Metal nanoclusters(MNCs)possess distinct chemical properties due to their diverse electronic structures.As a class of promising model catalysts,it is of importance to explore the relationship between their structures ...Metal nanoclusters(MNCs)possess distinct chemical properties due to their diverse electronic structures.As a class of promising model catalysts,it is of importance to explore the relationship between their structures and properties.However,it is still challenging to get highly active and stable MNCs as surface ligands can hinder their activities,while a complete lack of surface ligand protection can lead to instability.To address this concern,here a series of Pd_(6)nanoclusters(NCs)with varying ligand amounts were synthesized by using Pd_(6)(SC_(6)(C_(2))H_(17))_(12)as precursor and single-walled carbon nanotube(s-CNT)as carrier through treating the composite at different temperatures and times.展开更多
Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical p...Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.展开更多
Atomically precise coordination nanoclusters(NCs)constitute a pivotal and rapidly advancing domain in the realms of materials science and chemistry owing to their distinctive crystal structures and exceptional attribu...Atomically precise coordination nanoclusters(NCs)constitute a pivotal and rapidly advancing domain in the realms of materials science and chemistry owing to their distinctive crystal structures and exceptional attributes encompassing molecular magnetism[1],photoluminescence[2],and catalysis[3].Organic ligands play a crucial role in effectively shielding these NCs,serving two primary functions:firstly,vital in preventing NC aggregation,particularly for the formation of robust single-crystal structures;secondly,acting as either bridging or peripheral structural components of NCs[4].This characterization of organic-inorganic hybridization offers unique advantages for unraveling the intricate relationships between structure and properties[5].展开更多
To realize the application of electromagnetic wave absorption(EWA)devices in humid marine environments,bifunctional EWA materials with better EWA capacities and anticorrosion properties have great exploration signific...To realize the application of electromagnetic wave absorption(EWA)devices in humid marine environments,bifunctional EWA materials with better EWA capacities and anticorrosion properties have great exploration significance and systematic research re-quirements.By utilizing the low-cost and excellent magnetic and stable chemical characteristics of barium ferrite(BaFe_(12)O_(19))and using the high dielectric loss and excellent chemical inertia of nanocarbon clusters,a new type of nanocomposites with carbon nanoclusters en-capsulating BaFe_(12)O_(19)was designed and synthesized by combining an impregnation method and a high-temperature calcination strategy.Furthermore,Ce-Mn ions were introduced into the BaFe_(12)O_(19)lattice to improve the dielectric and magnetic properties of BaFe_(12)O_(19)cores significantly,and the energy band structure of the doped lattice and the orders of Ce replacing Fe sites were calculated.Benefiting from Ce-Mn ion doping and carbon nanocluster encapsulation,the composite material exhibited excellent dual functionality of corrosion resist-ance and EWA.When BaCe_(0.2)Mn_(0.3)Fe_(11.5)O_(19)-C(BCM-C)was calcined at 600°C,the minimum reflection loss of-20.1 dB was achieved at 14.43 GHz.The Ku band’s effective absorption bandwidth of 4.25 GHz was achieved at an absorber thickness of only 1.3 mm.The BCM-C/polydimethylsiloxane coating had excellent corrosion resistance in the simulated marine environment(3.5wt%NaCl solution).The|Z|0.01Hz value of BCM-C remained at 106Ω·cm^(2)after 12 soaking days.The successful preparation of the BaFe_(12)O_(19)composite en-capsulated with carbon nanoclusters provides new insights into the preparation of multifunctional absorbent materials and the fabrication of absorbent devices applied in humid marine environments in the future.展开更多
Herein,a one-pot chemical reduction method was reported to prepare folic acid(FA)-stabilized silver nanoclusters(FA@Ag NCs),in which FA,hydrazine hydrate,and silver nitrate were used as capping agent,reducing agent,an...Herein,a one-pot chemical reduction method was reported to prepare folic acid(FA)-stabilized silver nanoclusters(FA@Ag NCs),in which FA,hydrazine hydrate,and silver nitrate were used as capping agent,reducing agent,and precursor,respectively.Several technologies were employed to investigate the structures and optical properties of FA@Ag NCs,including transmission electron microscopy(TEM),X-ray photoelectron spectrometer(XPS),Fourier transform infrared spectrometer(FTIR),X-ray diffractometer(XRD),fluorescence spectrometer,and ultraviolet visible absorption spectrometer.FA@Ag NCs were suggested to be highly dispersed and spherical with a size of around 2.8 nm.Moreover,the maximum excitation and emission wavelengths of FA@Ag NCs were 370 and 447 nm,respectively.Under the optimal detection conditions,FA@Ag NCs could be used to effectively detect malachite green with the linear detection range of 0.5-200μmol·L^(-1).The detection limit was 0.084μmol·L^(-1).The fluorescence-quenching mechanism was ascribed to the static quenching.The detection system based on FA@AgNCs was successfully used for the detection of malachite green in actual samples with good accuracy and reproducibility.展开更多
Herein,copper nanoclusters(Cu NCs)were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand,with Cu(NO_(3))_(2)as copper source.Subse-quen...Herein,copper nanoclusters(Cu NCs)were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand,with Cu(NO_(3))_(2)as copper source.Subse-quently,composite fluorescent nanoparticles,chitosan-functionalized silica nanoparticles(CSNPs)-coated Cu NCs(Cu NCs/CSNPs),were synthesized via a reverse microemulsion method.Compared with Cu NCs,the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance.Based on the composite Cu NCs/CSNPs,a fluorescence method for the detection of cefixime fluorescence quenching was estab-lished.The technique was simple,sensitive,and selective for detecting cefixime.The fluorescence quenching effi-ciency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5µmol·L^(-1)(1.81-17.46 mg·L^(-1)),with a limit of detection of 0.0455µmol·L^(-1)(20.6µg·L^(-1)).展开更多
Photoluminescence(PL)is one of the most important properties of metal nanoclusters(NCs).Achieving effi⁃cient white light emission in metal NCs with a precise structures is important for practical applications but rema...Photoluminescence(PL)is one of the most important properties of metal nanoclusters(NCs).Achieving effi⁃cient white light emission in metal NCs with a precise structures is important for practical applications but remains a great challenge.Here,we report the efficient white emission from Au_(10) NCs by elaborately deploying the surface chemistry engi⁃neering strategy.Specifically,the bis-aldehyde ligands of 4-hydroxyisophthalaldehyde(HOA)are decorated on the surface of Au_(10)(SG)_(10) NCs(glutathione denoted as SG)through the cross-linking reaction of imine bonds(-CH==N-).The combination of 477 nm blue emission from HOA ligands and 620 nm orange-yellow emission from Au_(10)(SG)_(10) NCs generates white-light emission in HOA-Au_(10)(SG)_(10) NCs in the solvent mixture of ethanol and water.More importantly,dynamic color tuning from blue light to yellow light is achieved by controlling the volume fraction of ethanol in the solvent mixture.In addi⁃tion,the as-formed imine bonds significantly improve the structural rigidity of HOA-Au_(10)(SG)_(10) NCs,resulting in the 51.2%absolute photoluminescence quantum yield(PLQY)of white emission.The present study exemplifies the paradigm to control the emission color and improve the PLQY of metal NCs through rational surface chemistry engineering.展开更多
Achieving high-efficiency photoluminescence in trivalent lanthanides(Ln^(3+))requires precise crystalfield perturbation to overcome parity-forbidden 4f-transitions and suppress nonradiative decay.However,realizing suc...Achieving high-efficiency photoluminescence in trivalent lanthanides(Ln^(3+))requires precise crystalfield perturbation to overcome parity-forbidden 4f-transitions and suppress nonradiative decay.However,realizing such control remains challenging,even in well-optimized Ln^(3+) -doped nanocrystals.Here,by exploiting the atomically precise structure of metal nanoclusters,we demonstrate symmetry engineering in the Eu_(2)Ti_(4) nanoclusters through stepwise ligand substitution(BA/Phen→FBA/Phen→FBA/Bpy.BA:benzoicacid;Phen:1,10-phenanthroline;FBA:p-fluorobenzoicacid;Bpy:2,2'-bipyridine).The incorporation of FBA effectively suppresses nonradiative relaxation,while the flexible Bpy ligand induces symmetry reduction from D_(2d) to C_(2v) through coordination modulation,yielding a high photoluminescence quantum yield(PLQY)of 91.2%in the Ln^(3+) cluster systems.The transient-absorption,Judd-Ofelt theory,crystal-field analysis,and temperature-dependent photophysical studies elucidated the underlying modulation mechanisms.Furthermore,these clusters exhibit promising potential for optoelectronic applications,offering a new design strategy for high-performance luminescent materials.展开更多
Selenolate ligands are expected to endow fluorescent gold nanoclusters(AuNCs)with better stability and more bioactivity than thiolate ligands,making them promising in the biological field.However,there are few studies...Selenolate ligands are expected to endow fluorescent gold nanoclusters(AuNCs)with better stability and more bioactivity than thiolate ligands,making them promising in the biological field.However,there are few studies on the synthesis of water-soluble selenolate-protected AuNCs,and the impact of selenolate ligands on the optical properties of AuNCs is still unclear.In this study,we synthesized selenolatecostabilized water-soluble,near-infrared fluorescent AuNCs with four different amounts of benzeneselenol(PhSeH),and systematically investigated the role of PhSeH on their optical properties.It is discovered that an appropriate PhSeH content is favorable for the fluorescence enhancement of AuNCs due to the ligand to metal charge transfer effect.Moreover,AuNCs co-stabilized by selenolate ligands exhibit better photostability and long-term stability compared with AuNCs stabilized by thiolate ligands,owing to the introduction of Au-Se bond on their surfaces.Further cellular experiments revealed that selenolate ligands can also affect the cellular uptake efficiency of AuNCs and their imaging property.These results provide important knowledges for further development of new,robust selenolate-stabilized metal NCs for biological application.展开更多
Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunct...Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunctional catalysts remains challenging.Here,we report a bifunctional electrocatalyst of Ru NCs@NPC,embedding the ultrafine Ru nanoclusters into N-doped porous carbon via microwave reduction.Due to the ultrafine Ru nanoclusters and N doping,the composite exhibits exceptional activity for both HER and HzOR,requiring−55 and−67 mV to reach 10 mA·cm^(−2) in alkaline media.In the overall hydrazine splitting(OHzS)system,Ru NCs@NPC is used as both anode and cathode materials,achieving 10 mA·cm^(−2) only at 0.036 V.The zinc hydrazine(Zn-Hz)battery assembled with Ru NCs@NPC cathode and Zn foil anode can provide a stable voltage of 0.4 V and exhibit 98.5%energy efficiency.Therefore,integrating Zn-Hz battery with OHzS system enables self-powered H_(2) evolution.The density function theory calculations reveal that the Ru-N bond increases the metal-support interaction.展开更多
Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalit...Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalities.Among that,Cu nanoclusters have been gaining continuous increasing research attentions,thanks to the low cost,diversified structures,and superior catalytic performance for various reactions.In this review,we first summarize the recent progress regarding the synthetic methods of atomically precise Cu nanoclusters and the coordination modes between Cu and several typical ligands and then discuss the catalytic applications of these Cu nanoclusters with some explicit examples to explain the atomical-level structure-performance relationship.Finally,the current challenges and future research perspectives with some critical thoughts are elaborated.We hope this review can not only provide a whole picture of the current advances regarding the synthesis and catalytic applications of atomically precise Cu nanoclusters,but also points out some future research visions in this rapidly booming field.展开更多
Skins expose to kinds of risk factors for damage,such as the hormone drugs,skin care products and ultraviolet radiation,which is accompanied by the production of excessive reactive oxygen species(ROS)and eventually le...Skins expose to kinds of risk factors for damage,such as the hormone drugs,skin care products and ultraviolet radiation,which is accompanied by the production of excessive reactive oxygen species(ROS)and eventually leads to hypertrichosis.This skin disease is not aesthetically pleasing and even causes psychological and spiritual problems such as inferiority,anxiety and irritability.Current therapies are limited and often unsatisfactory,such as pharmacological and physical therapies,which have adverse effects and cause the irreversible destruction of hair follicles.Gold nanoclusters have good biocompatibility and their biosynthesis in vivo is responsive to oxidative stress microenvironment(OSM),which could be a safe and effective drug for ROS-induced skin injury.In our study,we demonstrated that zero valence fluorescent gold nanoclusters(FGNCs)were in situ biosynthesized in the plucking-induced damaged skin but not in the normal skin after the administration of gold precursors(+3),while FGNCs inhibited hair follicle regeneration by negatively regulating nuclear transcription factor kappa B(NFκB)-mediated inflammatory response signaling pathway(NFκB/tumor necrosis factor-α(TNF-α)axis).This OSM-responsive in situ biosynthesis method is facile and safe and holds great promise for curing hypertrichosis associated with skin dermatitis and injury.展开更多
Bovine serum albumin(BSA)and glycine(Gly)dual-ligand-modified copper nanoclusters(BSA-Gly CuNCs)with high fluorescence intensity were synthesized by a one-pot strategy.Based on the competitive fluorescence quenching a...Bovine serum albumin(BSA)and glycine(Gly)dual-ligand-modified copper nanoclusters(BSA-Gly CuNCs)with high fluorescence intensity were synthesized by a one-pot strategy.Based on the competitive fluorescence quenching and dynamic quenching effects of ornidazole(ONZ)on BSA-Gly CuNCs,a simple and sensitive detection method for ONZ was successfully developed.The experimental results demonstrate that the addition of the small molecule Gly can more effectively protect CuNCs,and thus enhance its fluorescence intensity and stability.The proposed assay allowed for the detection of ONZ in a linear range of 0.28 to 52.60μmol·L^(-1)and a detection limit of 0.069μmol·L^(-1).Compared with the single-ligand-modified CuNCs,dual-ligand-modified BSA-Gly CuNCs had higher fluorescence intensity,stability,and sensing ability and were successfully applied to evaluate ONZ in actual ONZ tablets.展开更多
The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;d...The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.展开更多
Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is sti...Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is still lacking for understanding the structure-performance relationship at atomical level.Herein,we report the synthesis,structure analysis,and OER catalytic properties of a novel atomically precise Cu nanocluster of[Cu_(6)(C≡CR)4(dppe)3](R=Fe(C_(5)H_(5))_(2),abbreviated as Cu_(6)NC).Cu_(6)NC possesses a unique metal core configuration and metal-ligand binding motifs.Interestingly,Cu_(6)NC has superior OER performance to pure phosphine ligand-protected Cu18 nanocluster(Cu18NC in short,same Cu amount)and Cu nanoparticle(CuNP)with larger size,manifested by the lower overpotential at 10 mA·cm^(−2),smaller Tafel slope,and reduced charge transfer resistance.Cu_(6)NC also demonstrated excellent long-term stability for prolonged operation.Density functional theory(DFT)calculations further confirm that the alkynyl ligand plays a critical role in promoting the catalytic performance,and Cu_(6)NC has a lower energy barrier in the rate-determining step of the OER process.This study not only highlights the unique advantages of employing ultrasmall Cu nanoclusters for OER,but also can shed light on designing ligand-functionalized metal nanoclusters for electrochemical energy conversion and beyond.展开更多
Metal-nanocluster materials have gradually become a promising electrode candidate for supercapaci-tor application.The high-efficient and rational architecture of these metal-nanocluster electrode mate-rials with satis...Metal-nanocluster materials have gradually become a promising electrode candidate for supercapaci-tor application.The high-efficient and rational architecture of these metal-nanocluster electrode mate-rials with satisfied supercapacitive performance are full of challenges.Herein,Fe-nanocluster anchored porous carbon(FAPC)nanosheets were constructed through a facile and low-cost impregnation-activation strategy.Various characterization methods documented that FAPC nanosheets possessed a mesopore-dominated structure with large surface area and abundant Fe-N4 active sites,which are crucial for su-percapacitive energy storage.The optimal FAPC electrode exhibited a high specific capacitance of 378 F/g at a specific current of 1 A/g and an excellent rate capability(271 F/g at 10 A/g),which are comparable or even superior to that of most reported carbon candidates.Furthermore,the FAPC-based device achieved a desired specific energy of 14.8 Wh/kg at a specific power of 700 W/kg.This work opens a new avenue to design metal-nanocluster materials for high-performance biomass waste-based supercapacitors.展开更多
Remarkable progress has characterized the field of electrocatalysis in recent decades,driven in part by an enhanced comprehension of catalyst structures and mechanisms at the nanoscale.Atomically precise metal nanoclu...Remarkable progress has characterized the field of electrocatalysis in recent decades,driven in part by an enhanced comprehension of catalyst structures and mechanisms at the nanoscale.Atomically precise metal nanoclusters,serving as exemplary models,significantly expand the range of accessible structures through diverse cores and ligands,creating an exceptional platform for the investigation of catalytic reactions.Notably,ligand‐protected Au nanoclusters(NCs)with precisely defined core numbers offer a distinct advantage in elucidating the correlation between their specific structures and the reaction mechanisms in electrocatalysis.The strategic modulation of the fine microstructures of Au NCs presents crucial opportunities for tailoring their electrocatalytic performance across various reactions.This review delves into the profound structural effects of Au NC cores and ligands in electrocatalysis,elucidating their underlying mechanisms.A detailed exploration of the fundamentals of Au NCs,considering core and ligand structures,follows.Subsequently,the interaction between the core and ligand structures of Au NCs and their impact on electrocatalytic performance in diverse reactions are examined.Concluding the discourse,challenges and personal prospects are presented to guide the rational design of efficient electrocatalysts and advance electrocatalytic reactions.展开更多
On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient ...On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient and eco-friendly process,mild conditions,and simple post-treatment.The experimental results reveal that a homogeneous deposited film(Cu NCs/CCS nanocomposite film)is generated on the Cu plate(the anode)after electrodeposition,which exhibits an obvious red florescence.The results from TEM observation suggest there are nanoparticles(with the average particle size of 2.3 nm)in the deposited film.Spectral analysis results both demonstrate the existence of Cu NCs in the deposited film.Moreover,the Cu NCs/CCS film modified electrode is directly created through electrodeposition of CCS,which enables promising application in the electrochemical sensing.By means of fluorescence properties of Cu NCs,the Cu NCs/CCS film also owns the potential in fluorescence detection.Therefore,this work builds a novel method for the green synthesis of Cu NCs,meanwhile it offers a convenient and new electrodeposition strategy to prepare polysaccharide-based Cu NCs nanocomposites for uses in functional nanocomposites and bioelectronic devices.展开更多
Herein,we propose a simple and rapid approach for synthesizing a CuS/Ru composite that serves as a bifunctional electrocatalyst to promote hydrogen production and concurrently convert sulfion into a value-added sulfur...Herein,we propose a simple and rapid approach for synthesizing a CuS/Ru composite that serves as a bifunctional electrocatalyst to promote hydrogen production and concurrently convert sulfion into a value-added sulfur product.This composite comprises Ru nanoclusters supported on the CuS nanostructure,achieved through simple pulsed laser irradiation in liquid approach.The optimized CuS/Ru-30 electrocatalyst demonstrates remarkable bifunctional electrocatalytic activity,exhibiting a negligible working potential of 0.28 V(vs.RHE)for the anodic sulfion oxidation reaction(SOR)and a minimal overpotential of 182 m V for cathodic hydrogen evolution reaction(HER)to achieve 10 mA cm^(-2)of current density.Moreover,the Cu S/Ru-30 electrocatalyst shows exceptional selectivity for converting sulfion into valuable sulfur during anodic oxidation reactions.Remarkably,in a two-electrode electrolyzer system utilizing Cu S/Ru-30 as both the anode and cathode,the SOR+HER coupled water electrolysis system demands only 0.52 V to reach 10 mA cm^(-2),which is considerably lesser compared to the OER+HER coupled water electrolysis(1.85 V).The experimental results and density function theory(DFT)calculations reveal that the strong electron interaction between CuS and Ru nanoclusters generates a built-in electric field,greatly enhancing electron transfer efficiency.This significantly boosts the HER performance and facilitates the adsorption and production of sulfur intermediates.This study presents a rapid and simple strategy for synthesizing a dual-functional catalyst suitable for low-voltage hydrogen generation while facilitating the recovery of valuable sulfur sources.展开更多
For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a...For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.展开更多
基金financially supported by the Natural Science Foundation of Guangxi,China(Nos.2019GXNSFGA245003 and 2021GXNSFBA220058)the National Natural Science Foundation of China(Nos.22272036 and 22362008)+2 种基金Guangxi Technology Base and Talent Subject,China(GUIKE AD23026272)Guangxi Normal University Research Grant,China(No.2022TD)Innovation Project of Guangxi Graduate Education(No.XYCSR2023018)。
文摘Metal nanoclusters(MNCs)possess distinct chemical properties due to their diverse electronic structures.As a class of promising model catalysts,it is of importance to explore the relationship between their structures and properties.However,it is still challenging to get highly active and stable MNCs as surface ligands can hinder their activities,while a complete lack of surface ligand protection can lead to instability.To address this concern,here a series of Pd_(6)nanoclusters(NCs)with varying ligand amounts were synthesized by using Pd_(6)(SC_(6)(C_(2))H_(17))_(12)as precursor and single-walled carbon nanotube(s-CNT)as carrier through treating the composite at different temperatures and times.
文摘Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.
基金financial support from the National Natural Science Foundation of China(Nos.22171094,21925104,92261204,and 22431005)Hubei Provincial Science and Technology Innovation Team Project[2022]The National Key R&D Program of China(No.2022YFB3807700)。
文摘Atomically precise coordination nanoclusters(NCs)constitute a pivotal and rapidly advancing domain in the realms of materials science and chemistry owing to their distinctive crystal structures and exceptional attributes encompassing molecular magnetism[1],photoluminescence[2],and catalysis[3].Organic ligands play a crucial role in effectively shielding these NCs,serving two primary functions:firstly,vital in preventing NC aggregation,particularly for the formation of robust single-crystal structures;secondly,acting as either bridging or peripheral structural components of NCs[4].This characterization of organic-inorganic hybridization offers unique advantages for unraveling the intricate relationships between structure and properties[5].
基金supported by the National Key R&D Program of China(Nos.2022YFB3504804 and 2023YFF0718303)the National Natural Science Foundation of China(Nos.51871219,52071324,52031014,and 52401255)+1 种基金Science and Technology Project of Shenyang City(No.22-101-0-27)Liaoning Institute of Science and Technology Doctoral Initiation Fund Project(No.2307B19).
文摘To realize the application of electromagnetic wave absorption(EWA)devices in humid marine environments,bifunctional EWA materials with better EWA capacities and anticorrosion properties have great exploration significance and systematic research re-quirements.By utilizing the low-cost and excellent magnetic and stable chemical characteristics of barium ferrite(BaFe_(12)O_(19))and using the high dielectric loss and excellent chemical inertia of nanocarbon clusters,a new type of nanocomposites with carbon nanoclusters en-capsulating BaFe_(12)O_(19)was designed and synthesized by combining an impregnation method and a high-temperature calcination strategy.Furthermore,Ce-Mn ions were introduced into the BaFe_(12)O_(19)lattice to improve the dielectric and magnetic properties of BaFe_(12)O_(19)cores significantly,and the energy band structure of the doped lattice and the orders of Ce replacing Fe sites were calculated.Benefiting from Ce-Mn ion doping and carbon nanocluster encapsulation,the composite material exhibited excellent dual functionality of corrosion resist-ance and EWA.When BaCe_(0.2)Mn_(0.3)Fe_(11.5)O_(19)-C(BCM-C)was calcined at 600°C,the minimum reflection loss of-20.1 dB was achieved at 14.43 GHz.The Ku band’s effective absorption bandwidth of 4.25 GHz was achieved at an absorber thickness of only 1.3 mm.The BCM-C/polydimethylsiloxane coating had excellent corrosion resistance in the simulated marine environment(3.5wt%NaCl solution).The|Z|0.01Hz value of BCM-C remained at 106Ω·cm^(2)after 12 soaking days.The successful preparation of the BaFe_(12)O_(19)composite en-capsulated with carbon nanoclusters provides new insights into the preparation of multifunctional absorbent materials and the fabrication of absorbent devices applied in humid marine environments in the future.
文摘Herein,a one-pot chemical reduction method was reported to prepare folic acid(FA)-stabilized silver nanoclusters(FA@Ag NCs),in which FA,hydrazine hydrate,and silver nitrate were used as capping agent,reducing agent,and precursor,respectively.Several technologies were employed to investigate the structures and optical properties of FA@Ag NCs,including transmission electron microscopy(TEM),X-ray photoelectron spectrometer(XPS),Fourier transform infrared spectrometer(FTIR),X-ray diffractometer(XRD),fluorescence spectrometer,and ultraviolet visible absorption spectrometer.FA@Ag NCs were suggested to be highly dispersed and spherical with a size of around 2.8 nm.Moreover,the maximum excitation and emission wavelengths of FA@Ag NCs were 370 and 447 nm,respectively.Under the optimal detection conditions,FA@Ag NCs could be used to effectively detect malachite green with the linear detection range of 0.5-200μmol·L^(-1).The detection limit was 0.084μmol·L^(-1).The fluorescence-quenching mechanism was ascribed to the static quenching.The detection system based on FA@AgNCs was successfully used for the detection of malachite green in actual samples with good accuracy and reproducibility.
文摘Herein,copper nanoclusters(Cu NCs)were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand,with Cu(NO_(3))_(2)as copper source.Subse-quently,composite fluorescent nanoparticles,chitosan-functionalized silica nanoparticles(CSNPs)-coated Cu NCs(Cu NCs/CSNPs),were synthesized via a reverse microemulsion method.Compared with Cu NCs,the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance.Based on the composite Cu NCs/CSNPs,a fluorescence method for the detection of cefixime fluorescence quenching was estab-lished.The technique was simple,sensitive,and selective for detecting cefixime.The fluorescence quenching effi-ciency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5µmol·L^(-1)(1.81-17.46 mg·L^(-1)),with a limit of detection of 0.0455µmol·L^(-1)(20.6µg·L^(-1)).
文摘Photoluminescence(PL)is one of the most important properties of metal nanoclusters(NCs).Achieving effi⁃cient white light emission in metal NCs with a precise structures is important for practical applications but remains a great challenge.Here,we report the efficient white emission from Au_(10) NCs by elaborately deploying the surface chemistry engi⁃neering strategy.Specifically,the bis-aldehyde ligands of 4-hydroxyisophthalaldehyde(HOA)are decorated on the surface of Au_(10)(SG)_(10) NCs(glutathione denoted as SG)through the cross-linking reaction of imine bonds(-CH==N-).The combination of 477 nm blue emission from HOA ligands and 620 nm orange-yellow emission from Au_(10)(SG)_(10) NCs generates white-light emission in HOA-Au_(10)(SG)_(10) NCs in the solvent mixture of ethanol and water.More importantly,dynamic color tuning from blue light to yellow light is achieved by controlling the volume fraction of ethanol in the solvent mixture.In addi⁃tion,the as-formed imine bonds significantly improve the structural rigidity of HOA-Au_(10)(SG)_(10) NCs,resulting in the 51.2%absolute photoluminescence quantum yield(PLQY)of white emission.The present study exemplifies the paradigm to control the emission color and improve the PLQY of metal NCs through rational surface chemistry engineering.
基金Project supported by the National Key Research and Development Program of China(2024YFE0206100)the National Natural Science Foundation of China(T2325015,U21A2068,12174151)。
文摘Achieving high-efficiency photoluminescence in trivalent lanthanides(Ln^(3+))requires precise crystalfield perturbation to overcome parity-forbidden 4f-transitions and suppress nonradiative decay.However,realizing such control remains challenging,even in well-optimized Ln^(3+) -doped nanocrystals.Here,by exploiting the atomically precise structure of metal nanoclusters,we demonstrate symmetry engineering in the Eu_(2)Ti_(4) nanoclusters through stepwise ligand substitution(BA/Phen→FBA/Phen→FBA/Bpy.BA:benzoicacid;Phen:1,10-phenanthroline;FBA:p-fluorobenzoicacid;Bpy:2,2'-bipyridine).The incorporation of FBA effectively suppresses nonradiative relaxation,while the flexible Bpy ligand induces symmetry reduction from D_(2d) to C_(2v) through coordination modulation,yielding a high photoluminescence quantum yield(PLQY)of 91.2%in the Ln^(3+) cluster systems.The transient-absorption,Judd-Ofelt theory,crystal-field analysis,and temperature-dependent photophysical studies elucidated the underlying modulation mechanisms.Furthermore,these clusters exhibit promising potential for optoelectronic applications,offering a new design strategy for high-performance luminescent materials.
基金support from the National Natural Science Foundation of China(No.22274131)Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHQ071)。
文摘Selenolate ligands are expected to endow fluorescent gold nanoclusters(AuNCs)with better stability and more bioactivity than thiolate ligands,making them promising in the biological field.However,there are few studies on the synthesis of water-soluble selenolate-protected AuNCs,and the impact of selenolate ligands on the optical properties of AuNCs is still unclear.In this study,we synthesized selenolatecostabilized water-soluble,near-infrared fluorescent AuNCs with four different amounts of benzeneselenol(PhSeH),and systematically investigated the role of PhSeH on their optical properties.It is discovered that an appropriate PhSeH content is favorable for the fluorescence enhancement of AuNCs due to the ligand to metal charge transfer effect.Moreover,AuNCs co-stabilized by selenolate ligands exhibit better photostability and long-term stability compared with AuNCs stabilized by thiolate ligands,owing to the introduction of Au-Se bond on their surfaces.Further cellular experiments revealed that selenolate ligands can also affect the cellular uptake efficiency of AuNCs and their imaging property.These results provide important knowledges for further development of new,robust selenolate-stabilized metal NCs for biological application.
基金supported by the National Natural Science Foundation of China(Nos.52371222 and 52271211)the Natural Science Foundation of Hunan Province in China(Nos.2024JJ4022,2023JJ30277 and 2023JJ50043)+1 种基金the Science and Technology Innovation Program of Hunan Province(No.2023RC3185),ChinaHORIZON-Marie Skłodowska-Curie Actions-2021-PF(No.101065098),European Union.
文摘Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunctional catalysts remains challenging.Here,we report a bifunctional electrocatalyst of Ru NCs@NPC,embedding the ultrafine Ru nanoclusters into N-doped porous carbon via microwave reduction.Due to the ultrafine Ru nanoclusters and N doping,the composite exhibits exceptional activity for both HER and HzOR,requiring−55 and−67 mV to reach 10 mA·cm^(−2) in alkaline media.In the overall hydrazine splitting(OHzS)system,Ru NCs@NPC is used as both anode and cathode materials,achieving 10 mA·cm^(−2) only at 0.036 V.The zinc hydrazine(Zn-Hz)battery assembled with Ru NCs@NPC cathode and Zn foil anode can provide a stable voltage of 0.4 V and exhibit 98.5%energy efficiency.Therefore,integrating Zn-Hz battery with OHzS system enables self-powered H_(2) evolution.The density function theory calculations reveal that the Ru-N bond increases the metal-support interaction.
基金supported by the open funds of Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, Chinathe funding from Guangdong Natural Science Funds (No. 2023A0505050107)。
文摘Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalities.Among that,Cu nanoclusters have been gaining continuous increasing research attentions,thanks to the low cost,diversified structures,and superior catalytic performance for various reactions.In this review,we first summarize the recent progress regarding the synthetic methods of atomically precise Cu nanoclusters and the coordination modes between Cu and several typical ligands and then discuss the catalytic applications of these Cu nanoclusters with some explicit examples to explain the atomical-level structure-performance relationship.Finally,the current challenges and future research perspectives with some critical thoughts are elaborated.We hope this review can not only provide a whole picture of the current advances regarding the synthesis and catalytic applications of atomically precise Cu nanoclusters,but also points out some future research visions in this rapidly booming field.
基金supported by the National Natural Science Foundation of China(Nos.82061148012,82027806,82372220,21974019)the National Key Research and Development Program of China(No.2017YFA0205300)the Primary Research&Development Plan of Jiangsu Province(No.BE2019716)。
文摘Skins expose to kinds of risk factors for damage,such as the hormone drugs,skin care products and ultraviolet radiation,which is accompanied by the production of excessive reactive oxygen species(ROS)and eventually leads to hypertrichosis.This skin disease is not aesthetically pleasing and even causes psychological and spiritual problems such as inferiority,anxiety and irritability.Current therapies are limited and often unsatisfactory,such as pharmacological and physical therapies,which have adverse effects and cause the irreversible destruction of hair follicles.Gold nanoclusters have good biocompatibility and their biosynthesis in vivo is responsive to oxidative stress microenvironment(OSM),which could be a safe and effective drug for ROS-induced skin injury.In our study,we demonstrated that zero valence fluorescent gold nanoclusters(FGNCs)were in situ biosynthesized in the plucking-induced damaged skin but not in the normal skin after the administration of gold precursors(+3),while FGNCs inhibited hair follicle regeneration by negatively regulating nuclear transcription factor kappa B(NFκB)-mediated inflammatory response signaling pathway(NFκB/tumor necrosis factor-α(TNF-α)axis).This OSM-responsive in situ biosynthesis method is facile and safe and holds great promise for curing hypertrichosis associated with skin dermatitis and injury.
文摘Bovine serum albumin(BSA)and glycine(Gly)dual-ligand-modified copper nanoclusters(BSA-Gly CuNCs)with high fluorescence intensity were synthesized by a one-pot strategy.Based on the competitive fluorescence quenching and dynamic quenching effects of ornidazole(ONZ)on BSA-Gly CuNCs,a simple and sensitive detection method for ONZ was successfully developed.The experimental results demonstrate that the addition of the small molecule Gly can more effectively protect CuNCs,and thus enhance its fluorescence intensity and stability.The proposed assay allowed for the detection of ONZ in a linear range of 0.28 to 52.60μmol·L^(-1)and a detection limit of 0.069μmol·L^(-1).Compared with the single-ligand-modified CuNCs,dual-ligand-modified BSA-Gly CuNCs had higher fluorescence intensity,stability,and sensing ability and were successfully applied to evaluate ONZ in actual ONZ tablets.
文摘The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.
基金supported by Guangdong Natural Science Funds(No.2023A0505050107)Hong Kong Research Grant Council General Research Fund(Nos.16201820 and 16201622)+1 种基金Green Tech Fund(No.GTF202020131)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(No.HZQB-KCZYB-2020083).
文摘Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is still lacking for understanding the structure-performance relationship at atomical level.Herein,we report the synthesis,structure analysis,and OER catalytic properties of a novel atomically precise Cu nanocluster of[Cu_(6)(C≡CR)4(dppe)3](R=Fe(C_(5)H_(5))_(2),abbreviated as Cu_(6)NC).Cu_(6)NC possesses a unique metal core configuration and metal-ligand binding motifs.Interestingly,Cu_(6)NC has superior OER performance to pure phosphine ligand-protected Cu18 nanocluster(Cu18NC in short,same Cu amount)and Cu nanoparticle(CuNP)with larger size,manifested by the lower overpotential at 10 mA·cm^(−2),smaller Tafel slope,and reduced charge transfer resistance.Cu_(6)NC also demonstrated excellent long-term stability for prolonged operation.Density functional theory(DFT)calculations further confirm that the alkynyl ligand plays a critical role in promoting the catalytic performance,and Cu_(6)NC has a lower energy barrier in the rate-determining step of the OER process.This study not only highlights the unique advantages of employing ultrasmall Cu nanoclusters for OER,but also can shed light on designing ligand-functionalized metal nanoclusters for electrochemical energy conversion and beyond.
基金supported by the National Key R&D Program of China(No.2023YFC3905804)the National Natural Science Foundation of China(Nos.22078374,22378434,22309210)+4 种基金the National Ten Thousand Talent Plan,the Key Realm Research and Development Program of Guangdong Province(No.2020B0202080001)Science and Technology Planning Project of Guangdong Province,China(No.2021B1212040008)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515011150)the Scientific and Technological Planning Project of Guangzhou(No.202206010145)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.23qnpy85).
文摘Metal-nanocluster materials have gradually become a promising electrode candidate for supercapaci-tor application.The high-efficient and rational architecture of these metal-nanocluster electrode mate-rials with satisfied supercapacitive performance are full of challenges.Herein,Fe-nanocluster anchored porous carbon(FAPC)nanosheets were constructed through a facile and low-cost impregnation-activation strategy.Various characterization methods documented that FAPC nanosheets possessed a mesopore-dominated structure with large surface area and abundant Fe-N4 active sites,which are crucial for su-percapacitive energy storage.The optimal FAPC electrode exhibited a high specific capacitance of 378 F/g at a specific current of 1 A/g and an excellent rate capability(271 F/g at 10 A/g),which are comparable or even superior to that of most reported carbon candidates.Furthermore,the FAPC-based device achieved a desired specific energy of 14.8 Wh/kg at a specific power of 700 W/kg.This work opens a new avenue to design metal-nanocluster materials for high-performance biomass waste-based supercapacitors.
基金Guangzhou Key R&D Program/Plan Unveiled Flagship Project,Grant/Award Number:20220602JBGS02Guangzhou Basic and Applied Basic Research Project,Grant/Award Number:202201011449+3 种基金Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology,Grant/Award Numbers:FC202220,FC202216Guangdong Basic and Applied Basic Research Foundation,Grant/Award Numbers:2021A1515010167,2022A1515011196National Natural Science Foundation of China,Grant/Award Numbers:21975292,21978331,22068008,52101186Training Program of the Major Research Plan of the National Natural Science Foundation of China,Grant/Award Number:92061124。
文摘Remarkable progress has characterized the field of electrocatalysis in recent decades,driven in part by an enhanced comprehension of catalyst structures and mechanisms at the nanoscale.Atomically precise metal nanoclusters,serving as exemplary models,significantly expand the range of accessible structures through diverse cores and ligands,creating an exceptional platform for the investigation of catalytic reactions.Notably,ligand‐protected Au nanoclusters(NCs)with precisely defined core numbers offer a distinct advantage in elucidating the correlation between their specific structures and the reaction mechanisms in electrocatalysis.The strategic modulation of the fine microstructures of Au NCs presents crucial opportunities for tailoring their electrocatalytic performance across various reactions.This review delves into the profound structural effects of Au NC cores and ligands in electrocatalysis,elucidating their underlying mechanisms.A detailed exploration of the fundamentals of Au NCs,considering core and ligand structures,follows.Subsequently,the interaction between the core and ligand structures of Au NCs and their impact on electrocatalytic performance in diverse reactions are examined.Concluding the discourse,challenges and personal prospects are presented to guide the rational design of efficient electrocatalysts and advance electrocatalytic reactions.
基金Funded by the National Natural Science Foundation of China(No.51873167)the Fundamental Research Funds for the Central Universities(WUT:2022-CL-A1-04)。
文摘On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient and eco-friendly process,mild conditions,and simple post-treatment.The experimental results reveal that a homogeneous deposited film(Cu NCs/CCS nanocomposite film)is generated on the Cu plate(the anode)after electrodeposition,which exhibits an obvious red florescence.The results from TEM observation suggest there are nanoparticles(with the average particle size of 2.3 nm)in the deposited film.Spectral analysis results both demonstrate the existence of Cu NCs in the deposited film.Moreover,the Cu NCs/CCS film modified electrode is directly created through electrodeposition of CCS,which enables promising application in the electrochemical sensing.By means of fluorescence properties of Cu NCs,the Cu NCs/CCS film also owns the potential in fluorescence detection.Therefore,this work builds a novel method for the green synthesis of Cu NCs,meanwhile it offers a convenient and new electrodeposition strategy to prepare polysaccharide-based Cu NCs nanocomposites for uses in functional nanocomposites and bioelectronic devices.
基金supported by the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(No.2019R1A6C1010042)the financial support from the National Research Foundation of Korea(NRF)(2022R1A2C2010686,2022R1A4A3033528,2021R1C1C2010726)。
文摘Herein,we propose a simple and rapid approach for synthesizing a CuS/Ru composite that serves as a bifunctional electrocatalyst to promote hydrogen production and concurrently convert sulfion into a value-added sulfur product.This composite comprises Ru nanoclusters supported on the CuS nanostructure,achieved through simple pulsed laser irradiation in liquid approach.The optimized CuS/Ru-30 electrocatalyst demonstrates remarkable bifunctional electrocatalytic activity,exhibiting a negligible working potential of 0.28 V(vs.RHE)for the anodic sulfion oxidation reaction(SOR)and a minimal overpotential of 182 m V for cathodic hydrogen evolution reaction(HER)to achieve 10 mA cm^(-2)of current density.Moreover,the Cu S/Ru-30 electrocatalyst shows exceptional selectivity for converting sulfion into valuable sulfur during anodic oxidation reactions.Remarkably,in a two-electrode electrolyzer system utilizing Cu S/Ru-30 as both the anode and cathode,the SOR+HER coupled water electrolysis system demands only 0.52 V to reach 10 mA cm^(-2),which is considerably lesser compared to the OER+HER coupled water electrolysis(1.85 V).The experimental results and density function theory(DFT)calculations reveal that the strong electron interaction between CuS and Ru nanoclusters generates a built-in electric field,greatly enhancing electron transfer efficiency.This significantly boosts the HER performance and facilitates the adsorption and production of sulfur intermediates.This study presents a rapid and simple strategy for synthesizing a dual-functional catalyst suitable for low-voltage hydrogen generation while facilitating the recovery of valuable sulfur sources.
基金supported by the National Natural Science Foundation of China(51672081)the Program of Tri-three Talents Project of Hebei Province(China,A202110002)+1 种基金the Young Top Talents Fund Program of Higher Education Institutions of Heibei Province(BJ2020009)the Project of Science and Technology Innovation Team,Tangshan(20130203D)。
文摘For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.
