Chemical Science最新文献

{"title":"Enhancing the photostability of red fluorescent proteins through FRET with Si-rhodamine for dynamic super-resolution fluorescence imaging.","authors":"Xuelian Zhou, Lu Miao, Wei Zhou, Yonghui Chen, Yiyan Ruan, Xiang Wang, Guangying Wang, Pengjun Bao, Qinglong Qiao, Zhaochao Xu","doi":"10.1039/d5sc02442k","DOIUrl":"10.1039/d5sc02442k","url":null,"abstract":"<p><p>Red fluorescent proteins (RFPs) are extensively utilized in biological imaging. However, their susceptibility to photobleaching restricts their effectiveness in super-resolution imaging where high photostability is crucial. In this study, we substantially improved the photostability of RFPs by incorporating a hybrid Förster resonance energy transfer (FRET) pair, utilizing RFPs as the energy donor and a photostable fluorophore, tetramethyl-Si-rhodamine (TMSiR), as the acceptor. TMSiR was selectively introduced through fusion with the HaloTag protein linked to the RFPs. We constructed a series of mApple/mCherry-TMSiR pairs with varying FRET efficiencies. Our findings reveal that higher FRET efficiency in the mApple/mCherry-TMSiR complexes correlates with enhanced photostability of RFPs. FRET competes with the singlet-to-triplet state transition of RFPs, while the spatial barrier introduced by the HaloTag protein prevents interaction between sensitized reactive oxygen species near Si-rhodamine and red fluorescent protein, enhancing the photostability of red fluorescent protein. The nearly 6-fold enhancement in mCherry's photostability allows for extended durations of dynamic structured illumination microscopy (SIM) imaging in living cells, facilitating the capture of finer details in organelle interactions. Leveraging the photostable mCherry protein, we tracked various mitochondrial fission processes and their interactions with lysosomes and the endoplasmic reticulum (ER). Interestingly, we observed the involvement of ER in all mitochondrial fission events, whereas lysosomes participated in only 66% of them.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12067651/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143978408","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":"Photocatalytic Hydrogen Peroxide Production with an External Quantum Yield of Almost 500%","authors":"Yaozong Yan, Shin-ichi Naya, Hisashi Sugime, Hiroaki Tada, Tetsuro Soejima","doi":"10.1039/d5sc01447f","DOIUrl":"https://doi.org/10.1039/d5sc01447f","url":null,"abstract":"From the perspective of energy and environmental issues, the development of green methods for H<small>₂</small>O<small>₂</small>production is demanded as an alternative to the conventional energy-intensive anthraquinone method. Among the candidates, photocatalytic H<small>₂</small>O<small>₂</small>production has recently attracted much interest. To withstand the use under harsh conditions, it is desirable that the photocatalyst be composed of robust inorganic materials. However, the external quantum yield (<em>ϕ</em><small>_ex</small>) of H<small>₂</small>O<small>₂</small> production by inorganic photocatalysts remains below 20% in most studies. Here we demonstrate that a nanohybrid photocatalyst consisting of antimony-doped SnO<small>₂</small> and ZnO can produce H<small>₂</small>O<small>₂</small> with a <em>ϕ</em><small>_ex</small> of ~500% from O<small>₂</small>-saturated ethanol aqueous solution under UV-light irradiation. In the photochemical reactions, the quantum yield is usually far below unity (&lt; 100%) due to the rapid recombination of photogenerated charge carriers. Breaking through this limit will pave the way for innovative photochemical reactions with the photocatalytic H<small>₂</small>O<small>₂</small>synthesis brought closer to practical application.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901209","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":"Bottom-up design of peptide shapes in water using oligomers of N-methyl-L/D-alanine","authors":"Jumpei Morimoto, Marin Yokomine, Yota Shiratori, Takumi Ueda, Takayuki Nakamuro, Kiyofumi Takaba, Saori Maki-Yonekura, Koji Umezawa, Koichiro Miyanishi, Yasuhiro Fukuda, Takumu Watanabe, Mayuko Suga, Ayumi Inayoshi, Takuya Yoshida, Wataru Mizukami, Koh Takeuchi, Koji Yonekura, Eiichi Nakamura, Shinsuke Sando","doi":"10.1039/d5sc01483b","DOIUrl":"https://doi.org/10.1039/d5sc01483b","url":null,"abstract":"<em>De novo</em> design of peptide shapes is of great interest in biomolecular science since the local peptide shapes formed by a short peptide chain in the proteins are often key to biological activities. Here, we show that the <em>de novo</em> design of peptide shapes with sub-nanometer conformational control can be realized using peptides consisting of <em>N</em>-methyl-L-alanine and <em>N</em>-methyl-D-alanine residues. The conformation of <em>N</em>-methyl-L/D-alanine residue is largely fixed because of the restricted bond rotation and hence can serve as a scaffold on which we can build a peptide into a designed shape. The local shape control by per-residue conformational restriction by torsional strains starkly contrasts with the global shape stabilization of proteins based on many remote interactions. The oligomers allow the bottom-up design of diverse peptide shapes with a small number of amino acid residues and would offer unique opportunities to realize the <em>de novo</em> design of biofunctional molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897802","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 hydrogen evolution via flexoelectric catalysis in gradient F-doped hydroxyapatite nanowires","authors":"Yucheng Zhang, Jiawei Huang, Lei Jiang, Jun Qiang, Zhouyang Zhang, Zhanfeng Liu, Yi Liu, Tingfang Tian, Zhao Wang, Linfeng Fei","doi":"10.1039/d5sc00710k","DOIUrl":"https://doi.org/10.1039/d5sc00710k","url":null,"abstract":"The emergence of flexoelectric effect, which refers to the linear electromechanical coupling between strain gradient and charge polarization in a wide range of materials, suggests a new catalytic mechanism to activate chemical bonds and reactions. Although pioneering studies have shown the remarkable potential for flexoelectric catalysis in a few scenarios, the lack of green, cheap, bio-compatible, and high-efficiency flexoelectric catalysts acts as a major barrier to its expanding applications. In this study, we report the effective design of a high-performance flexoelectric catalyst by simultaneous structural and compositional engineering on hydroxyapatite, a ubiquitous mineral and a well-known biomaterial. By synergizing atomic-scale and nanoscale strain gradients (which are respectively induced by surface lattice doping and geometry engineering) in F-doped hydroxyapatite nanowires (F-HAP NWs), the flexoelectric response together with the catalytic performance of the material are drastically improved, leading to a high hydrogen generation rate (322.7 μmol g<small>⁻¹</small> h<small>⁻¹</small>) in pure water. The findings highlight the potential of F-HAP NWs in flexoelectric catalysis and offer new insights into mechanocatalytic and electrochemical processes in biological systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"72 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897803","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":"A Salen-based Dinuclear Cobalt(II) Polymer with Direct and Indirect Synergy for Electrocatalytic Hydrogen Evolution","authors":"Xiao-Mei Hu, Wenjie Shi, Jianhua Mei, Yu-Chen Wang, Wei-Xue Tao, Dichang Zhong, Tongbu Lu","doi":"10.1039/d5sc02073e","DOIUrl":"https://doi.org/10.1039/d5sc02073e","url":null,"abstract":"Optimizing the spatial arrangement and geometric configuration of dinuclear metal sites within catalysts to leverage the dinuclear metal synergistic catalysis (DMSC) effect is a promising strategy for enhancing catalytic performance. In this work, we report a Salen-based dinuclear cobalt covalent organic polymer (Co<small>₂</small>-COP) that exhibits both direct and indirect DMSC synergistic effects, significantly improving catalytic efficiency for the electrocatalytic alkaline hydrogen evolution reaction (HER). Notably, one of the Co atoms in this structural unit features an OH<small>⁻</small> anion. The OH<small>⁻</small> anion facilitates both H<small>₂</small>O adsorption through <em>p</em>-<em>p</em> orbital overlapping interaction and the subsequent OH* intermediate removal by pre-attracting cations. As a result, Co<small>₂</small>-COP exhibits superior HER activity that surpasses its single-atom counterpart by a factor of 36. Control experiments and theoretical calculations revealed that the enhanced catalytic efficiency of Co<small>₂</small>-COP is attributed to both the direct DMSC effect between two Co<small>^II</small> ions, and the indirect DMSC involving the OH<small>⁻</small> anion and alkali cations. This synergistic interaction significantly facilitates water activation and accelerates the removal of the OH* intermediate, all of which are intricately linked to the unique dinuclear structure of the material.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897804","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":"A Cell-Permeable Fluorescent Probe Reveals Temporally Diverse PI(4,5)P2 Dynamics Evoked by Distinct GPCR Agonists in Neurons","authors":"Rajasree Kundu, Samsuzzoha Mondal, Akshay Kapadia, Antara Banerjee, Oleksandr A Kucherak, Andrey S Klymchenko, Sandhya Koushika, Ravindra Venkatramani, Vidita Vaidya, Ankona Datta","doi":"10.1039/d5sc01306b","DOIUrl":"https://doi.org/10.1039/d5sc01306b","url":null,"abstract":"Lipids, key constituents of cell-membranes, are the first responders to cell signals. At the crux of spatiotemporal dynamics of lipid-signaling response are phosphoinositides. Indeed, phosphoinositides like phosphatidylinositol-(4,5)-bisphosphate (PI(4,5)P2), present in the inner-leaflet of eukaryotic cell-membranes, form the link between signal reception and downstream signal-transmission. In this backdrop, reversible fluorescent probes that can track live PI(4,5)P2 dynamics on a seconds time-scale will afford key insights into lipid-mediated signaling. However, realizing cell-permeable PI(4,5)P2-selective sensors for imaging dynamics remains a challenge due to the presence of structurally similar lipids and low levels of PI(4,5)P2. We report a computationally-designed, rapid-response, reversible, photo-stable, fluorescent sensor that permeates living cells, neurons, and a multicellular organism within few min of direct incubation and distinctly visualizes PI(4,5)P2 pools. We used the sensor to interrogate the role of PI(4,5)P2 in driving heterogeneity of signaling responses and contrasting behavioral effects that ensue upon binding of distinct ligands to the same G protein-coupled receptor. Specifically, we asked whether probing PI(4,5)P2 dynamics using our novel sensor could uncover the earliest of signaling differences evoked by hallucinogenic versus non-hallucinogenic ligands at the serotonin2A (5-HT<small>_2A</small>) receptor. Our results reveal that a hallucinogenic ligand at the 5-HT<small>_2A</small> receptor leads to a slower rate of PI(4,5)P2-depletion when compared to a non-hallucinogenic ligand, within the initial seconds of ligand addition, but has a sustained effect. The ability of our designer chemical probe in timing early seconds-minute timescale lipid-dynamics in living cells opens avenues for tracking early time-point molecular events in neuronal response to chemical and physical stimuli.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"44 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901235","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":"Continuous Coordination Modulation with Differing Heteroatoms Unveils Favorable Single-atom Ni Sites for Near-unity CO Selectivity in CO2 Electroreduction","authors":"Shuangqun Chen, Tong Cao, Wen Yan, Ke Zhao, Yalin Guo, Tiantian Wu, Daliang Zhang, Ming Ma, Yu Han, Jianfeng Huang","doi":"10.1039/d5sc01998b","DOIUrl":"https://doi.org/10.1039/d5sc01998b","url":null,"abstract":"Coordination modulation is a key strategy for enhancing the catalytic activity of single-atom catalysts (SACs) in CO2 electroreduction. However, achieving such modulation within the same framework by incorporating an array of heteroatoms with differing electronic properties remains unexplored, despite its potential for optimizing active sites. Here, we investigate unprecedentedly three Ni-based SACs (N3Ni–C, N3Ni–N, and N3Ni–O), where varying coordinating atoms (C, N, O) modulate continuously the electronic structure to explore their effects on CO2 electroreduction. Compared to the N3Ni–N catalyst with classic Ni–N4 coordination, N3Ni–C demonstrates significantly enhanced CO2 conversion, achieving remarkably a near-unity Faradaic efficiency for CO (99.3%) at −0.7 VRHE in the H-cell and a CO partial current density of 396.8 mA cm–2 at –1.15 VRHE in the flow cell, whereas N3Ni–O exhibits inferior performance. Operando and computational investigations reveal that both C- and O-coordination enhance CO2 hydrogenation by elevating the Ni d-band center, thereby strengthening *COOH intermediate adsorption. However, the concurrent promotion of the hydrogen evolution reaction competes with CO2 reduction, ultimately leading to opposite effects on performance. This work provides atomic-level insights into CO2 electroreduction mechanisms and offers compelling strategies for improving SAC performance via coordination modulation with heteroatoms.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897806","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":"The hole mass in Car-Parrinello molecular dynamics: insights into the dynamics of excitation","authors":"Sherif Abdulkader Tawfik, Tiffany R Walsh","doi":"10.1039/d5sc00175g","DOIUrl":"https://doi.org/10.1039/d5sc00175g","url":null,"abstract":"In the Car-Parrinello molecular dynamics (CPMD) formalism, orbitals can be assigned different effective masses according to whether the orbital is occupied by a hole or an electron, and such masses affect the response of the orbitals to their environment. Inspired by this, we introduce and implement a novel modification of CPMD, HoleMass CPMD, in which a hole, which is a partially empty orbital, is assigned a fictitious mass that is different from fully occupied orbitals. Despite the simplicity of the approach, we find that it solves a key problem in first principles molecule dynamics simulation: for a set of carefully assigned mass values, the method is able to successfully simulate photoinduced chemical reactions, exemplified here by the ring-opening reaction in oxirane within a few femtoseconds, and cyclobutene, within a few picoseconds. Our method can reproduce the CO ring-opening of oxirane, and the correct isomerization sequence for cyclobutene: when the ring opens, the first isomer that forms is the cis isomer, followed by the trans isomer. Our method has been implemented in the Car-Parrinello package of QuantumEspresso and is available as an open-source contribution. The HoleMass CPMD method provides a new quantum chemistry tool for the simulation of excitation dynamics in molecules, and can also be applied for modelling charge localization effects in materials systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893966","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":"Enzyme-loaded Fe3+-doped ZIF-90 particles as catalytic bioreactor hybrids for operating catalytic cascades","authors":"Jin Wang, Yunlong Qin, Raanan Carmieli, Vitaly Gutkin, Eli Pikarsky, Zhen Zhang, Xinghua Chen, Itamar Willner","doi":"10.1039/d5sc01972a","DOIUrl":"https://doi.org/10.1039/d5sc01972a","url":null,"abstract":"Fe<small>³⁺</small>-doped ZIF-90 (Fe<small>³⁺</small>-ZIF-90), a metal–organic framework (MOF), was synthesized and characterized. The MOF particles reveal peroxidase-like activity reflected by catalyzing the H<small>₂</small>O<small>₂</small> oxidation of 3,3′,5,5′-tetramethylbenzidine, TMB, to TMB˙<small>⁺</small>. Integration of the two enzymes, β-galactosidase, β-Gal, and glucose oxidase, GOx, in the Fe<small>³⁺</small>-ZIF-90 provides an organized framework allowing the operation of a three-catalyst cascade, where the β-Gal-catalyzed oxidation of lactose yields glucose and galactose, and the resulting glucose is aerobically oxidized by GOx to gluconic acid and H<small>₂</small>O<small>₂</small>, followed by the Fe<small>³⁺</small>-ZIF-90-catalyzed H<small>₂</small>O<small>₂</small> oxidation of TMB to TMB˙<small>⁺</small>. The coupled bienzyme/nanozyme cascade in the MOFs is <em>ca.</em> 5-fold enhanced, as compared to a homogeneous mixture of the catalytic constituents. The enhanced catalytic activity of the enzyme cascades in the MOFs is attributed to the confined reaction framework, allowing product channeling across the multienzyme constituents and overcoming diffusion barriers. Moreover, the enzymes, acetylcholine esterase, AChE, and choline oxidase, ChOx, are encapsulated in the confined porous Fe<small>³⁺</small>-ZIF-90 particles. The catalytic cascade where the neurotransmitter acetylcholine is hydrolyzed by AChE followed by the stepwise ChOx-catalyzed oxidation of choline to betaine and H<small>₂</small>O<small>₂</small>, and the Fe<small>³⁺</small>-ZIF-90-catalyzed oxidation of TMB to colored TMB˙<small>⁺</small> by H<small>₂</small>O<small>₂</small> is demonstrated. The three-catalyst cascade is <em>ca.</em> 5-fold enhanced as compared to the mixture of separated catalysts. The integrated three-catalyst AChE/ChOx/Fe<small>³⁺</small>-ZIF-90 particles are applied as colorimetric sensors detecting the neurotransmitter acetylcholine and probing AChE inhibitors. The novelty of the systems is reflected by the assembly of multienzyme catalytic Fe<small>³⁺</small>-ZIF-90 hybrids in confined environments as bioreactor frameworks driving effective biocatalytic cascades.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893970","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":"Synthesis of synergistic catalysts: integrating defects, SMSI, and plasmonic effects for enhanced photocatalytic CO2 reduction","authors":"Rajesh Belgamwar, Charvi Singhvi, Gunjan Sharma, Vinod K. Paidi, Pieter Glatzel, Seiji Yamazoe, Pradip Sarawade, Vivek Polshettiwar","doi":"10.1039/d5sc01166c","DOIUrl":"https://doi.org/10.1039/d5sc01166c","url":null,"abstract":"This study explores how the strategic material design introduced synergetic coupling of strong metal–support interaction (SMSI) between copper (Cu) nanoparticles and titanium dioxide (TiO<small>₂</small>) loaded on dendritic fibrous nanosilica (DFNS), defects within TiO<small>₂</small>, and localized surface plasmon resonance (LSPR) of Cu. Mechanistic insights were gained using <em>in situ</em> high-energy radiation fluorescence detection X-ray absorption near edge structure (HERFD-XANES) spectroscopy, electron microscopy, and finite-difference time-domain (FDTD) simulations. The introduction of copper nanoparticles onto the TiO<small>₂</small> surface induces a change in the electronic structure and surface chemistry of TiO<small>₂</small>, due to the electronic interactions between Cu sites and TiO<small>₂</small> at the interface, inducing SMSI. This resulted in enhancing light absorption, efficient charge transfer, reducing electron–hole recombination and enhancing the overall catalytic efficiency. The activation energy for CO<small>₂</small> reduction was significantly reduced in light as compared to dark. Control experiments revealed a dominant role of photoexcited hot carriers, alongside photothermal effects, in driving CO<small>₂</small> reduction, supported by super-linear light intensity dependence and reduced activation energies. The unique interplay of O-vacancy defects, electron–hole separation in TiO<small>₂</small> and LSPR effects in Cu led to the excellent performance of the DFNS/TiO<small>₂</small>–Cu10 catalyst. The catalyst outperformed the reported photocatalytic systems with a CO production rate of ∼3600 mmol g<small>_Cu</small><small>⁻¹</small> h<small>⁻¹</small> (360 mmol g<small>_cat</small><small>⁻¹</small> h<small>⁻¹</small>) with nearly 100% selectivity. A reaction mechanism was proposed based on the intermediates observed using the <em>in situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and co-related to the electron transfer pathways to different reactants using HERFD-XANES. The study concluded that the synergistic coupling of Cu LSPR, charge carrier separation <em>via</em> SMSI at the Cu–TiO<small>₂</small> interface, and O-vacancy defects stabilized by SMSI enhance the photocatalytic CO<small>₂</small> reduction performance of this hybrid system.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"87 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893965","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}