Effective treatment of subcutaneous tumors remains a focal point in cancer therapy.Photothermal therapy,a novel therapeutic approach,has emerged as a promising alternative,offering a less invasive option for the treat...Effective treatment of subcutaneous tumors remains a focal point in cancer therapy.Photothermal therapy,a novel therapeutic approach,has emerged as a promising alternative,offering a less invasive option for the treatment of subcutaneous tumors.This study reports the exploration of novel supramolecular halogen-bonded organic frameworks(XOFs)based on[N…Br^(+)…N]halogen bonds through the ligand exchange strategy and their application in photothermal therapy.Through ligand exchange,XOF(Br)-TPy was successfully prepared,and its structure and properties were thoroughly characterized using NMR,XPS,FT-IR,and XRD techniques.Due to their cationic characteristics,these XOFs serve as effective carriers for the photothermal agent IR820.In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation,effectively inducing tumor cell ablation.Furthermore,in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model.This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br)and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.展开更多
Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growt...Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.展开更多
The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts c...The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.展开更多
In situ electron paramagnetic resonance(EPR)monitoring of the photocatalytic halogen atom transfer(XAT)reaction with organic amines has provided insights into the dynamic transformations of intermediates,including cat...In situ electron paramagnetic resonance(EPR)monitoring of the photocatalytic halogen atom transfer(XAT)reaction with organic amines has provided insights into the dynamic transformations of intermediates,including catalyst intermediate states,amine alkyl radicals,and the dehalogenation of halogenated hydrocarbons to form carbon-centered radicals.This approach facilitated the photocatalytic single-linear state oxygen-promoted halogen atom transfer quinoxalinone alkylation reaction.展开更多
Halogen substituents play a crucial role in the structural diversity and biological activity of natural products,and the synthesis of halogenated molecules remains an area of significant research interest.This study d...Halogen substituents play a crucial role in the structural diversity and biological activity of natural products,and the synthesis of halogenated molecules remains an area of significant research interest.This study describes the generation of 15 new halogenated angucyclinones through the incorporation of halogen-containing phenylamines into a biosynthetic C-ringcleaved angucyclinone under mild conditions.The newly synthesized compounds feature halogen substituents encompassing all four halogen atoms(F,Cl,Br,I),with some compounds containing multiple halogen types.Structural elucidation was accomplished through ultraviolet(UV),infrared spectroscopy(IR),mass spectrometry(MS),and nuclear magnetic resonance(NMR)spectroscopic analyses,expanding the structural diversity of angucyclinonetype polyketides.Cytotoxicity evaluations revealed that eight compounds demonstrated moderate cytotoxic activities against four human tumor cell lines,with half maximal inhibitory concentration(IC_(50))values ranging from 3.35±0.37 to 16.02±6.60μmol·L-1.These findings highlight the significant potential of combining biosynthetic and chemical approaches in generating bioactive halogenated molecules.展开更多
The piezocatalytic characteristic of bismuth oxyhalides(BiOX,X=Cl,Br,and I) has been increasingly capturing interest for its potential in hydrogen evolution reaction(HER) through water splitting process.The performanc...The piezocatalytic characteristic of bismuth oxyhalides(BiOX,X=Cl,Br,and I) has been increasingly capturing interest for its potential in hydrogen evolution reaction(HER) through water splitting process.The performance regarding these piezocatalysts is closely related to the halogen element present in BiOX;yet,the specific influence mechanisms remain unclear.In this study,we prepared BiOX catalysts via a hydrothermal process and explored their piezocatalytic HER activities.Owing to the layered bismuth s tructure,the resulting sheet-like piezocatalysts can efficiently capture the mechanic stimulus and allow the robust piezoelectric field,contributing to the piezocatalytic operation.It demonstrates that the BiOBr achieves a remarkable piezocatalytic HER efficiency of 813 μmol g^(-1)h^(-1),outperforming BiOCl and BiOI.The density functional theory(DFT)calculation results reveal that the BiOBr with moderate halogen atom size and lattice layer spacing possesses the strongest piezoelectricity,which enhances the separation and transfer of electron-hole pairs.Meanwhile,the exposed Br atom layer facilitates a large Bader charge and a low surface Gibbs free energy(ΔG_(H)),enhancing charge transfer for hydrogen reduction at the solid-liquid surface,thereby increasing the HER efficiency.This research sheds light on the halogen-dependent piezocatalytic activity of BiOX catalysts,offering valuable insights for the development of high-performance piezocatalysts.展开更多
Rice,a primary food staple for over half of the global population,is susceptible to environmental pollution.The presence of lipophilic halogenated contaminants,including halogenated polycyclic aromatic hydrocarbons(XP...Rice,a primary food staple for over half of the global population,is susceptible to environmental pollution.The presence of lipophilic halogenated contaminants,including halogenated polycyclic aromatic hydrocarbons(XPAHs),polychlorinated biphenyls(PCBs),organochlorine pesticides(OCPs),brominated flame retardants(BFRs),and polyfluoroalkyl substances(PFAS),has become a growing concern due to their potential health risks and environmental impact.This review focused on the research of lipophilic halogenated contaminants in rice.We summarized the physicochemical properties,toxicity profiles,and contamination levels in rice.Moreover,the strategies for reducing lipophilic halogenated contaminant levels in rice were summarized and proposed,such as phytoremediation and improved processing methods.These findings can provide a reference for the understanding and control of lipophilic halogenated contaminants during rice growing and processing,and therefore reduce the associated risks.展开更多
Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electroc...Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electrocatalysts for lithium-sulfur(Li-S)batteries.However,the correlation between the properties of doped atoms and adsorptio n-catalytic ability,as well as the interconnection between adsorption strength and catalytic activity,remains underexplored.Herein,we employed halogen atoms(F,Cl,and Br)with different electronegativities to dope nickel phosphide(Ni_(2)P),aiming to modulate the adsorption properties toward lithium polysulfides(LiPSs).We systematically explored the relationship between the electronegativity of the doping atoms and the adsorption strength,followed by exploring the connection between adsorption and catalytic capabilities.Combined experimental and theoretical analyses reveal that doping halogen atoms effectively strengthens d-p orbital hybridization between Ni atoms and S atoms,thereby enhancing LiPSs anchoring and conversion.Specifically,the chemical adsorption capability is enhanced as the electronegativity of the doped atoms increases.Moreover,the catalytic activity presents a volcano-like trend with the enhancement of adsorption performance,wherein the activity initially increases and subsequently diminishes.Therefore,Cl-doped Ni_(2)P with moderate chemisorption ability exhibits optimal redox kinetics in bidirectional sulfur conversion.Consequently,the Li-S batteries with Cl-Ni_(2)P-separators deliver a high-rate capacity of 790 mAh g^(-1)at 5 C and achieve a remarkable areal capacity of 7.36 mAh cm^(-2)under practical conditions(sulfur loading:7.10 mg cm^(-2);electrolyte/sulfur(E/S)ratio:5μL mg^(-1)).This work uncovers the significance of achieving a balance between adsorption and catalytic capabilities,offering insights into designing efficient electrocatalysts for lithium-sulfur batteries.展开更多
The rovibrational spectra of thioanisole(TA)and its halogenated derivatives,3-fluorothioanisole(3FTA)and 3-chlorothioanisole(3ClTA),were measured using synchrotron-based Fourier transform infrared spectroscopy(FTIR)at...The rovibrational spectra of thioanisole(TA)and its halogenated derivatives,3-fluorothioanisole(3FTA)and 3-chlorothioanisole(3ClTA),were measured using synchrotron-based Fourier transform infrared spectroscopy(FTIR)at the Canadian Light Source.Combined with density functional theory calculations,the stable structures and vibrational modes of TA,3FTA,and 3ClTA in their vibrational states were analyzed.The theoretical vibrational mode frequencies were corrected by simulating the rotational structure of a vibrational band.The contributions of the cis-and trans-isomers of 3FTA and 3ClTA to the FTIR spectra at 298 K were estimated using the Boltzmann distribution,revealing their coexistence in the experimental spectra.The results indicate that both fluorine and chlorine substitution significantly affect the vibrational modes,particularly in the benzene ring.Compared to TA,the FTIR spectra of 3FTA and 3ClTA show changes in the frequencies and intensities of some vibrational modes,with halogen substitution causing specific modes to shift to higher wavenumbers.A comparison of the FTIR spectra of TA,3FTA,and 3ClTA highlights the influence of halogen substitution on vibrational properties,emphasizing how the type and position of the substituent affect frequency shifts and spectral intensities.These findings provide deeper insights into how halogenation alters vibrational spectra,which is crucial for further spectral analysis and molecular structure determination.展开更多
Organic solar cells(OSCs)have emerged as promising candidates for next‐generation photovoltaics,yet traditional bulk heterojunction(BHJ)devices face inherent limitations in morphology control and phase separation.La...Organic solar cells(OSCs)have emerged as promising candidates for next‐generation photovoltaics,yet traditional bulk heterojunction(BHJ)devices face inherent limitations in morphology control and phase separation.Layer‐by‐layer(LbL)processing with a p–i–n configuration offers an innovative solution by enabling precise control over donor–acceptor distribution and interfacial characteristics.Here,we systematically investigate nine halogen‐functionalized additives across three categories—methyl halides,thiophene halides,and benzene halides—for optimizing LbL device performance.These additives,distinguished by their diverse thermal properties and solid–liquid transformation capabilities below 100°C,are functionalized as both nucleation centers and morphology‐modulating plasticizers during thermal treatment.Among them,2‐bromo‐5‐iodothiophene(BIT)demonstrates superior performance through synergistic effects of its bromine–iodine combination and thiophene core in mediating donor–acceptor interactions.LbL devices processed with BIT achieve exceptional metrics in the PM6/L8‐BO system,including a open‐circuit voltage of 0.916 V,a short‐circuit current density of 27.12 mA cm−2,and an fill factor of 80.97%,resulting in an impressive power conversion efficiency of 20.12%.This study establishes a molecular design strategy for halogen‐functionalized additives that simultaneously optimizes both donor and acceptor layers while maintaining processing simplicity for potential industrial applications.展开更多
Halogenated aromatic disinfection byproducts(DBPs)are gradually receiving attention due to their high detection frequency and usually higher toxicity than regulated DBPs.In this study,we established a solid phase extr...Halogenated aromatic disinfection byproducts(DBPs)are gradually receiving attention due to their high detection frequency and usually higher toxicity than regulated DBPs.In this study,we established a solid phase extraction(SPE)-LC-MS/MS method to simultaneously trace analyze 59 halogenated aromatic DBPs.The limits of detection and limits of quantification of halogenated aromatic DBPs ranged from 0.03 to 135.23 ng/L and from 0.1 to 450.76 ng/L,respectively.The range of recoveries and relative standard deviation(RSD)in river water were between 72.41%to 119.54%and 1.86%to 16.03%,respectively.Therefore,this method can be used to accurately analyze trace levels of halogenated aromatic DBPs in drinking water.The occurrence and transformation of halogenated aromatic DBPs were explored based on this method.In the chlorinated simulated source water and chlorinated river water,20 and 45 halogenated aromatic DBPs were determined,respectively.The active halogen species(HOCl,HOBr,and HOI)first reacted with natural organic matter(NOM)to form halogenated aromatic DBPs.Then,chlorine further reacted with the halogenated aromatic DBPs to convert them into small-molecule halogenated aliphatic DBPs through oxidation,electrophilic substitution,and hydrolysis reaction,etc.In the chlorinated simulated source water,chlorinated river water,and tap water,the toxicity contribution of bromoacetic acids(Br-HAAs)accounted for themajority(>71.16%).Given that halogenated aromatic DBPs are intermediate products of halogenated aliphatic DBPs,controlling the formation of halogenated aromatic DBPs is beneficial in decreasing the formation of halogenated aliphatic DBPs,thereby diminishing the toxicity of drinking water.展开更多
Efficient conversion and synergistic solar energy utilization are critical for advancing low-carbon and sustainable development.In this study,two Pt(Ⅱ)-based metal/halogen-bonded organic frameworks(MXOFBen and MXOF-A...Efficient conversion and synergistic solar energy utilization are critical for advancing low-carbon and sustainable development.In this study,two Pt(Ⅱ)-based metal/halogen-bonded organic frameworks(MXOFBen and MXOF-Anth)were designed to enhance photoconversion efficiency and enable multifunctional integration.The ligand L-terpyr is formed by coupling tripyridine with diphenylamine dipyridine,in which the tripyridine effectively acts as a metal-ligand to lower the band gap and promote nonradiative leaps,thereby enhancing the photoconversion ability.Meanwhile,diphenylamine dipyridine serves as a[N…I^(+)…N]halogen-bonding acceptor,imparting superhydrophilicity to the materials and increasing carrier density,further improving photocatalytic performance.Experimental results demonstrate that these two MXOFs achieve impressive interfacial water evaporation efficiencies of up to87.8%and 94.0%,respectively.Additionally,the materials exhibit excellent performance in photothermal power generation and photocatalysis of H_(2)O_(2).Notably,the MXOFs also deliver strong overall performance in integrated systems combining interfacial water evaporation with photothermal power generation or photocatalysis,underscoring their exceptional photoconversion efficiency and multifunctional potential.This work introduces a novel strategy by incorporating metal-ligand and halogen bonds,offering a pathway to enhance photoconversion efficiency and develop versatile materials for advanced solar energy applications,thereby fostering the progress of high-efficiency solar energy conversion and multifunctional organic materials.展开更多
Inverse halogen bonds interactions involving Br in the electronic deficiency systems of CH3＋...Br-Y （Y=H, CCH, CN, NC） have been investigated by B3LYP/6- 311＋＋G（d, p） and MP2/6-311＋＋G（d, p） methods. The cal...Inverse halogen bonds interactions involving Br in the electronic deficiency systems of CH3＋...Br-Y （Y=H, CCH, CN, NC） have been investigated by B3LYP/6- 311＋＋G（d, p） and MP2/6-311＋＋G（d, p） methods. The calculated interaction energies with basis set super-position error correction of the four IXBs complexes are 218.87, 219.48, 159.18, and 143.05kJ/mol （MP2/6-311＋＋G（d, p））, respectively. The relative stabilities of the four complexes increased in the order： CH3＋ … BrCN〈CH3＋…- BrNC〈CH3＋… BrH≈CH3＋ …BrCCH. Natural bond orbital theory analysis and the chemical shifts calculation of the related atoms revealed that the charges flow from Br-Y to CH3e. Here, the Br of Br-Y acts as both a halogen bond donor and an electron donor. Therefore, compared with conventional halogen bonds, the IXBs complexes formed between Br-Y and CH3＋. Atoms-in-molecules theory has been used to investigate the topological properties of the critical points of the four IXBs structures which have more covalent content.展开更多
Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from...Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22371218,82271518,21801194)Xianyang Bureau of Science and Technology(No.L2024-QCY-ZYYJJQ-260)+2 种基金The Interdisciplinary Innovative Talents Foundation from Renmin Hospital of Wuhan University(No.JCRCFZ-2022-030)Guiding Projects of Traditional Chinese Medicine in 2023~2024 by Hubei Provincial Administration of Traditional Chinese Medicine(No.ZY2023F038)the support of the Core Facility of Wuhan University and the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘Effective treatment of subcutaneous tumors remains a focal point in cancer therapy.Photothermal therapy,a novel therapeutic approach,has emerged as a promising alternative,offering a less invasive option for the treatment of subcutaneous tumors.This study reports the exploration of novel supramolecular halogen-bonded organic frameworks(XOFs)based on[N…Br^(+)…N]halogen bonds through the ligand exchange strategy and their application in photothermal therapy.Through ligand exchange,XOF(Br)-TPy was successfully prepared,and its structure and properties were thoroughly characterized using NMR,XPS,FT-IR,and XRD techniques.Due to their cationic characteristics,these XOFs serve as effective carriers for the photothermal agent IR820.In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation,effectively inducing tumor cell ablation.Furthermore,in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model.This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br)and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
基金support from the National Natural Science Foundation of China(22209089,22178187)Natural Science Foundation of Shandong Province(ZR2022QB048,ZR2021MB006)+2 种基金Excellent Youth Science Foundation of Shandong Province(Overseas)(2023HWYQ-089)the Taishan Scholars Program of Shandong Province(tsqn201909091)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.
文摘Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.
文摘The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.
基金Project supported by the Domestic Visiting Fellows Program of Hangzhou Normal University(No.4095C5022521106)。
文摘In situ electron paramagnetic resonance(EPR)monitoring of the photocatalytic halogen atom transfer(XAT)reaction with organic amines has provided insights into the dynamic transformations of intermediates,including catalyst intermediate states,amine alkyl radicals,and the dehalogenation of halogenated hydrocarbons to form carbon-centered radicals.This approach facilitated the photocatalytic single-linear state oxygen-promoted halogen atom transfer quinoxalinone alkylation reaction.
基金supported by the National Key Research and Development Program of China(Nos.2023YFC3503900,2023YFA0914102)National Natural Science Foundation of China(Nos.82325046,82273829,92357305,22377004,22077007)the key project at central government level:the ability establishment of sustainable use for valuable Chinese medicine resources(No.2060302-2201-17)。
文摘Halogen substituents play a crucial role in the structural diversity and biological activity of natural products,and the synthesis of halogenated molecules remains an area of significant research interest.This study describes the generation of 15 new halogenated angucyclinones through the incorporation of halogen-containing phenylamines into a biosynthetic C-ringcleaved angucyclinone under mild conditions.The newly synthesized compounds feature halogen substituents encompassing all four halogen atoms(F,Cl,Br,I),with some compounds containing multiple halogen types.Structural elucidation was accomplished through ultraviolet(UV),infrared spectroscopy(IR),mass spectrometry(MS),and nuclear magnetic resonance(NMR)spectroscopic analyses,expanding the structural diversity of angucyclinonetype polyketides.Cytotoxicity evaluations revealed that eight compounds demonstrated moderate cytotoxic activities against four human tumor cell lines,with half maximal inhibitory concentration(IC_(50))values ranging from 3.35±0.37 to 16.02±6.60μmol·L-1.These findings highlight the significant potential of combining biosynthetic and chemical approaches in generating bioactive halogenated molecules.
基金financially supported by the Natural Science Foundation of Shandong Province(No.ZR2023MB151)the Natural Science Foundation of Shandong Province for Excellent Young Scholars(No.ZR2022YQ13)+1 种基金the Science and Technology Special Project of Qingdao(No.24-1-8-xdny-18nsh)the Taishan Scholar Project of Shandong Province(No.tsqn202211159)
文摘The piezocatalytic characteristic of bismuth oxyhalides(BiOX,X=Cl,Br,and I) has been increasingly capturing interest for its potential in hydrogen evolution reaction(HER) through water splitting process.The performance regarding these piezocatalysts is closely related to the halogen element present in BiOX;yet,the specific influence mechanisms remain unclear.In this study,we prepared BiOX catalysts via a hydrothermal process and explored their piezocatalytic HER activities.Owing to the layered bismuth s tructure,the resulting sheet-like piezocatalysts can efficiently capture the mechanic stimulus and allow the robust piezoelectric field,contributing to the piezocatalytic operation.It demonstrates that the BiOBr achieves a remarkable piezocatalytic HER efficiency of 813 μmol g^(-1)h^(-1),outperforming BiOCl and BiOI.The density functional theory(DFT)calculation results reveal that the BiOBr with moderate halogen atom size and lattice layer spacing possesses the strongest piezoelectricity,which enhances the separation and transfer of electron-hole pairs.Meanwhile,the exposed Br atom layer facilitates a large Bader charge and a low surface Gibbs free energy(ΔG_(H)),enhancing charge transfer for hydrogen reduction at the solid-liquid surface,thereby increasing the HER efficiency.This research sheds light on the halogen-dependent piezocatalytic activity of BiOX catalysts,offering valuable insights for the development of high-performance piezocatalysts.
基金supported by the National Natural Science Foundation of China(No.32061160476).
文摘Rice,a primary food staple for over half of the global population,is susceptible to environmental pollution.The presence of lipophilic halogenated contaminants,including halogenated polycyclic aromatic hydrocarbons(XPAHs),polychlorinated biphenyls(PCBs),organochlorine pesticides(OCPs),brominated flame retardants(BFRs),and polyfluoroalkyl substances(PFAS),has become a growing concern due to their potential health risks and environmental impact.This review focused on the research of lipophilic halogenated contaminants in rice.We summarized the physicochemical properties,toxicity profiles,and contamination levels in rice.Moreover,the strategies for reducing lipophilic halogenated contaminant levels in rice were summarized and proposed,such as phytoremediation and improved processing methods.These findings can provide a reference for the understanding and control of lipophilic halogenated contaminants during rice growing and processing,and therefore reduce the associated risks.
基金supported by the Beijing Institute of Technology Research Fund Program for Young Scholars and 21C Innovation Laboratory Contemporary Amperex Technology Co.,Limited,Ninde,352100,China(21C-OP-202314)。
文摘Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electrocatalysts for lithium-sulfur(Li-S)batteries.However,the correlation between the properties of doped atoms and adsorptio n-catalytic ability,as well as the interconnection between adsorption strength and catalytic activity,remains underexplored.Herein,we employed halogen atoms(F,Cl,and Br)with different electronegativities to dope nickel phosphide(Ni_(2)P),aiming to modulate the adsorption properties toward lithium polysulfides(LiPSs).We systematically explored the relationship between the electronegativity of the doping atoms and the adsorption strength,followed by exploring the connection between adsorption and catalytic capabilities.Combined experimental and theoretical analyses reveal that doping halogen atoms effectively strengthens d-p orbital hybridization between Ni atoms and S atoms,thereby enhancing LiPSs anchoring and conversion.Specifically,the chemical adsorption capability is enhanced as the electronegativity of the doped atoms increases.Moreover,the catalytic activity presents a volcano-like trend with the enhancement of adsorption performance,wherein the activity initially increases and subsequently diminishes.Therefore,Cl-doped Ni_(2)P with moderate chemisorption ability exhibits optimal redox kinetics in bidirectional sulfur conversion.Consequently,the Li-S batteries with Cl-Ni_(2)P-separators deliver a high-rate capacity of 790 mAh g^(-1)at 5 C and achieve a remarkable areal capacity of 7.36 mAh cm^(-2)under practical conditions(sulfur loading:7.10 mg cm^(-2);electrolyte/sulfur(E/S)ratio:5μL mg^(-1)).This work uncovers the significance of achieving a balance between adsorption and catalytic capabilities,offering insights into designing efficient electrocatalysts for lithium-sulfur batteries.
基金supported by the National Natural Science Foundation of China(No.223B2306)the Innovation Capability Support Program of Shaanxi Province(2023-CX-TD-49)the Natural Science Basic Research Program of Shaanxi Province(2025JC-JCQN-043).
文摘The rovibrational spectra of thioanisole(TA)and its halogenated derivatives,3-fluorothioanisole(3FTA)and 3-chlorothioanisole(3ClTA),were measured using synchrotron-based Fourier transform infrared spectroscopy(FTIR)at the Canadian Light Source.Combined with density functional theory calculations,the stable structures and vibrational modes of TA,3FTA,and 3ClTA in their vibrational states were analyzed.The theoretical vibrational mode frequencies were corrected by simulating the rotational structure of a vibrational band.The contributions of the cis-and trans-isomers of 3FTA and 3ClTA to the FTIR spectra at 298 K were estimated using the Boltzmann distribution,revealing their coexistence in the experimental spectra.The results indicate that both fluorine and chlorine substitution significantly affect the vibrational modes,particularly in the benzene ring.Compared to TA,the FTIR spectra of 3FTA and 3ClTA show changes in the frequencies and intensities of some vibrational modes,with halogen substitution causing specific modes to shift to higher wavenumbers.A comparison of the FTIR spectra of TA,3FTA,and 3ClTA highlights the influence of halogen substitution on vibrational properties,emphasizing how the type and position of the substituent affect frequency shifts and spectral intensities.These findings provide deeper insights into how halogenation alters vibrational spectra,which is crucial for further spectral analysis and molecular structure determination.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB4200500)National Natural Science Foundation of China(NSFC,22379101 and 22422904)Sichuan Natural Science Foundation(2024NSFSC0001 and 2025ZNSFSC0960).
文摘Organic solar cells(OSCs)have emerged as promising candidates for next‐generation photovoltaics,yet traditional bulk heterojunction(BHJ)devices face inherent limitations in morphology control and phase separation.Layer‐by‐layer(LbL)processing with a p–i–n configuration offers an innovative solution by enabling precise control over donor–acceptor distribution and interfacial characteristics.Here,we systematically investigate nine halogen‐functionalized additives across three categories—methyl halides,thiophene halides,and benzene halides—for optimizing LbL device performance.These additives,distinguished by their diverse thermal properties and solid–liquid transformation capabilities below 100°C,are functionalized as both nucleation centers and morphology‐modulating plasticizers during thermal treatment.Among them,2‐bromo‐5‐iodothiophene(BIT)demonstrates superior performance through synergistic effects of its bromine–iodine combination and thiophene core in mediating donor–acceptor interactions.LbL devices processed with BIT achieve exceptional metrics in the PM6/L8‐BO system,including a open‐circuit voltage of 0.916 V,a short‐circuit current density of 27.12 mA cm−2,and an fill factor of 80.97%,resulting in an impressive power conversion efficiency of 20.12%.This study establishes a molecular design strategy for halogen‐functionalized additives that simultaneously optimizes both donor and acceptor layers while maintaining processing simplicity for potential industrial applications.
基金supported by the National Natural Science Foundation of China(No.52300005)China Postdoctoral Science Foundation(No.2023TQ0098)+5 种基金Heilongjiang Postdoctoral Fund(No.LBH-Z23175)Heilongjiang Touyan Innovation Team Program(No.HIT-SE-01)the Crossover Fund of Medical Engineering Science of Harbin Institute of Technology(No.IR2021107)the National Natural Science Foundation of International(Regional)Cooperation and Exchange Project(No.51961125104)the State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2022TS15)the Ecological and Environmental Protection Research Project of Heilongjiang Province(No.HST2022ST006).
文摘Halogenated aromatic disinfection byproducts(DBPs)are gradually receiving attention due to their high detection frequency and usually higher toxicity than regulated DBPs.In this study,we established a solid phase extraction(SPE)-LC-MS/MS method to simultaneously trace analyze 59 halogenated aromatic DBPs.The limits of detection and limits of quantification of halogenated aromatic DBPs ranged from 0.03 to 135.23 ng/L and from 0.1 to 450.76 ng/L,respectively.The range of recoveries and relative standard deviation(RSD)in river water were between 72.41%to 119.54%and 1.86%to 16.03%,respectively.Therefore,this method can be used to accurately analyze trace levels of halogenated aromatic DBPs in drinking water.The occurrence and transformation of halogenated aromatic DBPs were explored based on this method.In the chlorinated simulated source water and chlorinated river water,20 and 45 halogenated aromatic DBPs were determined,respectively.The active halogen species(HOCl,HOBr,and HOI)first reacted with natural organic matter(NOM)to form halogenated aromatic DBPs.Then,chlorine further reacted with the halogenated aromatic DBPs to convert them into small-molecule halogenated aliphatic DBPs through oxidation,electrophilic substitution,and hydrolysis reaction,etc.In the chlorinated simulated source water,chlorinated river water,and tap water,the toxicity contribution of bromoacetic acids(Br-HAAs)accounted for themajority(>71.16%).Given that halogenated aromatic DBPs are intermediate products of halogenated aliphatic DBPs,controlling the formation of halogenated aromatic DBPs is beneficial in decreasing the formation of halogenated aliphatic DBPs,thereby diminishing the toxicity of drinking water.
基金supported by the National Natural Science Foundation of China(Nos.22371218,21702153,52270070,and 21801194)the Wuhan Science and Technology Bureau(No.whkxjsj009)+1 种基金support of the Core Facility of Wuhan Universitythe Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘Efficient conversion and synergistic solar energy utilization are critical for advancing low-carbon and sustainable development.In this study,two Pt(Ⅱ)-based metal/halogen-bonded organic frameworks(MXOFBen and MXOF-Anth)were designed to enhance photoconversion efficiency and enable multifunctional integration.The ligand L-terpyr is formed by coupling tripyridine with diphenylamine dipyridine,in which the tripyridine effectively acts as a metal-ligand to lower the band gap and promote nonradiative leaps,thereby enhancing the photoconversion ability.Meanwhile,diphenylamine dipyridine serves as a[N…I^(+)…N]halogen-bonding acceptor,imparting superhydrophilicity to the materials and increasing carrier density,further improving photocatalytic performance.Experimental results demonstrate that these two MXOFs achieve impressive interfacial water evaporation efficiencies of up to87.8%and 94.0%,respectively.Additionally,the materials exhibit excellent performance in photothermal power generation and photocatalysis of H_(2)O_(2).Notably,the MXOFs also deliver strong overall performance in integrated systems combining interfacial water evaporation with photothermal power generation or photocatalysis,underscoring their exceptional photoconversion efficiency and multifunctional potential.This work introduces a novel strategy by incorporating metal-ligand and halogen bonds,offering a pathway to enhance photoconversion efficiency and develop versatile materials for advanced solar energy applications,thereby fostering the progress of high-efficiency solar energy conversion and multifunctional organic materials.
基金This work was supported by the National Natural Science Foundation of China （No.51063006 and No.50975273） and the ＂QingLan＂ Talent Engineering Funds of Tianshui Normal University.
文摘Inverse halogen bonds interactions involving Br in the electronic deficiency systems of CH3＋...Br-Y （Y=H, CCH, CN, NC） have been investigated by B3LYP/6- 311＋＋G（d, p） and MP2/6-311＋＋G（d, p） methods. The calculated interaction energies with basis set super-position error correction of the four IXBs complexes are 218.87, 219.48, 159.18, and 143.05kJ/mol （MP2/6-311＋＋G（d, p））, respectively. The relative stabilities of the four complexes increased in the order： CH3＋ … BrCN〈CH3＋…- BrNC〈CH3＋… BrH≈CH3＋ …BrCCH. Natural bond orbital theory analysis and the chemical shifts calculation of the related atoms revealed that the charges flow from Br-Y to CH3e. Here, the Br of Br-Y acts as both a halogen bond donor and an electron donor. Therefore, compared with conventional halogen bonds, the IXBs complexes formed between Br-Y and CH3＋. Atoms-in-molecules theory has been used to investigate the topological properties of the critical points of the four IXBs structures which have more covalent content.
基金supported by the financial support from the National Research Foundation,Singapore,under its Singapore-China Joint Flagship Project(Clean Energy).
文摘Aqueous Zn-iodine batteries(ZIBs)face the formidable challenges towards practical implementation,including metal corrosion and rampant dendrite growth on the Zn anode side,and shuttle effect of polyiodide species from the cathode side.These challenges lead to poor cycle stability and severe self-discharge.From the fabrication and cost point of view,it is technologically more viable to deploy electrolyte engineering than electrode protection strategies.More importantly,a synchronous method for modulation of both cathode and anode is pivotal,which has been often neglected in prior studies.In this work,cationic poly(allylamine hydrochloride)(Pah^(+))is adopted as a low-cost dual-function electrolyte additive for ZIBs.We elaborate the synchronous effect by Pah^(+)in stabilizing Zn anode and immobilizing polyiodide anions.The fabricated Zn-iodine coin cell with Pah^(+)(ZnI_(2) loading:25 mg cm^(−2))stably cycles 1000 times at 1 C,and a single-layered 3.4 cm^(2) pouch cell(N/P ratio~1.5)with the same mass loading cycles over 300 times with insignificant capacity decay.
