Wide-bandgap mixed-halide perovskites,particularly CsPbIBr_(2),hold great promise for multi-junction solar cells due to their well-matched bandgap and all-inorganic material system.However,their inherent susceptibilit...Wide-bandgap mixed-halide perovskites,particularly CsPbIBr_(2),hold great promise for multi-junction solar cells due to their well-matched bandgap and all-inorganic material system.However,their inherent susceptibility to light-induced phase segregation(LIPS)limits efficiency and stability.In this work,we investigate the effect of three organic additives-4-cyclopentene-1,3-dione(CPD),maleimide(HPD),and 3,4-dibromo-1H-pyrrole-2,5(2H,5H)-dione(BrPD)-on LIPS in wide-bandgap CsPbIBr_(2)perovskite films.The additives form various chemical interactions,including coordination bonds,hydrogen bonds,and ionic bonds,with I^(-)and undercoordinated Pb^(2+)ions,among which BrPD has the strongest interaction.This interaction regulates crystallization and improves film morphology.The BrPD-modified films have the largest grain size and the highest light stability,suppressing LIPS,enhancing carrier transfer,and improving device performance.BrPD-modified CsPbIBr_(2)-based solar cells achieve a power conversion efficiency(PCE)of 11.34%,outperforming the control(8.96%)and other additives.Moreover,BrPDmodified devices show excellent stability,retaining 94%of their initial PCE after 60 min of continuous light exposure.This work highlights the potential of strategically selected organic additives to enhance the stability and performance of perovskite solar cells,offering valuable insights for the design of high-efficiency and long-lasting perovskite-based optoelectronic devices.展开更多
Styrene epoxidation is a crucial reaction in the chemical industry.However,low Faradaic efficiency(FE)and product selectivity severely limit the efficiency of(photo)electrocatalytic styrene epoxidation processes.This ...Styrene epoxidation is a crucial reaction in the chemical industry.However,low Faradaic efficiency(FE)and product selectivity severely limit the efficiency of(photo)electrocatalytic styrene epoxidation processes.This study designs an efficient photothermal catalytic system based on an Au/NiCo_(2)O_(4)photoanode,which achieves the product selectivity of 98%and FE of 96%for bromide-mediated styrene epoxidation when the styrene conversion reaches 94%,surpassing most current reports on photoelectrocatalytic styrene epoxidation.A comprehensive mechanistic study reveals that the photothermal effect of the Au/NiCo_(2)O_(4)photoanode enhances local temperature,which facilitates bromine species mass transfer,reduces reaction activation energy and accelerates the oxidation kinetics of Br^(-).This study elucidates the photothermal-driven reaction mechanism of styrene epoxidation,providing guidelines for designing efficient and stable photothermal catalytic technologies.展开更多
The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere f...The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.展开更多
Organic ambipolar emitting materials hold immense potential for application in integrated optoelectrical devices yet challenging to design and synthesize.Cocrystals exhibit significant superiority in designing such ma...Organic ambipolar emitting materials hold immense potential for application in integrated optoelectrical devices yet challenging to design and synthesize.Cocrystals exhibit significant superiority in designing such materials because the properties of emission and transport can be flexibly tailored through the strategic pairing of donor and acceptor units.In this study,we report a new cocrystal system,DPA-5FDPA,derived from two high-mobility emissive molecules,2,6-diphenylanthracene(DPA)and 2,6-diperfluorophenyl anthracene(5FDPA).This cocrystal system exhibits outstanding emission and ambipolar semiconducting properties.Notably,the single-crystal field-effect transistor devices based on DPA-5FDPA achieve maximum hole and electron mobilities of 0.298 cm^(2) V^(-1) s^(-1) and 0.009 cm^(2) V^(-1) s^(-1),respectively.In comparison,the reference compound of 2-perfluorophenyl-6-phenylanthracene(5FBA)exhibits unipolar p-type transport with the hole mobility of 0.008 cm^(2) V^(-1) s^(-1).In addition,DPA-5FDPA exhibits excellent optical waveguide behavior with a small optical loss coefficient of 0.079 dB/µm at 508 nm,which is lower than most reported cocrystal systems.These results underscore the promise of co-crystallization as a versatile strategy for developing advanced ambipolar emissive semiconductors and provide deeper insights into the relationships among molecular structures,packing modes,intermolecular interactions,and charge-transport properties.展开更多
Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O cr...Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.展开更多
Biomarker-based sperm analysis elevates the treatment of human infertility and ameliorates reproductive performance in livestock. The negative biomarker-based approach focuses on proteins and ligands unique to defecti...Biomarker-based sperm analysis elevates the treatment of human infertility and ameliorates reproductive performance in livestock. The negative biomarker-based approach focuses on proteins and ligands unique to defective spermatozoa, regardless of their morphological phenotype, lending itself to analysis by flow cytometry （FC）. A prime example is the spermatid specific thioredoxin SPTRX3/TXNDC8, retained in the nuclear vacuoles and superfluous cytoplasm of defective human spermatozoa. Infertile couples with high semen SPTRX3 are less likely to conceive by assisted reproductive therapies （ART） and more prone to recurrent miscarriage while low SPTRX3 has been associated with multiple ART births. Ubiquitin, a small, proteolysis-promoting covalent posttranslational protein modifier is found on the surface of defective posttesticular spermatozoa and in the damaged protein aggregates, the aggresomes of spermiogenic origin. Semen ubiquitin content correlates negatively with fertility and conventional semen parameters, and with sperm binding of lectins LCA （Lens culinaris agglutinin; reveals altered sperm surface） and PNA （Arachis hypogaealpeanut agglutinin; reveals acrosomal malformation or damage）. The Postacrosomal Sheath WWl Domain Binding Protein （PAWP）, implicated in oocyte activation during fertilization, is ectopic or absent from defective human and animal spermatozoa. Consequently, FC-parameters of PAWP correlate with ART outcomes in infertile couples and with fertility in bulls. Assays based on the above biomarkers have been combined into multiplex FC semen screening protocols, and the surface expression of lectins and ubiquitin has been utilized to develop nanoparticle-based bull semen purification method validated by field artificial insemination trials. These advances go hand-in-hand with the innovation of FC-technology and genomics/proteomics-based biomarker discovery.展开更多
The van der Waals (vdW) interaction is very important in fields of physics, biology and chemistry, and its role in reaction dynamics is an issue of great interest. In this review, we focus on the recent progresses in ...The van der Waals (vdW) interaction is very important in fields of physics, biology and chemistry, and its role in reaction dynamics is an issue of great interest. In this review, we focus on the recent progresses in the theoretical and experimental studies on the vdW interaction in bimolecular reactions. In particular, we review those studies that have advanced our understanding of how the vdW interaction can strongly influence the dynamics in both direct activated and complex-forming reactions, and further extend the discussion to the polyatomic reactions involving more atoms and those occurring at cold and ultracold temperatures. We indicate that an accurate description of the delicate vdW structure and long-range potential remains a challenge nowadays in either ab initio calculations or the fitting of the potential energy surfaces. We also present an explanation on the concept of vdW saddle proposed by us recently which may have general importance.展开更多
Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very g...Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.展开更多
Side chains play a critical role in tuning intermolecular interaction and charge transport in organic semiconductors. Here, we have systematically investigated the impact of branching positions of the alkyl side chain...Side chains play a critical role in tuning intermolecular interaction and charge transport in organic semiconductors. Here, we have systematically investigated the impact of branching positions of the alkyl side chains on the molecular packing and electron transport properties of a series of bay-linked dimeric perylenediimide(PDI) derivatives by atomistic molecular dynamics simulations in combination with charge transfer rate theory and kinetic Monte Carlo simulations. The results show that despite of different branching positions of the alkyl chains,π–π stacking is effectively inhibited for all the dimeric PDI derivatives. As the branching position moves away from the PDI backbone, the appearance of the alkyl atoms around the PDI backbone will first decrease and then increase. Correspondingly, the short contacts between the PDI moieties are first enhanced and then reduced. In particular, when the branching position is at the third carbon atom, the intermolecular connectivity becomes the most effective and the electron mobility is significantly increased by 2 times.展开更多
Electronic polarization has an important impact on the site energies of charge carriers that play a key role in determining the charge transport in organic semiconductors.Dipolar molecules have strong intermolecular i...Electronic polarization has an important impact on the site energies of charge carriers that play a key role in determining the charge transport in organic semiconductors.Dipolar molecules have strong intermolecular interactions and widespread applications in organic optoelectronics.Howeve r,compared with nonpolar organic semiconductors,electronic polarization for dipolar systems has been rarely studied.Here,taking 1,2,3,4-tetrafluoro-6,7-dimethylnaphthalene as representative,we have calculated the electronic polarization energies of dipolar organic molecular crystals by means of a polarizable forcefield method.Surprisingly,our results point to that the polarization energies for this dipolar system are similar to those of nonpolar systems.In addition,theπ-πstack contributes only about 30%~40%to the total polarization energy,thus the polarization effects along the three dimensions should be treated equally even for the one-dimensional stacking crystals.展开更多
An efficient and accurate method for computing the equilibriurn reduced density matrix is presented for treating open quantum systems characterized by the systern-bath model. The method employs the rnultilayer nmltico...An efficient and accurate method for computing the equilibriurn reduced density matrix is presented for treating open quantum systems characterized by the systern-bath model. The method employs the rnultilayer nmlticonfiguration tirne-dependent Hartree theory for imag- inary time propagation and an importance sampling procedure for calculating the quantum mechanical trace. The method is applied to the spin-boson Harniltonian, which leads to ac- curate results in agreement with those produced by the rnulti-electronic-state path integral molecular dynamics method.展开更多
The effect of chromophores to the glass transition temperature of polyimide ensemble has been investigated by means of molecular dynamics simulation in conjunction with barrier analysis. Simulated Tg results indicated...The effect of chromophores to the glass transition temperature of polyimide ensemble has been investigated by means of molecular dynamics simulation in conjunction with barrier analysis. Simulated Tg results indicated a good agreement with experimental value. This study showed the MD simulation could estimate the effect of chromophores to the Tg of polyimide ensemble conveniently and an estimation approach method had a surprising deviation of Tg from experiment. At the same time, a polyimide structure with higher barrier energy was designed and validated by MD simulation.展开更多
The densities of n-pentane, methane-n-pentane, propane-n-pentane, n-heptane-n-pentane, and n-decane-n-pentane binary mixtures were determined at 476.5K in the pressure range from 2 to 5 MPa. The partial molar volumes ...The densities of n-pentane, methane-n-pentane, propane-n-pentane, n-heptane-n-pentane, and n-decane-n-pentane binary mixtures were determined at 476.5K in the pressure range from 2 to 5 MPa. The partial molar volumes of the solutes in n-pentane were calculated using the density data. It was found that the partial molar volumes of methane and propane are positive, while those of n-heptane and n-decane are negative.展开更多
Snow and freezing disasters are recurrent weather and climate phenomena that affect the world annually.These events exert a significant influence on numerous aspects of life,including transportation,power supply,and d...Snow and freezing disasters are recurrent weather and climate phenomena that affect the world annually.These events exert a significant influence on numerous aspects of life,including transportation,power supply,and daily activities,and result in considerable economic losses.This study aims to provide a comprehensive analysis of the regions affected by these disasters,the preventive and responsive measures employed,recent advancements in key materials,and the challenges encountered.By doing so,we can gain a deeper understanding of the vital role,significant advantages,and untapped potential of key materials for effectively preventing and responding to snow and freezing disasters.Furthermore,promoting research and utilization of these materials not only contributes to the development of the safety and emergency equipment industry but also strengthens the supply of advanced and suitable safety and emergency equipment.展开更多
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture.Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectivene...Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture.Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness.In this work,a bio-derived shellac incorporated with polydodecyl trimethoxysilane(SL-PDTMS)capsule was developed for long-term controlled releasing urea.Due to enhanced hydrophobicity and thus water resistance,the SL-PDTMS encapsulated urea fertilizer(SPEU)demonstrated a long-term effectiveness of 60 d,compared with SL encapsulated urea fertilizer(SEU,30 d)and pure urea fertilizer(U,5 min).In addition,SPEU showed a broad pH tolerance from 5.0 to 9.0,covering most various soil pH conditions.In the pot experiments,promoted growth of maize seedlings was observed after applying SPEU,rendering it promising as a high-performance controlled-released fertilizer.展开更多
Zn metal batteries are highly attractive because of their high theoretical specific capacity,intrinsic safety and resource availability.However,further development is significantly hindered by low Coulomb efficiency,w...Zn metal batteries are highly attractive because of their high theoretical specific capacity,intrinsic safety and resource availability.However,further development is significantly hindered by low Coulomb efficiency,which is closely linked to reaction processes occurring at electrode/electrolyte interfaces.Herein,we have achieved a real-time visualization and comprehensive analysis of the interfacial evolution of Zn metal anode via in situ AFM in organic and aqueous electrolytes,respectively.The processes of uneven nucleation,dendrite growth,the Zn O formation and the dissolution of Zn substrate are directly probed in aqueous electrolyte,which induces interfacial deterioration and ultimately results in battery failure.In organic electrolyte,the in situ observations show that the homogeneous nuclei form on the Zn surface to induce the dendrite-free deposition,however,exhibiting poor Zn plating/stripping reversibility.This work delves into the dynamic evolution and electrochemical behaviors regulated by solvents,which provides in-depth understanding of structure-reactivity correlations and further interfacial engineering.展开更多
Unstable electrode/electrolyte interfaces and heterogeneous Zn deposition would reduce the Coulombic efficiency and cycle life of Zn metal batteries(ZMBs). Applying water-in-salt(WIS) electrolytes has proven to be an ...Unstable electrode/electrolyte interfaces and heterogeneous Zn deposition would reduce the Coulombic efficiency and cycle life of Zn metal batteries(ZMBs). Applying water-in-salt(WIS) electrolytes has proven to be an effective strategy to address the above issues. However, an understanding of the reaction mechanisms on the Zn anode at nanoscale is still elusive. Here we utilize in situ atomic force microscopy to visualize the solid electrolyte interphase(SEI) formation and Zn deposition/dissolution processes in WIS electrolyte and construct relationships between interfacial behavior and electrochemical performance. The formation processes, chemical properties, and structure of the on-site formed SEI are deeply explored.The SEI with a “plum-pudding” model can guide uniform Zn deposition and reversible dissolution. Mechanistic understanding of the interfacial evolution of the SEI layer and Zn deposition/dissolution has been achieved and will benefit the structural optimization and interfacial engineering of ZMBs.展开更多
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis.It is the first time that allene was introduced into transition metal an...An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis.It is the first time that allene was introduced into transition metal and NHC synergetic catalysis,which demonstrated a versatile three-component reaction pattern,thus enabling two C-C bonds forged regioselectively in the reaction.The important reaction intermediates were successfully captured and characterized by HRMS analysis,and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.展开更多
Ring polymers are ubiquitous in various fields including biomaterials,drug release and gene therapy.All of these applications involve the dynamics and diffusion process of ring polymers in a confined environment.By us...Ring polymers are ubiquitous in various fields including biomaterials,drug release and gene therapy.All of these applications involve the dynamics and diffusion process of ring polymers in a confined environment.By using dynamic light scattering(DLS),we discovered a dynamical transition for charged ring polymers with increasing ring concentration in the gel matrix from a diffusive state to a non-diffusive topological frustrated state with a more compact conformation.When the ring polymer size is smaller than the mesh size of the gel matrix,the rings are diffusive at low concentration of 5 g/L.The ring diffusion coefficient in the gel matrix is an order of magnitude smaller than that of rings in solution,obeying the Ogston's model.At high ring concentration of 40 g/L,the collective dynamical behavior of the charged rings exhibits a topologically frustrated non-diffusive state,which may originate from the inter-ring threading with the external confinement from the gel matrix.Based on our previous theoretical work,we also conjectured that in such a non-diffusive state,the ring polymers might adopt a more compact conformation with the overall size exponentν=1/3.展开更多
基金supported financially by the National Key R&D Program of China(Grant No.2023YFE0111500)the National Natural Science Foundation of China(Grant Nos.52321006,T2394480,T2394484,22109143,22475196,22479131)+11 种基金the Research Grants Council of Hong Kong(CRF C4005-22YRGC Senior Research Fellowship Scheme(SRFS2223-5S01))the Joint Fund for Provincial Science and Technology R&D Program of Henan(grant no.242301420051)the Opening Project of the State Key Laboratory of Advanced Technology for Float Glass(grant no.2022KF04)the China Postdoctoral Innovative Talent Support Program(grant no.BX2021271)the China Postdoctoral Science Foundation(grant no.2022M712851)the Graduate Education Reform Project of Henan Province(Grant No.2023SJGLX136Y)the Key R&D Special Program of Henan Province(Grant No.241111242000)the Program for Science&Technology Innovation Talents in Universities of Henan Province(Grant No.25HASTIT005)the Training Plan for Young Backbone Teachers of Zhengzhou University(Grant No.2023ZDGGJS017)the Joint Research Project of Puyang ShengtongJuyuan New Materials Co.Ltd.(Grant No.20230128A)。
文摘Wide-bandgap mixed-halide perovskites,particularly CsPbIBr_(2),hold great promise for multi-junction solar cells due to their well-matched bandgap and all-inorganic material system.However,their inherent susceptibility to light-induced phase segregation(LIPS)limits efficiency and stability.In this work,we investigate the effect of three organic additives-4-cyclopentene-1,3-dione(CPD),maleimide(HPD),and 3,4-dibromo-1H-pyrrole-2,5(2H,5H)-dione(BrPD)-on LIPS in wide-bandgap CsPbIBr_(2)perovskite films.The additives form various chemical interactions,including coordination bonds,hydrogen bonds,and ionic bonds,with I^(-)and undercoordinated Pb^(2+)ions,among which BrPD has the strongest interaction.This interaction regulates crystallization and improves film morphology.The BrPD-modified films have the largest grain size and the highest light stability,suppressing LIPS,enhancing carrier transfer,and improving device performance.BrPD-modified CsPbIBr_(2)-based solar cells achieve a power conversion efficiency(PCE)of 11.34%,outperforming the control(8.96%)and other additives.Moreover,BrPDmodified devices show excellent stability,retaining 94%of their initial PCE after 60 min of continuous light exposure.This work highlights the potential of strategically selected organic additives to enhance the stability and performance of perovskite solar cells,offering valuable insights for the design of high-efficiency and long-lasting perovskite-based optoelectronic devices.
基金supported by the National Key R&D Program of China(2022YFA1505000)。
文摘Styrene epoxidation is a crucial reaction in the chemical industry.However,low Faradaic efficiency(FE)and product selectivity severely limit the efficiency of(photo)electrocatalytic styrene epoxidation processes.This study designs an efficient photothermal catalytic system based on an Au/NiCo_(2)O_(4)photoanode,which achieves the product selectivity of 98%and FE of 96%for bromide-mediated styrene epoxidation when the styrene conversion reaches 94%,surpassing most current reports on photoelectrocatalytic styrene epoxidation.A comprehensive mechanistic study reveals that the photothermal effect of the Au/NiCo_(2)O_(4)photoanode enhances local temperature,which facilitates bromine species mass transfer,reduces reaction activation energy and accelerates the oxidation kinetics of Br^(-).This study elucidates the photothermal-driven reaction mechanism of styrene epoxidation,providing guidelines for designing efficient and stable photothermal catalytic technologies.
基金supported by the National Key Research and Development Program of China(2022YFB3805600,2022YFB3805604)the National Natural Science Foundation of China(52201286)+3 种基金the National 111 Project(B20002)the Key R&D Program of Shandong Province,China(2023CXGC010314)the Hubei Provincial Natural Science Foundation of China(2024AFB195)the Fundamental Research Funds for the Central Universities(104972025KFYzxk0014,104972024KFYjlb0008)。
文摘The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.
基金supported by the National Natural Science Foundation of China(Nos.22090021,52203225).
文摘Organic ambipolar emitting materials hold immense potential for application in integrated optoelectrical devices yet challenging to design and synthesize.Cocrystals exhibit significant superiority in designing such materials because the properties of emission and transport can be flexibly tailored through the strategic pairing of donor and acceptor units.In this study,we report a new cocrystal system,DPA-5FDPA,derived from two high-mobility emissive molecules,2,6-diphenylanthracene(DPA)and 2,6-diperfluorophenyl anthracene(5FDPA).This cocrystal system exhibits outstanding emission and ambipolar semiconducting properties.Notably,the single-crystal field-effect transistor devices based on DPA-5FDPA achieve maximum hole and electron mobilities of 0.298 cm^(2) V^(-1) s^(-1) and 0.009 cm^(2) V^(-1) s^(-1),respectively.In comparison,the reference compound of 2-perfluorophenyl-6-phenylanthracene(5FBA)exhibits unipolar p-type transport with the hole mobility of 0.008 cm^(2) V^(-1) s^(-1).In addition,DPA-5FDPA exhibits excellent optical waveguide behavior with a small optical loss coefficient of 0.079 dB/µm at 508 nm,which is lower than most reported cocrystal systems.These results underscore the promise of co-crystallization as a versatile strategy for developing advanced ambipolar emissive semiconductors and provide deeper insights into the relationships among molecular structures,packing modes,intermolecular interactions,and charge-transport properties.
基金the financial support from the National Natural Science Foundation of China (Nos.U23A20677,22022610 and 52400137)"Pioneer" and "Leading Goose" R&D Program of Zhejiang (Nos.2022C03146 and 2023C03017)+2 种基金China Postdoctoral Science Foundation (No.2024T170805)Zhejiang Provincial Natural Science Foundation of China (No.LDT23E06015B06)the support of the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University for assistance with the calculations。
文摘Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.
文摘Biomarker-based sperm analysis elevates the treatment of human infertility and ameliorates reproductive performance in livestock. The negative biomarker-based approach focuses on proteins and ligands unique to defective spermatozoa, regardless of their morphological phenotype, lending itself to analysis by flow cytometry （FC）. A prime example is the spermatid specific thioredoxin SPTRX3/TXNDC8, retained in the nuclear vacuoles and superfluous cytoplasm of defective human spermatozoa. Infertile couples with high semen SPTRX3 are less likely to conceive by assisted reproductive therapies （ART） and more prone to recurrent miscarriage while low SPTRX3 has been associated with multiple ART births. Ubiquitin, a small, proteolysis-promoting covalent posttranslational protein modifier is found on the surface of defective posttesticular spermatozoa and in the damaged protein aggregates, the aggresomes of spermiogenic origin. Semen ubiquitin content correlates negatively with fertility and conventional semen parameters, and with sperm binding of lectins LCA （Lens culinaris agglutinin; reveals altered sperm surface） and PNA （Arachis hypogaealpeanut agglutinin; reveals acrosomal malformation or damage）. The Postacrosomal Sheath WWl Domain Binding Protein （PAWP）, implicated in oocyte activation during fertilization, is ectopic or absent from defective human and animal spermatozoa. Consequently, FC-parameters of PAWP correlate with ART outcomes in infertile couples and with fertility in bulls. Assays based on the above biomarkers have been combined into multiplex FC semen screening protocols, and the surface expression of lectins and ubiquitin has been utilized to develop nanoparticle-based bull semen purification method validated by field artificial insemination trials. These advances go hand-in-hand with the innovation of FC-technology and genomics/proteomics-based biomarker discovery.
基金supported by the National Natural Science Foundation of China (No.21773251 and No.91741106)the Beijing National Laboratory for Molecular Sciences and Chinese Academy of Sciences
文摘The van der Waals (vdW) interaction is very important in fields of physics, biology and chemistry, and its role in reaction dynamics is an issue of great interest. In this review, we focus on the recent progresses in the theoretical and experimental studies on the vdW interaction in bimolecular reactions. In particular, we review those studies that have advanced our understanding of how the vdW interaction can strongly influence the dynamics in both direct activated and complex-forming reactions, and further extend the discussion to the polyatomic reactions involving more atoms and those occurring at cold and ultracold temperatures. We indicate that an accurate description of the delicate vdW structure and long-range potential remains a challenge nowadays in either ab initio calculations or the fitting of the potential energy surfaces. We also present an explanation on the concept of vdW saddle proposed by us recently which may have general importance.
基金supported by the National Natural Science Foundation of China(No.21773251 and No.21973098)the Youth Innovation Promotion Association CAS(No.2018045)the Beijing National Laboratory for Molecular Sciences。
文摘Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.
基金supported by the National Natural Science Foundation of China(Grant no.51773208,51803216)the Ministry of Science and Technology of China(Grant no.2014CB643506)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDB12020200)
文摘Side chains play a critical role in tuning intermolecular interaction and charge transport in organic semiconductors. Here, we have systematically investigated the impact of branching positions of the alkyl side chains on the molecular packing and electron transport properties of a series of bay-linked dimeric perylenediimide(PDI) derivatives by atomistic molecular dynamics simulations in combination with charge transfer rate theory and kinetic Monte Carlo simulations. The results show that despite of different branching positions of the alkyl chains,π–π stacking is effectively inhibited for all the dimeric PDI derivatives. As the branching position moves away from the PDI backbone, the appearance of the alkyl atoms around the PDI backbone will first decrease and then increase. Correspondingly, the short contacts between the PDI moieties are first enhanced and then reduced. In particular, when the branching position is at the third carbon atom, the intermolecular connectivity becomes the most effective and the electron mobility is significantly increased by 2 times.
基金support from the Ministry of Science and Technology of China(No.2017YFA0204502)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB12020200)。
文摘Electronic polarization has an important impact on the site energies of charge carriers that play a key role in determining the charge transport in organic semiconductors.Dipolar molecules have strong intermolecular interactions and widespread applications in organic optoelectronics.Howeve r,compared with nonpolar organic semiconductors,electronic polarization for dipolar systems has been rarely studied.Here,taking 1,2,3,4-tetrafluoro-6,7-dimethylnaphthalene as representative,we have calculated the electronic polarization energies of dipolar organic molecular crystals by means of a polarizable forcefield method.Surprisingly,our results point to that the polarization energies for this dipolar system are similar to those of nonpolar systems.In addition,theπ-πstack contributes only about 30%~40%to the total polarization energy,thus the polarization effects along the three dimensions should be treated equally even for the one-dimensional stacking crystals.
基金supported by the U.S.National Science Foundation CHE-1500285used resources from the National Energy Research Scientific Computing Center,which is supported by the Office of Science of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231+2 种基金supported by the Ministry of Science and Technology of China(No.2017YFA0204901 and No.2016YFC0202803)the National Natural Science Foundation of China(No.21373018 and No.21573007)the Recruitment Program of Global Experts,and Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund(the second phase) under grant No.U1501501
文摘An efficient and accurate method for computing the equilibriurn reduced density matrix is presented for treating open quantum systems characterized by the systern-bath model. The method employs the rnultilayer nmlticonfiguration tirne-dependent Hartree theory for imag- inary time propagation and an importance sampling procedure for calculating the quantum mechanical trace. The method is applied to the spin-boson Harniltonian, which leads to ac- curate results in agreement with those produced by the rnulti-electronic-state path integral molecular dynamics method.
基金This project has been supported by the National Natural Science FoundationChina Special Funds for Major Slate Basic Research Project(G1999064800).
文摘The effect of chromophores to the glass transition temperature of polyimide ensemble has been investigated by means of molecular dynamics simulation in conjunction with barrier analysis. Simulated Tg results indicated a good agreement with experimental value. This study showed the MD simulation could estimate the effect of chromophores to the Tg of polyimide ensemble conveniently and an estimation approach method had a surprising deviation of Tg from experiment. At the same time, a polyimide structure with higher barrier energy was designed and validated by MD simulation.
基金the National Natural Science Foundation of China for the financial support(29725308,29633020)
文摘The densities of n-pentane, methane-n-pentane, propane-n-pentane, n-heptane-n-pentane, and n-decane-n-pentane binary mixtures were determined at 476.5K in the pressure range from 2 to 5 MPa. The partial molar volumes of the solutes in n-pentane were calculated using the density data. It was found that the partial molar volumes of methane and propane are positive, while those of n-heptane and n-decane are negative.
基金supported by the National Natural Science Foundation of China(Nos.52273220 and 22205243)。
文摘Snow and freezing disasters are recurrent weather and climate phenomena that affect the world annually.These events exert a significant influence on numerous aspects of life,including transportation,power supply,and daily activities,and result in considerable economic losses.This study aims to provide a comprehensive analysis of the regions affected by these disasters,the preventive and responsive measures employed,recent advancements in key materials,and the challenges encountered.By doing so,we can gain a deeper understanding of the vital role,significant advantages,and untapped potential of key materials for effectively preventing and responding to snow and freezing disasters.Furthermore,promoting research and utilization of these materials not only contributes to the development of the safety and emergency equipment industry but also strengthens the supply of advanced and suitable safety and emergency equipment.
基金the National Natural Science Foundation of China(Nos.22278415 and 52225309)Chinese Academy of Sciences(No.027GJHZ2022033GC).
文摘Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture.Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness.In this work,a bio-derived shellac incorporated with polydodecyl trimethoxysilane(SL-PDTMS)capsule was developed for long-term controlled releasing urea.Due to enhanced hydrophobicity and thus water resistance,the SL-PDTMS encapsulated urea fertilizer(SPEU)demonstrated a long-term effectiveness of 60 d,compared with SL encapsulated urea fertilizer(SEU,30 d)and pure urea fertilizer(U,5 min).In addition,SPEU showed a broad pH tolerance from 5.0 to 9.0,covering most various soil pH conditions.In the pot experiments,promoted growth of maize seedlings was observed after applying SPEU,rendering it promising as a high-performance controlled-released fertilizer.
基金financially supported by the CAS Project for Young Scientists in Basic Research(No.YSBR-058)the National Key R&D Program of China(No.2021YFB2500300)+1 种基金the National Natural Science Foundation of China(Nos.92372125,22205241)the National Postdoctoral Program for Innovative Talents(No.BX20220306)of the Chinese Postdoctoral Science Foundation。
文摘Zn metal batteries are highly attractive because of their high theoretical specific capacity,intrinsic safety and resource availability.However,further development is significantly hindered by low Coulomb efficiency,which is closely linked to reaction processes occurring at electrode/electrolyte interfaces.Herein,we have achieved a real-time visualization and comprehensive analysis of the interfacial evolution of Zn metal anode via in situ AFM in organic and aqueous electrolytes,respectively.The processes of uneven nucleation,dendrite growth,the Zn O formation and the dissolution of Zn substrate are directly probed in aqueous electrolyte,which induces interfacial deterioration and ultimately results in battery failure.In organic electrolyte,the in situ observations show that the homogeneous nuclei form on the Zn surface to induce the dendrite-free deposition,however,exhibiting poor Zn plating/stripping reversibility.This work delves into the dynamic evolution and electrochemical behaviors regulated by solvents,which provides in-depth understanding of structure-reactivity correlations and further interfacial engineering.
基金financially supported by the National Key R&D Program of China (No. 2021YFB2500300)the CAS Project for Young Scientists in Basic Research (No. YSBR-058)+1 种基金the National Science Foundation of China (No. 22205241)the National Postdoctoral Program for Innovative Talents (No. BX20220306) of the Chinese Postdoctoral Science Foundation。
文摘Unstable electrode/electrolyte interfaces and heterogeneous Zn deposition would reduce the Coulombic efficiency and cycle life of Zn metal batteries(ZMBs). Applying water-in-salt(WIS) electrolytes has proven to be an effective strategy to address the above issues. However, an understanding of the reaction mechanisms on the Zn anode at nanoscale is still elusive. Here we utilize in situ atomic force microscopy to visualize the solid electrolyte interphase(SEI) formation and Zn deposition/dissolution processes in WIS electrolyte and construct relationships between interfacial behavior and electrochemical performance. The formation processes, chemical properties, and structure of the on-site formed SEI are deeply explored.The SEI with a “plum-pudding” model can guide uniform Zn deposition and reversible dissolution. Mechanistic understanding of the interfacial evolution of the SEI layer and Zn deposition/dissolution has been achieved and will benefit the structural optimization and interfacial engineering of ZMBs.
基金the National Natural Science Foundation of China(Nos.21831008,22025109,22101286)CAS Project for Young Scientists in Basic Research(No.YSBR-050)+1 种基金Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-201901)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(No.KF2102)are gratefully acknowledged.
文摘An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis.It is the first time that allene was introduced into transition metal and NHC synergetic catalysis,which demonstrated a versatile three-component reaction pattern,thus enabling two C-C bonds forged regioselectively in the reaction.The important reaction intermediates were successfully captured and characterized by HRMS analysis,and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
基金supported by the National Natural Science Foundation of China(No.22273114)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0770101)+1 种基金the National Key R&D Program of China(No.2023YFE0124500),the National Key R&D Program of China(No.2023YFC2411203)International Partnership Program of the Chinese Academy of Sciences(No.027GJHZ2022061FN)。
文摘Ring polymers are ubiquitous in various fields including biomaterials,drug release and gene therapy.All of these applications involve the dynamics and diffusion process of ring polymers in a confined environment.By using dynamic light scattering(DLS),we discovered a dynamical transition for charged ring polymers with increasing ring concentration in the gel matrix from a diffusive state to a non-diffusive topological frustrated state with a more compact conformation.When the ring polymer size is smaller than the mesh size of the gel matrix,the rings are diffusive at low concentration of 5 g/L.The ring diffusion coefficient in the gel matrix is an order of magnitude smaller than that of rings in solution,obeying the Ogston's model.At high ring concentration of 40 g/L,the collective dynamical behavior of the charged rings exhibits a topologically frustrated non-diffusive state,which may originate from the inter-ring threading with the external confinement from the gel matrix.Based on our previous theoretical work,we also conjectured that in such a non-diffusive state,the ring polymers might adopt a more compact conformation with the overall size exponentν=1/3.
