Chemical Science最新文献

{"title":"Engineering hydrophobic covalent organic frameworks for electroreduction of nitrate to ammonia.","authors":"Fuzhen Li, Huan Lin, Chunying Chen, Li-Lin Tan, Dawei Wang, Cunyuan Zhao, Li Zhang, Cheng-Yong Su","doi":"10.1039/d6sc01645f","DOIUrl":"https://doi.org/10.1039/d6sc01645f","url":null,"abstract":"<p><p>The development of efficient electrocatalysts for the nitrate reduction reaction (NO₃RR) to ammonia is crucial for sustainable nitrogen management, but remains challenging due to its intricate multi-step mechanism and competing side reactions. A key bottleneck is the severe imbalance between the generation and consumption of H*, which critically constrains ammonia selectivity and yield. Herein, a molecular engineering strategy was developed through the incorporation of Pd-porphyrin to promote the generation of H*, while grafting ethoxyphenyl groups to create a hydrophobic microenvironment and inhibit the hydrogen evolution reaction. The covalent organic framework of Pd-PCOF-2(Cu₃), which was prepared from the reaction of Pd(ii) diaminoporphyrin and trinuclear copper cluster aldehyde, achieved a high NH₃ faradaic efficiency of 94.7% and a production rate of 15.09 mg h^-1 cm^-2. A rechargeable Zn-NO₃ ^- battery with Pd-PCOF-2(Cu₃) as the cathode was further constructed, which served as a dual-function system for both power output and ammonia production.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13148548/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147834404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Band-bending engineering in Cu2ZnSnS4 photocathodes using a composite (Zn,Ti)O electron transport layer for solar water splitting","authors":"Siyuan Ren, Muhammad Abbas, Zhibin Xie, Zilin Lu, Jasim Yousaf, Muhammad Ishaq, Zhuanghao Zheng, Jun Zhao, Shuo Chen, Guangxing Liang","doi":"10.1039/d6sc00648e","DOIUrl":"https://doi.org/10.1039/d6sc00648e","url":null,"abstract":"The development of efficient and stable photocathodes from earth-abundant materials is a critical challenge for photoelectrochemical (PEC) hydrogen production. While Cu<small>₂</small>ZnSnS<small>₄</small> (CZTS) is a promising absorber due to its ideal bandgap and non-toxic constituents, its performance is plagued by severe interfacial recombination. This work addresses this limitation through the precise engineering of a zinc-titanium oxide (Zn,Ti)O electron transport layer (ETL) in Mo/CZTS/CdS/(Zn,Ti)O/Pt photocathodes. We systematically investigate the influence of atomic-layer-deposited (Zn,Ti)O on the heterojunction's microstructure, band alignment, and charge transfer kinetics. A suite of characterization studies reveals that a suitable ETL thickness forms a dense, conformal coating and establishes an optimal spike-like conduction band offset at the CdS/(Zn,Ti)O interface, which minimizes bulk and interfacial charge-transfer resistance. Consequently, the optimized photocathode achieves a remarkable photocurrent density of 29.2 mA cm<small>⁻²</small> at 0 V<small>_RHE</small> and a high half-cell solar-to-hydrogen efficiency (HC-STH) of 7.02%. This study demonstrates that fine control of composite ETLs is a powerful strategy to unlock the potential of CZTS and related earth-abundant absorbers for scalable solar fuel production.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"70 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755274","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":"CPL-active supramolecular polymers","authors":"Carmen Atienza, Fátima García, Luis Sanchez","doi":"10.1039/d6sc00729e","DOIUrl":"https://doi.org/10.1039/d6sc00729e","url":null,"abstract":"Supramolecular polymers constitute a highly dynamic and rapidly evolving research field, characterized by the continuous development of systems with increasing structural and functional complexity. Theoretical and mathematical models aimed at understanding the mechanisms of supramolecular polymer formation have played a crucial role in guiding the design of these systems, enabling the discovery of novel assembly pathways and emergent functionalities in both self- and co-assembled architectures. Within this broad landscape, chiral supramolecular polymers occupy a particularly prominent position, as they provide an effective platform for generating well-defined helical structures that can serve as models for the emergence of homochirality in nature, while simultaneously enabling a wide range of advanced functional properties. Of particular interest is the incorporation of emissive moieties into the monomeric building blocks of chiral supramolecular polymers, which can lead to the formation of emissive aggregated species exhibiting circularly polarized luminescence (CPL). The CPL activity of these systems significantly enhances their relevance across multiple research areas, extending their impact beyond fundamental supramolecular chemistry to applied materials science. This review focuses on representative examples of the diverse strategies employed to obtain CPL-active supramolecular polymers, including the introduction of chiral elements—such as point or axial chirality—into monomeric units, as well as the integration of metallic components. Furthermore, the collected examples demonstrate the high responsiveness of CPL-active supramolecular polymers to external stimuli such as light, solvent polarity and temperature, highlighting their exceptional versatility. These adaptive properties enable the realization of systems with notably high dissymmetry factors (g<small>_lum</small>) and circularly polarized luminescence brightness (B<small>_CPL</small>). Finally, the review presents both metallo-organic and purely organic CPL-active supramolecular polymers, together with selected examples of their outstanding applications in areas such as optoelectronic devices, anticounterfeiting technologies, and information encryption.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755278","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":"Highly Cα-regio-, enantio- and diastereoselective Mukaiyama-type annulation of siloxyfurans: stereodivergent synthesis of multi-stereogenic tricyclic γ-lactones.","authors":"Lifei Gan, Zi-Qing Li, Tao Chen, Xuanchen Wan, Junyang Zhang, Jiangtao Ren, Ming Jiang, Penglong Cao, Jinhai Huang, Yu-Hua Deng, Fangzhi Peng, Run Tian, Yingcheng Wang, Zhihan Zhang, Zhihui Shao","doi":"10.1039/d6sc01491g","DOIUrl":"https://doi.org/10.1039/d6sc01491g","url":null,"abstract":"<p><p>The first Cα-selective asymmetric reaction of 2-siloxyfurans, a class of versatile nucleophiles, has been developed with both high enantioselectivity and diastereoselectivity. Moreover, by changing the achiral co-catalyst to a newly developed combined co-catalyst, a rare diastereoselective reversal was achieved, selectively yielding the thermodynamically less stable diastereomer. DFT and experimental studies reveal that the observed Cα-selectivity results from dispersion and electrostatic interactions between 2-siloxyfurans and the electrophile/catalyst, while the diastereodivergent synthesis arises from a divergent C-O bond formation <i>via</i> dynamic kinetic lactonization-driven epimerization. This work not only provides a method to overcome the challenges of Cα-selective asymmetric reactions of 2-siloxyfurans, but also offers a stereodivergent synthesis of chiral tricyclic γ-lactones. Importantly, the resulting chiral tricyclic γ-lactones are not only the core structures in natural products and bioactive molecules but also serve as an appealing platform for diversity-oriented synthesis (DOS), streamlining the construction of other valuable enantioenriched compounds.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13147288/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147834398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Symmetry-Directed Complex Tessellation of Irregular Polygons from a Single Molecular Precursor","authors":"Wenya Zhai, Ye Chen, Haoyuan Zang, Donghui Guo, Jingcheng Li, Zengfu Ou","doi":"10.1039/d6sc00180g","DOIUrl":"https://doi.org/10.1039/d6sc00180g","url":null,"abstract":"The construction of two-dimensional tessellations using irregular polygonal motifs remains a significant challenge in supramolecular chemistry, primarily due to the difficulty in achieving periodic ordering without intrinsic geometric regularity. Herein, we report the fabrication of molecular tessellations based on two irregular hexagons, highlighting the role of symmetry in the tiling of asymmetric building blocks. By precisely tuning the intramolecular hydrogen-transfer mediated reaction processes, three molecular superlattices are synthesized on a metallic substrate from a single fluorene-based precursor. Scanning tunneling microscopy (STM) measurements demonstrate that all three superlattices are assembled via Br-mediated hydrogen bonds, with building blocks adopting irregular hexagonal or decagonal geometries. Structural analysis indicates that one hexagon with mirror symmetry (Cs ) and one without intrinsic symmetry achieve tiling by dimerization (C2 symmetry) or hexamerization (C6 symmetry) under specific conditions. This work opens a route to constructing complex supramolecular architectures driven by geometric symmetry at the molecular scale.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755276","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":"Non-equilibrium preparation of (<i>E</i>)-phosphinimine (HPNH, X¹A') - a precursor to prebiotic phosphorylating agents.","authors":"Jia Wang, Bing-Jian Sun, Alexandre Bergantini, Zesen Wang, Mason McAnally, Joshua H Marks, Agnes H H Chang, André K Eckhardt, Ralf I Kaiser","doi":"10.1039/d6sc01818a","DOIUrl":"https://doi.org/10.1039/d6sc01818a","url":null,"abstract":"<p><p>Phosphorus-nitrogen compounds play crucial roles as intermediates in aza-Wittig reactions and serve as key precursors to prebiotic phosphorylating agents such as amidophosphonates linked to the Origins of Life. However, their formation mechanisms under astrophysical conditions remain largely unexplored. Here, we report the first formation of (<i>E</i>)-phosphinimine (HPNH, X¹A') - the simplest iminophosphane - in low-temperature interstellar model ices composed of phosphine (PH₃) and ammonia (NH₃) exposed to galactic cosmic ray proxies in the form of high-energy electrons. Utilizing vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry in tandem with computed adiabatic ionization energies permits the very first identification of (<i>E</i>)-phosphinimine in the gas phase during the temperature-programmed desorption of irradiated ices. Our study reveals a critical formation pathway for iminophosphanes <i>via</i> non-equilibrium chemistry through nitrogen- and phosphorus-centered radicals in interstellar environments preceding the formation of stars and planets thus affording useful insights into the interstellar phosphorus-nitrogen chemistry essential for the origin of prebiotic molecules.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13142847/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147833731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Promoting effect of nickel-chromium hydroxide on nickel phosphide nanosheets for efficient hydrogen production coupled with sulfion degradation","authors":"Xiaojun Wang, Jieting Li, Xinyu Zhu, Zehua Xu, Shuixiang Xie, Shutong Chen, Yuxuan Wan, Guangyu Zhang, Mingzheng Ge, Wei Zhang, Chao Wang, Ruiqing Li","doi":"10.1039/d6sc02309f","DOIUrl":"https://doi.org/10.1039/d6sc02309f","url":null,"abstract":"Electrochemical hydrogen production represents a sustainable approach for hydrogen generation. However, its large-scale practical application is largely limited by the sluggish oxygen evolution reaction (OER). In this study, the thermodynamically favorable sulfion oxidation reaction (SOR) is employed to replace slow OER and nickel phosphide/nickel-chromium hydroxide (Ni2P/NiCr(OH)2) nanosheets are constructed to achieve low-energy hydrogen production. Benefiting from the interfacial water structure reorganization and electronic structure optimization caused by NiCr(OH)2) introduction, and uniform nanosheet morphology, Ni2P/NiCr(OH)2 can achieve a current density of 10 mA cm-2 at low overpotentials for both hydrogen evolution reaction and SOR. The assembled hybrid water electrolyzer requires small voltages of 0.513 and 0.698 V to reach 10 and 100 mA cm-2, significantly lower than those of conventional water electrolysis. Moreover, Ni2P/NiCr(OH)2 exhibits excellent stability for 800 h at 200 mA cm-2 and realizes the conversion of sulfion into valuable elemental sulfur. This work presents a promising strategy for achieving energy-efficient hydrogen generation and resource utilization of sulfide-containing pollutants.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755275","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":"Atroposelective construction of indole-fused diazocines via gold(I)-catalysed 8-endo-dig cyclisation","authors":"Silvia Meraviglia, Alessandra Romanelli, Paola Iannelli, Silvia Rizzato, Alessandro Contini, Giorgio Abbiati, Valentina Pirovano","doi":"10.1039/d6sc00020g","DOIUrl":"https://doi.org/10.1039/d6sc00020g","url":null,"abstract":"Axially chiral N-bridged biaryls embedded in medium-sized rings remain largely unexplored because of the combined challenges associated with C–N axial chirality and medium-ring formation. Here we report a gold(I)-catalysed atroposelective intramolecular cyclisation of indole-derived aryl propiolamides that enables direct access to indole-fused diazocines combining a C–N stereogenic axis with a conformationally constrained diazocine core. The transformation proceeds through a stereocontrolled 8-endo-dig hydroarylation promoted by a cationic gold complex bearing a BINOL-derived phosphoramidite ligand, affording the target scaffolds in high yields and excellent enantioselectivities across a broad substrate scope. DFT and QTAIM analyses reveal that stereocontrol originates from differential non-covalent interactions in key cyclisation intermediates. The resulting diazocines exhibit high barriers to racemisation and can be further diversified through downstream functionalisation without erosion of enantiopurity. Preliminary spectroscopic and DNA-interaction studies indicate that these rigid atropisomeric frameworks may be relevant for applications in molecular recognition. Overall, this work establishes a general catalytic strategy for the construction of medium-sized N-bridged atropisomers and expands the scope of gold-catalysed asymmetric cyclisations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753516","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":"Electrochemical Deoxygenative Trifluoromethylallenylation of Propargylic Alcohols via Sodium-Mediated Pre-association","authors":"Jihoon Jang, Hyunwoo Kim, Eun Jin Cho","doi":"10.1039/d6sc02203k","DOIUrl":"https://doi.org/10.1039/d6sc02203k","url":null,"abstract":"We report an electrochemical protocol that enables the direct conversion of free propargylic alcohols into trifluoromethylated allenes through sodium-mediated radical C–O bond activation. The transformation proceeds via a pre-association mechanism between the propargylic alcohol and a trifluoromethyl sulfinate reagent, which organizes the reactive complex through Na<small>⁺</small> coordination. This interaction lowers the energetic barrier of the intrinsically endothermic C–O bond cleavage, allowing a concerted radical addition pathway under mild electrochemical conditions. Combined experimental and computational studies, including NMR titration, kinetic analysis, and DFT calculations, reveal that sodium acts as an ion bridge, enabling selective CF<small>₃</small> incorporation. The reaction exhibits broad substrate scope and high chemoselectivity, tolerating halogens, heteroarenes, and sensitive functional groups, and proving effective for the late-stage trifluoromethylation of natural products and pharmaceuticals.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753537","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":"Turn-on fluorescence switching and radical formation of a dual-functional negative photochromic dimethyldihydropyrene","authors":"Sariful Molla Molla, Samyadeb Mahato, Avinash Kumar Ray, Subhajit Bandyopadhyay","doi":"10.1039/d6sc01682k","DOIUrl":"https://doi.org/10.1039/d6sc01682k","url":null,"abstract":"High-contrast fluorescent switchable systems are highly coveted dyes for bioimaging. Here, we report a molecular system that integrates reversible fluorescence modulation and, in addition, radical formation in a series of covalently linked triphenylamine(TPA)-dimethyldihydropyrene(DHP) photochromic systems. The DHP units having different substitutions directly alter the electron-density of the photochromic unit, thereby regulating electronic communication TPA. Photoinduced ring opening of the DHP core activates a charge transfer pathway, resulting in a dramatic enhancement of fluorescence, as reflected in the enhancement of quantum yield from 0.01 to 0.31. The emission can be reversibly turned-off by ultraviolet irradiation or heating. Importantly, the bright state is accessed using visible light, making this negative photochromic system particularly attractive for bioimaging applications. Beyond emission control, irradiation of the same molecule at 370 nm in chloroform generates a long-lived radical. The coexistence of controlled fluorescence switching and radical formation highlights the potential of this design strategy to create multifunctional molecular systems. Such bifunctional platforms open new opportunities for accessing optical readout and chemical activity on demand within a single molecular scaffold.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"5 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755280","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}