Small-sized Cd_(x) Zn_(1-x) S solid solution nanomaterial is an important candidate for efficient photocatalytic hydrogen evolution(PHE),but it still suffers from easy agglomeration,severe photo corrosion,and fast pho...Small-sized Cd_(x) Zn_(1-x) S solid solution nanomaterial is an important candidate for efficient photocatalytic hydrogen evolution(PHE),but it still suffers from easy agglomeration,severe photo corrosion,and fast photogenerated electron-hole recombination.To tackle these issues,herein,we propose a new strategy to modify Cd_(x) Zn_(1-x) S nanoreactors by the simultaneous utilization of ionic-liquid-assisted morphology engineering and MXene-incorporating method.That is,we designed and synthesized a novel hierarchi-cal Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction composite through the in-situ deposition of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets on unique IL-modified Ti_(3) C_(2) MXenes by a one-pot solvothermal method for efficiently PHE.The unique construction strategy tailors the thickness of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets and prevents them from stacking and agglomeration,and especially,optimizes their charge transfer pathways during the photocatalytic process.Compared with pristine Cd_(0.8) Zn_(0.2) S nanosheets,Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) has abun-dant photogenerated electrons available on the Ti_(3) C_(2) surface for proton reduction reaction,owing to the absence of deep-trapped electrons,suppression of electron-hole recombination in Cd_(0.8) Zn_(0.2) S and high-efficiency charge separation at the Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction interface.Moreover,the hy-drophilicity,electrical conductivity,visible-light absorption capacity,and surficial hydrogen desorption of Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) heterostructure are significantly improved.As a result,the heterostructure exhibits out-standing photocatalytic stability and super high apparent quantum efficiency,being rendered as one of the best noble-metal-free Cd-Zn-S-based photocatalysts.This work illustrates the mechanisms of mor-phology control and heterojunction construction in controlling the catalytic behavior of photocatalysts and highlights the great potential of the IL-assisted route in the synthesis of high-performance MXene-based heterostructures for photocatalytic hydrogen evolution.展开更多
The pore structure and pseudo-graphitic phase(domain size and content)of a hard carbon anode play key roles in improving the plateau capacity of sodium-ion batteries(SIBs),while it is hard to regulate them effectively...The pore structure and pseudo-graphitic phase(domain size and content)of a hard carbon anode play key roles in improving the plateau capacity of sodium-ion batteries(SIBs),while it is hard to regulate them effectively and simultaneously.This study delves into the synthesis of hard carbons with tailored microstructures from esterified sodium carboxymethyl cellulose(CMC-Na).The hard carbon(EHC-500)with maximized pseudo-graphitic content(73%)and abundant uniformly dispersed closed pores was fabricated,which provides sufficient active sites for sodium ion intercalation and pore filling.Furthermore,minimized lateral width(L_(a))of pseudo-graphitic domains in EHC-500 is simultaneously realized to improve the accessibility of sodium ions to the intercalation sites and filling sites.Therefore,the optimized microstructure of EHC-500 contributes to a remarkable reversible capacity of 340 mAh/g with a high plateau capacity of 236.7 mAh/g(below 0.08 V).These findings underscore the pivotal role of microcrystalline structure and pore structure in the electrochemical performance of hard carbons and provide a novel route to guide the design of hard carbons with optimal microstructures towards enhanced sodium storage performance.展开更多
Manganese-based chalcogenides have significant potential as anodes for sodium-ion batteries(SIBs) due to their high theoretical specific capacity, abundant natural reserves, and environmental friendliness. However, th...Manganese-based chalcogenides have significant potential as anodes for sodium-ion batteries(SIBs) due to their high theoretical specific capacity, abundant natural reserves, and environmental friendliness. However, their application is hindered by poor cycling stability, resulting from severe volume changes during cycling and slow reaction kinetics due to their complex crystal structure. Here, an efficient and straightforward strategy was employed to in-situ encapsulate single-phase porous nanocubic MnS_(0.5)Se_(0.5) into carbon nanofibers using electrospinning and the hard template method, thus forming a necklace-like porous MnS_(0.5)Se_(0.5)-carbon nanofiber composite(MnS_(0.5)Se_(0.5)@N-CNF). The introduction of Se significantly impacts both the composition and microstructure of MnS_(0.5)Se_(0.5), including lattice distortion that generates additional defects, optimization of chemical bonds, and a nano-spatially confined design. In situ/ex-situ characterization and density functional theory calculations verified that this MnS_(0.5)Se_(0.5)@N-CNF allevi- ates the volume expansion and facilitates the transfer of Na+/electron. As expected, MnS_(0.5)Se_(0.5)@N-CNF anode demonstrates excellent sodium storage performance, characterized by high initial Coulombic efficiency(90.8%), high-rate capability(370.5 m Ahg^(-1) at 10 Ag^(-1)) and long durability(over 5000 cycles at 5 Ag^(-1)). The MnS_(0.5)Se_(0.5)@N-CNF//NVP@C full cell, assembled with MnS_(0.5)Se_(0.5)@N-CNF as anode and Na_(3)V_(2)(PO_4)_(3)@C as cathode, exhibits a high energy density of 254 Wh kg^(-1) can be provided. This work presents a novel strategy to optimize the design of anode materials through structural engineering and Se substitution, while also elucidating the underlying reaction mechanisms.展开更多
Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imida...Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.展开更多
With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk che...With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).展开更多
Lanthanide(Ln^(3+))-doped luminescent nanocrystals(NCs)with excitation and emission in the second near-infrared biological window(NIRII,1000-1700 nm)have attracted considerable attention in the fields of deep-tissue b...Lanthanide(Ln^(3+))-doped luminescent nanocrystals(NCs)with excitation and emission in the second near-infrared biological window(NIRII,1000-1700 nm)have attracted considerable attention in the fields of deep-tissue bioimaging and non-invasive biodetection,owing to their superior advantages including good photochemical stability,sharp emission peaks,large penetration depth,and high signal-to-noise ratio[1].Conventionally,Yb3t-and Nd3t-sensitized NCs have been utilized as NIR-II luminescent nanoprobes for in vivo bioimaging upon excitation with 980 and 808 nm diode laser,respectively[2].展开更多
Acidic water splitting,essential for sustainable hydrogen production,is limited by the sluggish oxygen evolution reaction(OER).This study presents a series of iridium-based sub-nanocluster electrocatalysts supported o...Acidic water splitting,essential for sustainable hydrogen production,is limited by the sluggish oxygen evolution reaction(OER).This study presents a series of iridium-based sub-nanocluster electrocatalysts supported on a porous carbon matrix(CBC-Ir-T,T=300,400,and 500°C)for efficient overall water splitting.Impressively,CBC-Ir-400,with an ultralow Ir loading of 1.4μg·cm^(−2),exhibits exceptional bifunctional activity,achieving 10 mA·cm^(−2) at overpotentials of only 240 mV for OER and 30 mV for hydrogen evolution reaction(HER).In practical acidic water splitting,it delivers a cell voltage of 1.53 V at 10 mA·cm^(−2),outperforming the commercial Ir/C||Pt/C system.Comprehensive characterization reveals that the cucurbit[6]uril-derived porous carbon matrix,rich in defects and high specific surface area,promotes the formation of uniformly dispersed sub-nano Ir clusters.This optimizes the iridium electronic structure for enhanced intermediate adsorption,while strong electrical coupling with carbon support boosts charge transfer and mass transport.This synergy drives its superior performance.Our findings offer a scalable strategy for designing high-performance,ultralow-loading iridium sub-nanocluster catalysts,paving the way for cost-effective and sustainable hydrogen production via water electrolysis.展开更多
Two-dimensional(2D)transition metal borides(MBenes)have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and ex-cellent electric...Two-dimensional(2D)transition metal borides(MBenes)have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and ex-cellent electrical conductivity.Unlike well-studied graphene,perovskite and MXene materials in various fields,the research about MBene is still in its infancy.The inadequate exploration of efficient etching methods impedes their further study.Herein,we put forward an efficient microwave-assisted hydrother-mal alkaline solution etching strategy for exfoliating MoAlB MAB phase into 2D MoB MBenes with a well accordion-like structure,which displays a remarkable electrochemical performance in sodium ion batter-ies(SIBs)with a reversible specific capacity of 196.5 mAh g^(-1)at the current density of 50 mA g^(-1),and 138.6 mAh g^(-1)after 500 cycles at the current density of 0.5 A g^(-1).The underlying mechanism toward excellent electrochemical performance are revealed by comprehensive theoretical simulations.This work proves that MBene is a competitive candidate as the next generation anode of sodium ion batteries.展开更多
2D Ruddlesden-Popper(RP)polar perovskite,displaying the intrinsic optical anisotropy and structural polarity,has a fantastic application perspective in self-powered polarized light detection.However,the weak van der W...2D Ruddlesden-Popper(RP)polar perovskite,displaying the intrinsic optical anisotropy and structural polarity,has a fantastic application perspective in self-powered polarized light detection.However,the weak van der Waals interaction between the organic spacing bilayers is insufficient to preserve the stability of RP-type materials.Hence,it is of great significance to explore new stable 2D RP-phase candidates.In this work,we have successfully constructed a highly-stable polar 2D perovskite,(t-ACH)_(2)PbI_(4)(1,where t-ACH^(+)is HOOC_(8)H_(12)NH_(3)^(+)),by adopting a hydrophobic carboxylate trans-isomer of tranexamic acid as the spacing component.Strikingly,strong O-H…O hydrogen bonds between t-ACH^(+)organic bilayers compose the dimer,thus decreasing van der Waals gap and enhancing structural stability.Besides,such orientational hydrogen bonds contribute to the formation of structural polarity and generate an obvious bulk photovoltaic effect in 1,which facilitates its self-powered photodetection.As predicted,the combination of inherent anisotropy and polarity leads to self-powered polarized-light detection with a high ratio of around∼5.3,superior to those of inorganic 2D counterparts.This work paves a potential way to design highly-stable 2D perovskites for high-performance optoelectronic devices.展开更多
To address the high cost and limited electrochemical endurance of Pt-based electrocatalysts,the appropriate introduction of transition metal-based compounds as supports to disperse and anchor Pt species offers a promi...To address the high cost and limited electrochemical endurance of Pt-based electrocatalysts,the appropriate introduction of transition metal-based compounds as supports to disperse and anchor Pt species offers a promising approach for improving catalytic efficiency.In this study,sub-1 nm Pt nanoclusters were uniformly confined on NiO supports with a hierarchical nanotube/nanosheet structure(Pt/NiO/NF)through a combination of spatial domain confinement and annealing.The resulting catalyst exhibited excellent electrocatalytic activity and stability for hydrogen evolution(HER)and urea oxidation reactions(UOR)under alkaline conditions.Structural characterization and density functional theory calculations demonstrated that sub-1 nm Pt nanoclusters were immobilized on the NiO supports by Pt–O–Ni bonds at the interface.The strong metal-support interaction induced massive charge redistribution around the heterointerface,leading to the formation of multiple active sites.The Pt/NiO/NF catalyst only required an overpotential of 12 and 136 mV to actuate current densities of 10 and 100 mA cm^(-2) for the HER,respectively,and maintained a voltage retention of 96%for 260 h of continuous operation at a current density of 500 mA cm^(-2).Notably,in energy-efficient hydrogen production systems coupled with the HER and UOR,the catalyst required cell voltages of 1.37 and 1.53 V to drive current densities of 10 and 50 mA cm^(-2),respectively—approximately 300 mV lower than conventional water electrolysis systems.This study presents a novel pathway for designing highly efficient and robust sub-nanometer metal cluster catalysts.展开更多
Metallabenzenes, a type of aromatic compound that includes metal atoms, have opened up new avenues for creating materials with unique properties. A distinctive feature of metallabenzenes is the significant deviation o...Metallabenzenes, a type of aromatic compound that includes metal atoms, have opened up new avenues for creating materials with unique properties. A distinctive feature of metallabenzenes is the significant deviation of their metal atoms from the planar configuration of the C5 ring, a phenomenon that paradoxically enhances their aromatic character. In this investigation, we propose that this counterintuitive increase in aromaticity upon geometric distortion is governed by the interactions of frontier orbitals in the σ-space. This insight not only corroborates the previously suggested role of σ-space orbitals in inducing geometric non-planarity in metallabenzenes but also underscores their pivotal contribution to the compounds' enhanced aromaticity. As a result, this work broadens the scope of the σ-control mechanism,highlighting its usefulness for the rational design of functional metalla-aromatic materials.展开更多
The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis.Especially,the sustainable photocatalytic,electroc...The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis.Especially,the sustainable photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane at ambient conditions is regarded as an alternative technology to replace with thermocatalysis.In this review,we summarize recent advances in photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane into alcohols.We firstly introduce the general principles of photocatalysis,electrocatalysis and photoelectrocatalysis.Then,we discuss the mechanism for selective activation of C-H bond and following oxygenation over metal,inorganic semiconductor,organic semiconductor,and heterojunction composite systems in the photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation in detail.Later,we present insights into the construction of effective photocatalyst,electrocatalyst and photoelectrocatalyst for methane conversion into alcohols from the perspective of band structures and active sites.Finally,the challenges and outlook for future designs of photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation systems are also proposed.展开更多
Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as high...Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.展开更多
Photodynamic therapy(PDT)is widely used in cancer treatment because of its noninvasiveness and minimal side effects.However,low therapeutic efficiency and the challenge of treatment visualization limit its development...Photodynamic therapy(PDT)is widely used in cancer treatment because of its noninvasiveness and minimal side effects.However,low therapeutic efficiency and the challenge of treatment visualization limit its development.Herein,we constructed a simple yet efficient lanthanide-doped theranostic nanoplatform termed as LiLuF_(4):Yb,Er,Ce@LiYF_(4)@LiLuF_(4):Nd-chlorine 6(TNPs-Ce6)that enables real-time monitoring of the therapeutic effects of PDT.Upon orthogonal excitation by near-infrared(NIR)light,the Nd^(3+)-doped TNPs activated the triplets of Ce6 photosensitizers via a direct lanthanide-triplet energy transfer process,which allowed to directly active the low-lying triplet state of the photosensitizer without undergoing singlet-triplet intersystem crossing(ISC)process,thereby significantly enhancing the efficiency of the photodynamic process.Meanwhile,the incorporation of Er^(3+)ions within the core endowed the nanoplatform with NIR-Ⅱb imaging capabilities,allowing convenient real-time monitoring of the photodynamic treatment process.Characterization tests revealed that the TNPs-Ce6 nanoplatform,exhibiting an NIR quantum yield of 21.7%at an ultralow excitation power density of 0.1 W cm^(-2),provides a real-time imaging resolution as low as75μm in the NIR-Ⅱb range and achieves a tumor suppression rate of 94%.Therefore,this highly efficient theranostic nanoplatform,with real-time treatment monitoring capability,demonstrates significant potential in cancer therapy.展开更多
Although lots of efforts have been devoted on new less hygroscopic dopants to address problems in hole transport materials(HTM),the long-time post-oxidation and the volatilization of 4-tert-butylpyridine(tBP)are still...Although lots of efforts have been devoted on new less hygroscopic dopants to address problems in hole transport materials(HTM),the long-time post-oxidation and the volatilization of 4-tert-butylpyridine(tBP)are still issues.A new doping mechanism for spiro-OMeTAD by disulfiram(TETD)is revealed in this work.Owing to its disulfide bond,TETD can be activated easily to produce reactive sulfur for the rapid oxidation of spiro-OMeTAD in the absence of oxygen with formation of[spiro-OMeTAD•]+[SC(S)N(C_(2)H_(5))_(2)]^(-).Thus,in this situation,the Li+ion has the opportunity to coordinate tBP and fix each other in HTM film.DFT calculations suggest that the resulting favorable energy(with a△E of−1.29 eV)must come from the mutual interactions among Li^(+),TFSI^(−),and tBP,which is different from the well-known doping process that tBP would not participate in the doping reaction.As a result,the introduction of a new radical into the HTM greatly reduce device performance fluctuations due to the environmental dependence and inhibit tBP volatilizing for enhanced long-term stability.展开更多
Incorporating low-dimensionalization technologies effectively tackle the challenge of inadequate long-term stability in hybrid halide perovskites,however their wide bandgap and strong quantum well confinement remain s...Incorporating low-dimensionalization technologies effectively tackle the challenge of inadequate long-term stability in hybrid halide perovskites,however their wide bandgap and strong quantum well confinement remain substantial obstacle for various optoelectronic applications.Addressing these issues without compromising longterm stability has emerged as a pivotal focus in materials science,in particular exploring the effects of the functional groups within spacer cations.Our simulations reveal that the robustπ-πstacking interactions involving PEA^(+)and the strong hydrogen bonding interactions between PEA^(+)and MX^(4-)_(6)contribute to narrowing the electronic bandgap in 2D monolayer PEA_(2)MX_(4)(e.g.2D monolayer PEA_(2)SnI_(4):1.34 eV)for reasonable visible-light absorption while simultaneously ensuring their favorable long-term stability.Moreover,the delocalized orbitals and relatively high dielectric constants in PEA^(+),attributed to the conjugated benzene ring,has been observed to weaken the potential barrier,exciton binding effect and quantum well confinement in 2D monolayer PEA2MX4,thus facilitating photogenerated electron-hole separations and out-of-plane carrier transport.The impact of spacer cations on the optoelectronic and transport properties of 2D monolayer perovskites highlights the critical role of meticulously chosen and well-designed spacer cations,especially functional groups,in shaping their photophysical properties and ensuring long-term stability even under extremely operating conditions.展开更多
Selective separation of phenanthrene(PHE)from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene(ANT).Herein,we report the self-a...Selective separation of phenanthrene(PHE)from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene(ANT).Herein,we report the self-assembly of a water-soluble Pd_(2)L_(2) cage 1 with a large hydrophobic cavity,formed from novel macrocyclic ligands(L)and cis-Pd(Ⅱ).Cage 1 can selectively encapsulate PHE instead of ANT.Based on host-vip recognition followed by extraction,we achieve a remarkable 99%purity of PHE separation from an equimolar mixture of PHE and ANT using cage 1 in aqueous solution.Importantly,the separation performance of PHE using cage 1 remains unaffected even after five extraction cycles,demonstrating its robustness.This work highlights the potential of supramolecular cages for efficient and cost-effective PHE separation from the isomer ANT in aqueous solutions using such promising host-vip strategy.展开更多
Crystal defects and morphological modifications are popular strategies to enhance the catalytic activity of heterogeneous semiconductor photocatalysts.Despite defect engineering and morphology control show their succe...Crystal defects and morphological modifications are popular strategies to enhance the catalytic activity of heterogeneous semiconductor photocatalysts.Despite defect engineering and morphology control show their successful applications in ZnO,the effects of curved surface modifications on the photocatalytic performance of ZnO and their interplay with the defect formation remain unclear.To resolve this puzzle,we systemically investigate the joint effects of curvature and defect formation on the electronic structure,optoelectronic properties,and photocatalytic performance of ZnO slabs using first-principles calculations.We find that curvature deformation effectively narrows the electronic bandgap by up to 1.6 eV and shifts the p-/d-band centers,thereby enhancing light absorption in the visible and near-ultraviolet regions.Besides,curvature deformation stimulates self-polarization,facilitating the separation of photogenerated electrons and holes.Also,curvature deformation promotes the formation of defects by reducing defect formation energy(by up to 1.0 eV),thus creating abundant reaction sites for photocatalysis.Intriguingly,the synergistic interaction between curvature and defect deformation further strengthens the self-polarization,narrows the electronic bandgaps,adjusts the p-/d-band centers to improve the optoelectronic properties,and influences the dissociation and free energy barriers of intermediates.Consequently,our findings reveal that this synergy substantially enhances the photocatalytic performance of ZnO slabs,providing deeper insights into the role of defect engineering and morphology control on photocatalysis.展开更多
The heterostructures incorporated with two or more distinctive two-dimensional(2D)materials have attracted great attention be-cause they could give rise to enhanced prop-erty in comparison with their individual counte...The heterostructures incorporated with two or more distinctive two-dimensional(2D)materials have attracted great attention be-cause they could give rise to enhanced prop-erty in comparison with their individual counterparts.Here,a water-assisted two-step rapid physical vapor deposition(rPVD)method was explored and used to synthesize Bi_(2)Te_(3)-Sb_(2)Te_(3)lateral het-erostructures(LHS)successfully.The Bi_(2)Te_(3)-Sb_(2)Te_(3)LHS is in nearly uniform size,and grows along three particular orientations with the intersection angles of 120°.Inter-estingly,we found that the water molecules play a significant role in determining the growth orientation,namely whether it will grow along the vertical or lateral direction in 2D structure.Hence,a growth mechanism of LHS based on the water-assisted two-step rPVD was present,which can be used as a general strategy and extended to the growth of other 2D heterostruc-tures or homostructures,such as SnS-SnSe LHS and SnS-SnS lateral homostructures.Fur-thermore,the second-harmonic generation intensity of the Bi_(2)Te_(3)-Sb_(2)Te_(3)LHS is much stronger than that of the Bi_(2)Te_(3)/Sb_(2)Te_(3)vertical heterostructures(VHS).This work opens a new approach for the synthesis of water-assisted lateral 2D heterostructures or homostruc-tures and offers a new method to enhance the second-harmonic generation properties of topo-logical insulating materials.展开更多
Na-Se batteries have caught tremendous attention because of natural abundant of element sodium and their high volumetric energy density(2530 Wh/L).However,the low utilization ratio of Se is the main obstacle for pract...Na-Se batteries have caught tremendous attention because of natural abundant of element sodium and their high volumetric energy density(2530 Wh/L).However,the low utilization ratio of Se is the main obstacle for practical application.Herein,an advanced Se-based electrode is designed and prepared by using tea stem-derived micropore carbon matrix(TSC)as Se host and coating TSC/Se with cyclic polyacrylonitrile(cPAN).TSC/Se/cPAN electrode shows rate capacity of 318.3 mAh/g at 2 C(1 C=675 mA/g)and great discharge capacity of 420.6 mAh/g after 300 cycles at 0.2 C.The impressive electrochemical performance is mainly ascribed to the interface design of c PAN coating,resulting in the enhanced electronic conductivity of whole electrode and high ratio of robust inorganic salt NaCl in CEI film.The TSC/Se/c PAN||NVP full cell also exhibits great discharge capacity of 556.6 mAh/g after 55 cycles at 0.1 C.展开更多
基金financial supports pro-vided by the National Natural Science Foundation of China(No.21905279)the Natural Science Foundation of Fujian Province(No.2020J05086).
文摘Small-sized Cd_(x) Zn_(1-x) S solid solution nanomaterial is an important candidate for efficient photocatalytic hydrogen evolution(PHE),but it still suffers from easy agglomeration,severe photo corrosion,and fast photogenerated electron-hole recombination.To tackle these issues,herein,we propose a new strategy to modify Cd_(x) Zn_(1-x) S nanoreactors by the simultaneous utilization of ionic-liquid-assisted morphology engineering and MXene-incorporating method.That is,we designed and synthesized a novel hierarchi-cal Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction composite through the in-situ deposition of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets on unique IL-modified Ti_(3) C_(2) MXenes by a one-pot solvothermal method for efficiently PHE.The unique construction strategy tailors the thickness of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets and prevents them from stacking and agglomeration,and especially,optimizes their charge transfer pathways during the photocatalytic process.Compared with pristine Cd_(0.8) Zn_(0.2) S nanosheets,Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) has abun-dant photogenerated electrons available on the Ti_(3) C_(2) surface for proton reduction reaction,owing to the absence of deep-trapped electrons,suppression of electron-hole recombination in Cd_(0.8) Zn_(0.2) S and high-efficiency charge separation at the Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction interface.Moreover,the hy-drophilicity,electrical conductivity,visible-light absorption capacity,and surficial hydrogen desorption of Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) heterostructure are significantly improved.As a result,the heterostructure exhibits out-standing photocatalytic stability and super high apparent quantum efficiency,being rendered as one of the best noble-metal-free Cd-Zn-S-based photocatalysts.This work illustrates the mechanisms of mor-phology control and heterojunction construction in controlling the catalytic behavior of photocatalysts and highlights the great potential of the IL-assisted route in the synthesis of high-performance MXene-based heterostructures for photocatalytic hydrogen evolution.
基金financial support of the National Natural Science Foundation of China(NSFC,No.21905278)the Natural Science Foundation of Hunan Province(No.2023JJ30015).
文摘The pore structure and pseudo-graphitic phase(domain size and content)of a hard carbon anode play key roles in improving the plateau capacity of sodium-ion batteries(SIBs),while it is hard to regulate them effectively and simultaneously.This study delves into the synthesis of hard carbons with tailored microstructures from esterified sodium carboxymethyl cellulose(CMC-Na).The hard carbon(EHC-500)with maximized pseudo-graphitic content(73%)and abundant uniformly dispersed closed pores was fabricated,which provides sufficient active sites for sodium ion intercalation and pore filling.Furthermore,minimized lateral width(L_(a))of pseudo-graphitic domains in EHC-500 is simultaneously realized to improve the accessibility of sodium ions to the intercalation sites and filling sites.Therefore,the optimized microstructure of EHC-500 contributes to a remarkable reversible capacity of 340 mAh/g with a high plateau capacity of 236.7 mAh/g(below 0.08 V).These findings underscore the pivotal role of microcrystalline structure and pore structure in the electrochemical performance of hard carbons and provide a novel route to guide the design of hard carbons with optimal microstructures towards enhanced sodium storage performance.
基金financially supported by the National Natural Science Foundation of China (No. 22225902, U22A20436, 22209185)National Key Research&Development Program of China (2022YFE0115900, 2023YFA1507101, 2021YFA1501500)+1 种基金the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences (No. CXZX-2022-GH04, CXZX-2023-JQ08)Science and Technology Program of Fuzhou (2023-P-009)。
文摘Manganese-based chalcogenides have significant potential as anodes for sodium-ion batteries(SIBs) due to their high theoretical specific capacity, abundant natural reserves, and environmental friendliness. However, their application is hindered by poor cycling stability, resulting from severe volume changes during cycling and slow reaction kinetics due to their complex crystal structure. Here, an efficient and straightforward strategy was employed to in-situ encapsulate single-phase porous nanocubic MnS_(0.5)Se_(0.5) into carbon nanofibers using electrospinning and the hard template method, thus forming a necklace-like porous MnS_(0.5)Se_(0.5)-carbon nanofiber composite(MnS_(0.5)Se_(0.5)@N-CNF). The introduction of Se significantly impacts both the composition and microstructure of MnS_(0.5)Se_(0.5), including lattice distortion that generates additional defects, optimization of chemical bonds, and a nano-spatially confined design. In situ/ex-situ characterization and density functional theory calculations verified that this MnS_(0.5)Se_(0.5)@N-CNF allevi- ates the volume expansion and facilitates the transfer of Na+/electron. As expected, MnS_(0.5)Se_(0.5)@N-CNF anode demonstrates excellent sodium storage performance, characterized by high initial Coulombic efficiency(90.8%), high-rate capability(370.5 m Ahg^(-1) at 10 Ag^(-1)) and long durability(over 5000 cycles at 5 Ag^(-1)). The MnS_(0.5)Se_(0.5)@N-CNF//NVP@C full cell, assembled with MnS_(0.5)Se_(0.5)@N-CNF as anode and Na_(3)V_(2)(PO_4)_(3)@C as cathode, exhibits a high energy density of 254 Wh kg^(-1) can be provided. This work presents a novel strategy to optimize the design of anode materials through structural engineering and Se substitution, while also elucidating the underlying reaction mechanisms.
文摘Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.
基金supported by the National Natural Science Foundation of China(Nos.22175174 and 52332007).
文摘With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).
基金supported by the National Natural Science Foundation of China(Nos.12474418,U22A20398,and 22135008).
文摘Lanthanide(Ln^(3+))-doped luminescent nanocrystals(NCs)with excitation and emission in the second near-infrared biological window(NIRII,1000-1700 nm)have attracted considerable attention in the fields of deep-tissue bioimaging and non-invasive biodetection,owing to their superior advantages including good photochemical stability,sharp emission peaks,large penetration depth,and high signal-to-noise ratio[1].Conventionally,Yb3t-and Nd3t-sensitized NCs have been utilized as NIR-II luminescent nanoprobes for in vivo bioimaging upon excitation with 980 and 808 nm diode laser,respectively[2].
基金the financial support from the National Key R&D Program of China(Nos.2023YFA507101 and 2022YFA1503900)the National Natural Science Foundation of China(Nos.22471270,22033008,and 22220102005).
文摘Acidic water splitting,essential for sustainable hydrogen production,is limited by the sluggish oxygen evolution reaction(OER).This study presents a series of iridium-based sub-nanocluster electrocatalysts supported on a porous carbon matrix(CBC-Ir-T,T=300,400,and 500°C)for efficient overall water splitting.Impressively,CBC-Ir-400,with an ultralow Ir loading of 1.4μg·cm^(−2),exhibits exceptional bifunctional activity,achieving 10 mA·cm^(−2) at overpotentials of only 240 mV for OER and 30 mV for hydrogen evolution reaction(HER).In practical acidic water splitting,it delivers a cell voltage of 1.53 V at 10 mA·cm^(−2),outperforming the commercial Ir/C||Pt/C system.Comprehensive characterization reveals that the cucurbit[6]uril-derived porous carbon matrix,rich in defects and high specific surface area,promotes the formation of uniformly dispersed sub-nano Ir clusters.This optimizes the iridium electronic structure for enhanced intermediate adsorption,while strong electrical coupling with carbon support boosts charge transfer and mass transport.This synergy drives its superior performance.Our findings offer a scalable strategy for designing high-performance,ultralow-loading iridium sub-nanocluster catalysts,paving the way for cost-effective and sustainable hydrogen production via water electrolysis.
基金supported by the National Key Re-search and Development Program of China(No.2020YFC1909604)SZIIT Startup Fund(No.SZIIT2022KJ072)+1 种基金Shenzhen Peacock Project Startup Fund(No.RC2023-002)Shenzhen Steady General Projects(No.KJ2024C010).
文摘Two-dimensional(2D)transition metal borides(MBenes)have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and ex-cellent electrical conductivity.Unlike well-studied graphene,perovskite and MXene materials in various fields,the research about MBene is still in its infancy.The inadequate exploration of efficient etching methods impedes their further study.Herein,we put forward an efficient microwave-assisted hydrother-mal alkaline solution etching strategy for exfoliating MoAlB MAB phase into 2D MoB MBenes with a well accordion-like structure,which displays a remarkable electrochemical performance in sodium ion batter-ies(SIBs)with a reversible specific capacity of 196.5 mAh g^(-1)at the current density of 50 mA g^(-1),and 138.6 mAh g^(-1)after 500 cycles at the current density of 0.5 A g^(-1).The underlying mechanism toward excellent electrochemical performance are revealed by comprehensive theoretical simulations.This work proves that MBene is a competitive candidate as the next generation anode of sodium ion batteries.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22125110,U23A2094,22205233,22193042,21921001,22305248 and U21A2069)the Natural Science Foundation of Fujian Province(No.2023J02028)+3 种基金the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(No.ZDBS-LY-SLH024)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR126)the National Key Research and Development Program of China(No.2019YFA0210402)the China Postdoctoral Science Foundation(Nos.2022TQ0337 and 2023M733497).
文摘2D Ruddlesden-Popper(RP)polar perovskite,displaying the intrinsic optical anisotropy and structural polarity,has a fantastic application perspective in self-powered polarized light detection.However,the weak van der Waals interaction between the organic spacing bilayers is insufficient to preserve the stability of RP-type materials.Hence,it is of great significance to explore new stable 2D RP-phase candidates.In this work,we have successfully constructed a highly-stable polar 2D perovskite,(t-ACH)_(2)PbI_(4)(1,where t-ACH^(+)is HOOC_(8)H_(12)NH_(3)^(+)),by adopting a hydrophobic carboxylate trans-isomer of tranexamic acid as the spacing component.Strikingly,strong O-H…O hydrogen bonds between t-ACH^(+)organic bilayers compose the dimer,thus decreasing van der Waals gap and enhancing structural stability.Besides,such orientational hydrogen bonds contribute to the formation of structural polarity and generate an obvious bulk photovoltaic effect in 1,which facilitates its self-powered photodetection.As predicted,the combination of inherent anisotropy and polarity leads to self-powered polarized-light detection with a high ratio of around∼5.3,superior to those of inorganic 2D counterparts.This work paves a potential way to design highly-stable 2D perovskites for high-performance optoelectronic devices.
文摘To address the high cost and limited electrochemical endurance of Pt-based electrocatalysts,the appropriate introduction of transition metal-based compounds as supports to disperse and anchor Pt species offers a promising approach for improving catalytic efficiency.In this study,sub-1 nm Pt nanoclusters were uniformly confined on NiO supports with a hierarchical nanotube/nanosheet structure(Pt/NiO/NF)through a combination of spatial domain confinement and annealing.The resulting catalyst exhibited excellent electrocatalytic activity and stability for hydrogen evolution(HER)and urea oxidation reactions(UOR)under alkaline conditions.Structural characterization and density functional theory calculations demonstrated that sub-1 nm Pt nanoclusters were immobilized on the NiO supports by Pt–O–Ni bonds at the interface.The strong metal-support interaction induced massive charge redistribution around the heterointerface,leading to the formation of multiple active sites.The Pt/NiO/NF catalyst only required an overpotential of 12 and 136 mV to actuate current densities of 10 and 100 mA cm^(-2) for the HER,respectively,and maintained a voltage retention of 96%for 260 h of continuous operation at a current density of 500 mA cm^(-2).Notably,in energy-efficient hydrogen production systems coupled with the HER and UOR,the catalyst required cell voltages of 1.37 and 1.53 V to drive current densities of 10 and 50 mA cm^(-2),respectively—approximately 300 mV lower than conventional water electrolysis systems.This study presents a novel pathway for designing highly efficient and robust sub-nanometer metal cluster catalysts.
基金supported by the National Natural Science Foundation of China(Nos.22173105,22173104,21973094)。
文摘Metallabenzenes, a type of aromatic compound that includes metal atoms, have opened up new avenues for creating materials with unique properties. A distinctive feature of metallabenzenes is the significant deviation of their metal atoms from the planar configuration of the C5 ring, a phenomenon that paradoxically enhances their aromatic character. In this investigation, we propose that this counterintuitive increase in aromaticity upon geometric distortion is governed by the interactions of frontier orbitals in the σ-space. This insight not only corroborates the previously suggested role of σ-space orbitals in inducing geometric non-planarity in metallabenzenes but also underscores their pivotal contribution to the compounds' enhanced aromaticity. As a result, this work broadens the scope of the σ-control mechanism,highlighting its usefulness for the rational design of functional metalla-aromatic materials.
文摘The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis.Especially,the sustainable photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane at ambient conditions is regarded as an alternative technology to replace with thermocatalysis.In this review,we summarize recent advances in photocatalytic,electrocatalytic and photoelectrocatalytic conversion of methane into alcohols.We firstly introduce the general principles of photocatalysis,electrocatalysis and photoelectrocatalysis.Then,we discuss the mechanism for selective activation of C-H bond and following oxygenation over metal,inorganic semiconductor,organic semiconductor,and heterojunction composite systems in the photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation in detail.Later,we present insights into the construction of effective photocatalyst,electrocatalyst and photoelectrocatalyst for methane conversion into alcohols from the perspective of band structures and active sites.Finally,the challenges and outlook for future designs of photocatalytic,electrocatalytic and photoelectrocatalytic methane oxidation systems are also proposed.
基金financial supports provided by the Natural Science Foundation of Fujian Province(No.2024J01195)the National Nature Science Foundation of China(No.21905279)+1 种基金Sanming University(Nos.22YG11 and PYT2201)the Education Scientific Research Project of Youth Teachers in the Education Department of Fujian Province(No.JAT220351).
文摘Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.
基金supported by the Major Research plan of the National Natural Science Foundation of China(No.92361202)National Natural Science Foundation of China(No.12204481)+3 种基金Fund of Fujian Science&Technology Innovation Laboratory for Optoelectronic Information(No.2020ZZ114)Natural Science Foundation of Fujian Province(Nos.2022J05102 and 2024J09062)National Key Research and Development Program of China(Nos.2022YFB3503700 and 2023YFF0713605)Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(No.CXZX-2022-GS01)
文摘Photodynamic therapy(PDT)is widely used in cancer treatment because of its noninvasiveness and minimal side effects.However,low therapeutic efficiency and the challenge of treatment visualization limit its development.Herein,we constructed a simple yet efficient lanthanide-doped theranostic nanoplatform termed as LiLuF_(4):Yb,Er,Ce@LiYF_(4)@LiLuF_(4):Nd-chlorine 6(TNPs-Ce6)that enables real-time monitoring of the therapeutic effects of PDT.Upon orthogonal excitation by near-infrared(NIR)light,the Nd^(3+)-doped TNPs activated the triplets of Ce6 photosensitizers via a direct lanthanide-triplet energy transfer process,which allowed to directly active the low-lying triplet state of the photosensitizer without undergoing singlet-triplet intersystem crossing(ISC)process,thereby significantly enhancing the efficiency of the photodynamic process.Meanwhile,the incorporation of Er^(3+)ions within the core endowed the nanoplatform with NIR-Ⅱb imaging capabilities,allowing convenient real-time monitoring of the photodynamic treatment process.Characterization tests revealed that the TNPs-Ce6 nanoplatform,exhibiting an NIR quantum yield of 21.7%at an ultralow excitation power density of 0.1 W cm^(-2),provides a real-time imaging resolution as low as75μm in the NIR-Ⅱb range and achieves a tumor suppression rate of 94%.Therefore,this highly efficient theranostic nanoplatform,with real-time treatment monitoring capability,demonstrates significant potential in cancer therapy.
基金supported by the National Natural Science Foundation of China(Nos.52001066,21805039,22375045,22373015 and 22271046)the Natural Science Foundation of Fujian Province(No.2023J01500)Young teacher training program of Fujian Normal University(No.SDPY2023013).
文摘Although lots of efforts have been devoted on new less hygroscopic dopants to address problems in hole transport materials(HTM),the long-time post-oxidation and the volatilization of 4-tert-butylpyridine(tBP)are still issues.A new doping mechanism for spiro-OMeTAD by disulfiram(TETD)is revealed in this work.Owing to its disulfide bond,TETD can be activated easily to produce reactive sulfur for the rapid oxidation of spiro-OMeTAD in the absence of oxygen with formation of[spiro-OMeTAD•]+[SC(S)N(C_(2)H_(5))_(2)]^(-).Thus,in this situation,the Li+ion has the opportunity to coordinate tBP and fix each other in HTM film.DFT calculations suggest that the resulting favorable energy(with a△E of−1.29 eV)must come from the mutual interactions among Li^(+),TFSI^(−),and tBP,which is different from the well-known doping process that tBP would not participate in the doping reaction.As a result,the introduction of a new radical into the HTM greatly reduce device performance fluctuations due to the environmental dependence and inhibit tBP volatilizing for enhanced long-term stability.
基金supported by the National Natural Science Foundation of China(Grant Nos.22103012,22173104)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(FJOEL,Grant No.2021ZR109)the Future-prospective and Stride-across Programs of Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(Grant No.CXZX-2022-GH02)。
文摘Incorporating low-dimensionalization technologies effectively tackle the challenge of inadequate long-term stability in hybrid halide perovskites,however their wide bandgap and strong quantum well confinement remain substantial obstacle for various optoelectronic applications.Addressing these issues without compromising longterm stability has emerged as a pivotal focus in materials science,in particular exploring the effects of the functional groups within spacer cations.Our simulations reveal that the robustπ-πstacking interactions involving PEA^(+)and the strong hydrogen bonding interactions between PEA^(+)and MX^(4-)_(6)contribute to narrowing the electronic bandgap in 2D monolayer PEA_(2)MX_(4)(e.g.2D monolayer PEA_(2)SnI_(4):1.34 eV)for reasonable visible-light absorption while simultaneously ensuring their favorable long-term stability.Moreover,the delocalized orbitals and relatively high dielectric constants in PEA^(+),attributed to the conjugated benzene ring,has been observed to weaken the potential barrier,exciton binding effect and quantum well confinement in 2D monolayer PEA2MX4,thus facilitating photogenerated electron-hole separations and out-of-plane carrier transport.The impact of spacer cations on the optoelectronic and transport properties of 2D monolayer perovskites highlights the critical role of meticulously chosen and well-designed spacer cations,especially functional groups,in shaping their photophysical properties and ensuring long-term stability even under extremely operating conditions.
基金supported by the National Key Research and Development Program of China(Nos.2022YFA1503300 and 2021YFA1500400)the National Natural Science Foundation of China(Nos.22171262,21825107 and 22171264)the Science Foundation of Fujian Province(Nos.2021J01516 and 2021J02016)。
文摘Selective separation of phenanthrene(PHE)from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene(ANT).Herein,we report the self-assembly of a water-soluble Pd_(2)L_(2) cage 1 with a large hydrophobic cavity,formed from novel macrocyclic ligands(L)and cis-Pd(Ⅱ).Cage 1 can selectively encapsulate PHE instead of ANT.Based on host-vip recognition followed by extraction,we achieve a remarkable 99%purity of PHE separation from an equimolar mixture of PHE and ANT using cage 1 in aqueous solution.Importantly,the separation performance of PHE using cage 1 remains unaffected even after five extraction cycles,demonstrating its robustness.This work highlights the potential of supramolecular cages for efficient and cost-effective PHE separation from the isomer ANT in aqueous solutions using such promising host-vip strategy.
基金supported by the National Key R&D Program of China(No.2021YFA1502300)the National Natural Science Foundation of China(Nos.22103012,22173105)+2 种基金the Natural Science Foundation of Fujian Province(Nos.2024J01456,2024J01191)the Selfdeployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(No.CXZX-2022-GH10)the CAS Youth Interdisciplinary Team.
文摘Crystal defects and morphological modifications are popular strategies to enhance the catalytic activity of heterogeneous semiconductor photocatalysts.Despite defect engineering and morphology control show their successful applications in ZnO,the effects of curved surface modifications on the photocatalytic performance of ZnO and their interplay with the defect formation remain unclear.To resolve this puzzle,we systemically investigate the joint effects of curvature and defect formation on the electronic structure,optoelectronic properties,and photocatalytic performance of ZnO slabs using first-principles calculations.We find that curvature deformation effectively narrows the electronic bandgap by up to 1.6 eV and shifts the p-/d-band centers,thereby enhancing light absorption in the visible and near-ultraviolet regions.Besides,curvature deformation stimulates self-polarization,facilitating the separation of photogenerated electrons and holes.Also,curvature deformation promotes the formation of defects by reducing defect formation energy(by up to 1.0 eV),thus creating abundant reaction sites for photocatalysis.Intriguingly,the synergistic interaction between curvature and defect deformation further strengthens the self-polarization,narrows the electronic bandgaps,adjusts the p-/d-band centers to improve the optoelectronic properties,and influences the dissociation and free energy barriers of intermediates.Consequently,our findings reveal that this synergy substantially enhances the photocatalytic performance of ZnO slabs,providing deeper insights into the role of defect engineering and morphology control on photocatalysis.
基金supported by the Natural Science Foundation of Fujian Province of China(2022J01646)。
文摘The heterostructures incorporated with two or more distinctive two-dimensional(2D)materials have attracted great attention be-cause they could give rise to enhanced prop-erty in comparison with their individual counterparts.Here,a water-assisted two-step rapid physical vapor deposition(rPVD)method was explored and used to synthesize Bi_(2)Te_(3)-Sb_(2)Te_(3)lateral het-erostructures(LHS)successfully.The Bi_(2)Te_(3)-Sb_(2)Te_(3)LHS is in nearly uniform size,and grows along three particular orientations with the intersection angles of 120°.Inter-estingly,we found that the water molecules play a significant role in determining the growth orientation,namely whether it will grow along the vertical or lateral direction in 2D structure.Hence,a growth mechanism of LHS based on the water-assisted two-step rPVD was present,which can be used as a general strategy and extended to the growth of other 2D heterostruc-tures or homostructures,such as SnS-SnSe LHS and SnS-SnS lateral homostructures.Fur-thermore,the second-harmonic generation intensity of the Bi_(2)Te_(3)-Sb_(2)Te_(3)LHS is much stronger than that of the Bi_(2)Te_(3)/Sb_(2)Te_(3)vertical heterostructures(VHS).This work opens a new approach for the synthesis of water-assisted lateral 2D heterostructures or homostruc-tures and offers a new method to enhance the second-harmonic generation properties of topo-logical insulating materials.
基金financially supported by Fujian Science and Technology Planning Projects of China(Nos.2022T3067 and 2023H0045)the Self-deployment Project Research Programs of Haixi Institutes,Chinese Academy of Sciences(No.CXZX2022-JQ12)the XIREM autonomously deployment project(No.2023GG02)。
文摘Na-Se batteries have caught tremendous attention because of natural abundant of element sodium and their high volumetric energy density(2530 Wh/L).However,the low utilization ratio of Se is the main obstacle for practical application.Herein,an advanced Se-based electrode is designed and prepared by using tea stem-derived micropore carbon matrix(TSC)as Se host and coating TSC/Se with cyclic polyacrylonitrile(cPAN).TSC/Se/cPAN electrode shows rate capacity of 318.3 mAh/g at 2 C(1 C=675 mA/g)and great discharge capacity of 420.6 mAh/g after 300 cycles at 0.2 C.The impressive electrochemical performance is mainly ascribed to the interface design of c PAN coating,resulting in the enhanced electronic conductivity of whole electrode and high ratio of robust inorganic salt NaCl in CEI film.The TSC/Se/c PAN||NVP full cell also exhibits great discharge capacity of 556.6 mAh/g after 55 cycles at 0.1 C.
