preparation of methyl 5-methyl-2-furoate. Beyond synthetic efficiency, this strategy demonstrates how whole plants of <em>P. stratiotes</em> can be transformed into value-added catalytic materials, offering a green and reproducible synthetic route that supports IAS management.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 41","pages":"18709–18722"},"PeriodicalIF":7.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Integrated Electrode Design Enables Ampere-Level CO2 Electroreduction in Aqueous Electrolytes","authors":"Shilei Zhang,&nbsp;Yingwei Li,&nbsp;Hang Wang,&nbsp;Chuanjun Wang,&nbsp;Yang Wang,&nbsp;Min Zhang,&nbsp;Xun Zhu,&nbsp;Qian Fu","doi":"10.1021/acssuschemeng.6c05782","DOIUrl":"10.1021/acssuschemeng.6c05782","url":null,"abstract":"<p>Gas-fed CO₂ reduction reaction (CO₂RR) electrolyzers suffer from inherent salt precipitation and performance decay due to hindered salt removal within electrodes. Although electrolyzers that reduce CO₂ carried by aqueous electrolytes (e.g., H-cells) naturally avoid salt accumulation, their low CO₂ solubility and sluggish mass transport restrict current densities to typically &lt;0.1 A cm^–2. Here, resolving the electrode–transport mismatch is shown to be the key factor for enabling ampere-level electrolyte-fed CO₂RR. In a pressurized zero-gap electrolyzer, where CO₂ is supplied by a flowing aqueous electrolyte, the conventional layered electrode is reconstructed into a hierarchically porous integrated electrode by directly growing Ni single-atom-anchored CNT arrays on carbon fiber paper. The interconnected micrometer-scale pores facilitate the transport of CO₂-saturated electrolytes throughout the electrode thickness while maintaining high intrinsic catalytic activity. Under a CO₂ pressure of 0.5 MPa, a CO partial current density of 0.760 A cm^–2 is achieved, representing a 3.67-fold enhancement compared with the conventional layered electrode under identical pressure. <em>Operando</em> impedance and voltage loss analyses reveal that the integrated structure reduces concentration polarization by 37%, confirming that improved CO₂ accessibility within the electrode is decisive for high-rate operation. This work establishes a general electrode design principle for enabling ampere-level electrolyte-fed CO₂RR, providing a scalable pathway toward stable CO₂ electrolysis.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 41","pages":"18428–18435"},"PeriodicalIF":7.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boosting Reductive N-Formylation of Nitroarenes via Co Single-Atom/Nanoparticle Synergy with Formic Acid","authors":"Jinxia Zhu,&nbsp;Yujie Xing,&nbsp;Junling Zhao,&nbsp;Jingjie Guo,&nbsp;De-Li Chen,&nbsp;Qiang Xiao,&nbsp;Weidong Zhu,&nbsp;Fumin Zhang","doi":"10.1021/acssuschemeng.6c07944","DOIUrl":"10.1021/acssuschemeng.6c07944","url":null,"abstract":"<p>The direct reductive N-formylation of nitroarenes using formic acid as both a hydrogen donor and a C1 source provides an atom-economical and sustainable route to formamides, which are essential building blocks in the pharmaceutical, agrochemical, and polymer industries. Nevertheless, achieving this transformation under mild, additive-free conditions with non-noble-metal heterogeneous catalysts remains a significant challenge. Herein, we report a cobalt hybrid catalyst supported on nitrogen-doped carbon (Co₁–Co_n/NC), which features the coexistence of atomically dispersed Co single atoms and metallic Co nanoparticles and is derived from a bimetallic ZnCo-ZIF precursor via a simple pyrolysis strategy. The Co₁–Co_n/NC catalyst achieves near-quantitative conversion (99.9%) and selectivity (99.9%) in the N-formylation of nitrobenzene at 373 K under ambient pressure, considerably exceeding its single-atom-only (Co₁/NC) and nanoparticle-only (Co_n/NC) counterparts. The catalyst exhibits a broad substrate scope, excellent functional-group tolerance, good recyclability over five cycles, and a low apparent activation energy (83.4 kJ mol^–1). Experiments combined with DFT calculations revealed a synergistic mechanism: the Co nanoparticles serve as the primary sites for HCOOH dissociation and act as an *H reservoir, while the adjacent Co single atoms are the preferred adsorption and reaction sites for nitrobenzene and its hydrogenated intermediates. This work provides an efficient non-noble-metal catalytic system for sustainable formamide synthesis and offers design principles for synergistic single-atom/nanoparticle catalysts.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 41","pages":"18759–18773"},"PeriodicalIF":7.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149150950","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}