The emergence of precision electronic devices and wearable electronic products urgently requires high-performance multifunctional electromagnetic wave(EMW)absorbers to meet the applicability and versatility in various...The emergence of precision electronic devices and wearable electronic products urgently requires high-performance multifunctional electromagnetic wave(EMW)absorbers to meet the applicability and versatility in various applications.Herein,a dual-network(DN)gel was successfully prepared using acrylamide and sodium lignosulphonate as the basic units by simple chemical cross-linking and physical cross-linking methods.Specifically,the hydrogel forms two types of cross-linking networks through metal coordination and hydrogen bonding.Benefiting from the combined effects of dipole polarization and conductivity loss,the gel achieves an effective absorption bandwidth(EAB)of 6.74 GHz at a thickness of only 1.89 mm,demonstrating excellent EMW absorption performance.In addition,this unique structural configuration endows the EMW absorber with multifunctional features,such as remarkable tensile strength,good environmental compatibility,ultraviolet(UV)resistance,and excellent adhesion.Integrating multiple functional features into the EMW gels displays a broad application prospect in a variety of application scenarios.This research reveals the significance of DN structure design in the electromagnetic wave absorption(EWA)performance of gel-based materials,providing a substantial foundation for the multifunctional design of gel-based absorbers.展开更多
Spiropyrans(SPs) are a well-known class of photochromic compounds and have found widespread application due to their unique properties. However, for many conventional SPs, high energy ultraviolet(UV)light is commonly ...Spiropyrans(SPs) are a well-known class of photochromic compounds and have found widespread application due to their unique properties. However, for many conventional SPs, high energy ultraviolet(UV)light is commonly essential to drive photoisomerization, leading to poor fatigue resistance. Moreover, the practical application of spiropyrans is hindered by their fast fading speed due to the instability of closed forms(SP) or open forms(MC). Herein, we disclose a novel strategy to address these challenges through introducing both electron-donating substituents to stabilize the SP and dynamic coordination bonds to stabilize the MC. The resulting new spiropyrans complexes exhibit negative photochromic properties, with fast visible light response, good stability of both SP and MC, and significantly improved fatigue resistance.展开更多
Inspired by natural photosynthesis,fabricating high-performance S-scheme heterojunction is regarded as a successful tactic to address energy and environmental issues.Herein,NH_(2)-MIL-125(Ti)/Zn_(0.5)Cd_(0.5)S/NiS(NMT...Inspired by natural photosynthesis,fabricating high-performance S-scheme heterojunction is regarded as a successful tactic to address energy and environmental issues.Herein,NH_(2)-MIL-125(Ti)/Zn_(0.5)Cd_(0.5)S/NiS(NMT/ZCS/NiS)S-scheme heterojunction with interfacial coordination bonds is successfully synthesized through in-situ solvothermal strategy.Notably,the optimal NMT/ZCS/NiS S-scheme heterojunction exhibits comparable photocatalytic H_(2)evolution(PHE)rate of about 14876.7μmol h^(−1)g^(−1)with apparent quantum yield of 24.2%at 420 nm,which is significantly higher than that of recently reported MOFs-based photocatalysts.The interfacial coordination bonds(Zn–N,Cd–N,and Ni–N bonds)accelerate the separation and transfer of photogenerated charges,and the NiS as cocatalyst can provide more catalytically active sites,which synergistically improve the photocatalytic performance.Moreover,theoretical calculation results display that the construction of NMT/ZCS/NiS S-scheme heterojunction also optimize the binding energy of active site-adsorbed hydrogen atoms to enable fast adsorption and desorption.Photoassisted Kelvin probe force microscopy,in-situ irradiation X-ray photoelectron spectroscopy,femtosecond transient absorption spectroscopy,and theoretical calculations provide sufficient evidence of the S-scheme charge migration mechanism.This work offers unique viewpoints for simultaneously accelerating the charge dynamics and optimizing the binding strength between the active sites and hydrogen adsorbates over S-scheme heterojunction.展开更多
The fundamental issues associated with Zn anodes prevent the commercialization of aqueous Zn ion batteries.To address this,a simple dip-coating method was used to coordinate a thin layer of branched polyethyleneimine(...The fundamental issues associated with Zn anodes prevent the commercialization of aqueous Zn ion batteries.To address this,a simple dip-coating method was used to coordinate a thin layer of branched polyethyleneimine(b-PEI)polymer onto the electrode surface.This process increases hydrophilicity and reduces interfacial resistance between the electrode and aqueous electrolyte.Consequently,electrolyte leaching from the hydrophilic polymer coating layer is prevented,charge distribution is uniform,and stable electrochemical performance is maintained over extended periods.In symmetric cell testing,the b-PEI@Zn anode exhibits a lifespan of over 1400 h(3 mA cm^(-2),1 mAh cm^(-2)).Furthermore,full-cell tests,the b-PEI@Zn anode demonstrates higher capacity(+26.05%)and improved stability(95.4%)compared to the bare Zn anode(0.5 A g−1).This study presents a practical surface modification strategy for Zn anodes and underscores the potential of innovative polymer-based electrode coatings for aqueous battery applications.展开更多
Fluorinated fused azobenzene boron(FBAz)is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells(all-PSC).The B←N bridging units impart a fixed configuration and low-lyin...Fluorinated fused azobenzene boron(FBAz)is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells(all-PSC).The B←N bridging units impart a fixed configuration and low-lying LUMO/HOMO energy.Three polymer acceptor materials(P2f,P3f and P5f)with different fluorine substitution positions by copolymerizing FBAz with indacenodithiophene(IDT),are synthesized and investigated to study the influence of fluorinated forms on the all-polymer solar cell performance.The FBAz units are synthesized in just three steps,facilitating the straightforward production of polymer acceptors P2f,P3f,and P5f.These acceptors exhibit strong light absorption in the visible to near-infrared range of 500-1000nm and possess suitable LUMO/HOMO energy levels of-3.99/-5.66 eV which are very complementary to that(E_(LUMO/HOMO)=-3.59/-5.20 eV)of the widely-used polymer donor poly[(ethylhexylthiophenyl)-benzodithiophene-(ethylhexyl)-thienothiophene](PTB7-Th).All-polymer solar cells(all-PSCs)with PTB7-Th as electron donor and P3f as electron acceptor exhibits highest power conversion efficiencies(PCE)2.70%.When PC_(61)BM is added as the third component,the device efficiency can reach 5.36%.These preliminary results indicate that FBAz is a promising strong electron acceptor for the development of n-type polymer semiconductors,especially in organic photovoltaics(OPVs).To the best of our knowledge,this is the first example demonstrating the unique photovoltaic properties of the N=N double bond as an acceptor material.展开更多
Due to the special viscoelastic property, traditional rubber with high performance has been widely used in human life and production. However, it is challenging to improve the damping property without sacrificing the ...Due to the special viscoelastic property, traditional rubber with high performance has been widely used in human life and production. However, it is challenging to improve the damping property without sacrificing the extensibility. In this work, a novel type of second-generation polyurethane dendrimer terminated with pyridine(G2-Py) was synthesized by using thiolactone chemistry and subsequently complexed with Zn ions. The structure and morphology of G2-Py were characterized. G2-Py-Zn2+was then mixed with chlorinated butyl rubber(CIIR) by a two-roll mill. A series of CIIR/G2-Py-Zn2+elastomers were obtained through vulcanization. CIIR/G2-Py-Zn2+elastomers could achieve high stretchability(a strain of ~1035%), high mechanical strength(a tensile stress of 7.64 MPa). This was benefitted from the friction between G2-Py and CIIR as well as variety of non-covalent bonds provided by G2-Py-Zn2+,which can dissipate energy to further improve the strength and extensibility. The coordination of Zn2+-pyridine was confirmed by Fourier transform infrared spectroscopy, stress relaxation and cycle tensile test. To further investigate the morphology and damping properties of the elastomers, scanning electron microscopy and dynamic mechanical analysis were performed. CIIR-5 showed the best damping performance with higher tan δ_(max) and wider effective damping temperatures. Therefore, this dendrimer modification technology provides wider applications for CIIR elastomers in daily life.展开更多
Synthesized struvite was innovatively applied to removing Cu（II） from aqueous solution. The Cu（II） adsorption behavior and relative mechanisms were studied and analyzed. The maximum Cu（II） adsorption under pH=4....Synthesized struvite was innovatively applied to removing Cu（II） from aqueous solution. The Cu（II） adsorption behavior and relative mechanisms were studied and analyzed. The maximum Cu（II） adsorption under pH=4.0 and 318 K calculated from adsorption thermodynamic analysis was 145.1 mg/g. The sorption kinetics can be favorably described by pseudo-second order model. The activation energy （Ea） of 17.5 kJ/mol suggested that the adsorption process was a chemical adsorption. The calculated thermodynamic parameters indicated that the adsorption was a spontaneous and endothermic one. On the basis of characterization upon struvite before and after adsorption, it was found that the electrostatic attraction and coordination bonding supported the ion sorption on struvite surface, and the transformation of copper ion into copper hydroxide occurred on struvite surface and within its crevices.展开更多
B-N coordination bond can be used to develop polymer electron acceptors for efficient all-polymer solar cells （all-PSCs）. Here, we report a new alternating conjugated polymer containing two building blocks based on ...B-N coordination bond can be used to develop polymer electron acceptors for efficient all-polymer solar cells （all-PSCs）. Here, we report a new alternating conjugated polymer containing two building blocks based on B-N unit. The polymer exhibits strong light absorption in the visible range, low-lying LUMO/HOMO energy levels and moderate electron mobility. The resulting all-PSC devices exhibit power conversion efficiencies of 1.50%-2.47%.展开更多
Polymer electron acceptors for all-polymer solar cells （all-PSCs） are usually conjugated copolymers, which contain alternating electron-rich units and electron-deficient units. In this manuscript, we report a conjug...Polymer electron acceptors for all-polymer solar cells （all-PSCs） are usually conjugated copolymers, which contain alternating electron-rich units and electron-deficient units. In this manuscript, we report a conjugated homopolymer （P-BNBP） based on an electron-deficient unit of double B,--N bridged bipyridine, which can be used as electron acceptor for all-polymer solar cells. P-BNBP shows low-lying LUMO energy level of -3.59eV, high absorption coefficient of 1.6 ×10^5Lmo1^-1 cm^-1 at 626nm and moderate electron mobility of 4.37 ×10^-6cm^2V^-1s^-1. AII-PSC devices exhibit power conversion efficiencies of 2.44%-3.04%. These results demonstrate that conjugated homopolymers are promising as electron acceptor materials for alI-PSCs.展开更多
The chemical bonding nature of rare earth（RE） elements can be studied by a quantitative analysis of electron domain of an atom. The outer electrons of RE elements are within the valence shell 4f^（0-14）5d^（0-1）6s...The chemical bonding nature of rare earth（RE） elements can be studied by a quantitative analysis of electron domain of an atom. The outer electrons of RE elements are within the valence shell 4f^（0-14）5d^（0-1）6s^2, which are involved in all chemical bonding features. We in this work found that the chemical bonding characteristics of 4f electrons are a kind of hybridizations, and classified them into three types of chemical bonding of 4f^（0-14）5d^（0-1）6s^2, furthermore, the coordination number ranging from 2 to 16 could thus be determined. We selected Y（NO_3）_3, La（NO_3）_3, Ce（NO_3）_3, YCl_3, LaCl_3, and CeCl_3 as examples to in-situ observe their IR spectra of chemical bonding behaviors of Y^（3＋）, La^（3＋） and Ce^（3＋） cations, which could show different chemical bonding modes of 4f and 5d electrons. In the present study, we obtained the direct criterion to confirm whether 4f electrons can participate in chemical bonding, that is, only when the coordination number of RE cations is larger than 9.展开更多
The unique interactions between hexadecanoic acid(HA)and albumin(ALB)molecules on the surface of the porous layer of AZ31 Mg alloy were exploited to fabricate a novel hybrid composite film with excellent electrochemic...The unique interactions between hexadecanoic acid(HA)and albumin(ALB)molecules on the surface of the porous layer of AZ31 Mg alloy were exploited to fabricate a novel hybrid composite film with excellent electrochemical stability in a 3.5 wt.%Na Cl solution.Herein,the inorganic layer(IL)obtained by plasma electrolytic oxidation of AZ31 Mg alloy in an alkaline-phosphate-WO_(3)electrolyte was soaked in an organic solution composed of ALB and HA for 10 and 24 h at 60℃.Although albumin and HA may coexist on the same surface of IL,the higher reactivity of ALB molecules would prevent the formation of a thick layer of HA.The donor-acceptor complexes formed due to the unique interactions between ALB and/or HA and IL surface would reduce the area exposed to the corrosive species which in turn would efficiently protect the substrate from corrosion.The porous structure of the IL would provide preferable sites for the physical and chemical locking triggered by charge-transfer phenomena,leading to the inhomogeneous nucleation and crystal growth of a flowery flakes-like organic layer.DFT calculations were performed to reveal the primary bonding modes between the ALB,HA,and IL and to assess the mechanistic insights into the formation of such novel hybrid composites.展开更多
Cardanol-aldehyde condensation polymer containing boron-nitrogen coordinate bond (CFBN) has been synthesized and characterized by IR, XPS, HPLC and DTA-TG. Its properties were also investigated. The results show tha...Cardanol-aldehyde condensation polymer containing boron-nitrogen coordinate bond (CFBN) has been synthesized and characterized by IR, XPS, HPLC and DTA-TG. Its properties were also investigated. The results show that the coating film of CFBN has excellent physico-mechanical properties, good anticorrosive properties and stable at high temperature. (Author abstract) 8 Refs.展开更多
Two novel coordination polymers with molecular structures（2MI）＋[Zn（2MI）Cl3]-（1） and（2MI）＋NO3-（2） based on ligand 2-methylimidazole（2MI） were synthesized under solution method. Compound 1 crystallizes in ...Two novel coordination polymers with molecular structures（2MI）＋[Zn（2MI）Cl3]-（1） and（2MI）＋NO3-（2） based on ligand 2-methylimidazole（2MI） were synthesized under solution method. Compound 1 crystallizes in the monoclinic system, space group Cc with a=7.489（2）, b=13.448（4）, c=13.983（4） , β=98.402（2）°, Z=4 and V=102.246（2） 3. Compound 2 crystallizes in the orthorhombic system, space group pnma with a=14.296（3）, b=6.3180（12）, c=7.3862（13） , β=90°, Z=4 and V=667.1（2） 3. Dielectric measurements show compounds 1 and 2 have reversible dielectric anomalous behaviors with variation frequencies at different temperature.展开更多
For organnoboron co mpounds,the substituents on boron atoms are very important because they not only impact on the molecular stability but also significantly modulate the electronic structu res and prope rties.In this...For organnoboron co mpounds,the substituents on boron atoms are very important because they not only impact on the molecular stability but also significantly modulate the electronic structu res and prope rties.In this manuscript,we synthesized two new B←N-co ntaining azaacenes with propynyl groups on boron atoms through one-step Grignard reaction.Replacing fluorine atoms by propynyl groups greatly impacts on the electronic energy levels,especially enhancing the HOMO levels,thus leading to the narrowed HOMO-LUMO bandgaps.These B←N-containing azaacenes exhibit the NIR light-absorption(λabs=706 nm for 2 a and 762 nm for 2 b)and fluorescence properties(λem=740 nm for 2 a and802 nm for 2 b),as well as multiple reversible redox behaviors,which are significantly different from the analogs with fluorine atoms.This study thus provides a functional substituent of boron atom,which may lead to new organoboron materials with fascinating properties.展开更多
The development of new polymer acceptors strongly paves the power conversion efficiency(PCE)improvement of all polymer solar cells(all-PSCs).Herein,we develop a new polymer acceptor PBN26,which is the alternating copo...The development of new polymer acceptors strongly paves the power conversion efficiency(PCE)improvement of all polymer solar cells(all-PSCs).Herein,we develop a new polymer acceptor PBN26,which is the alternating copolymer of 2,2′-((2Z,2′Z)-((12,13-bis(2-octyldodecyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1 H-indene-2,1-diylidene))dimalononitrile and B←N bridged thienylthiazole(BNTT).The optimized all-PSCs device based on PBN26 exhibits a PCE of 15.09%,which is the highest value of the all-PSCs based on B←N-based polymer acceptors at present.Moreover,we also fabricate an all-PSC module with active area of 10 cm2 by blade coating,which exhibits a PCE of 8.78%.These results prove that polymer acceptors containing B←N units are promising for all-PSC device applications.展开更多
Aiming to reduce the defects of perovskite film and improve carrier transport,an organic small molecule,benzo[d]isothiazol-3(2H)-one 1,1-dioxide(OBS),is introduced as an additive in the solution-processing of perovski...Aiming to reduce the defects of perovskite film and improve carrier transport,an organic small molecule,benzo[d]isothiazol-3(2H)-one 1,1-dioxide(OBS),is introduced as an additive in the solution-processing of perovskite and prepare uniform perovskite films with a continuous distribution of OBS at grain boundaries.Fourier trans-form infrared spectroscopy and X-ray photoelectron spectroscopy are conducted to reveal the interactions of hydrogen bonding and coordina tion bonding between OBS and perovskite.Various characterizations(including X-ray diffraction,UV-vis spectroscopy,electrochemical impedance spectroscopy,etc.)are conducted to uncover the effect of OBS on device performance.Consequently,high efficiency of 23.26%is obtained for the OBS-treated device,while the control device shows only a companion efficiency of 21.60%.展开更多
Urushiol polymer containing B-N bond (PUBN) was synthesized with urushiol-boron polymer and diethylene triamine. Its structure was characterized by XPS, IR, UV, HPLC, DTA-TG and elemental analysis. The physico-mechani...Urushiol polymer containing B-N bond (PUBN) was synthesized with urushiol-boron polymer and diethylene triamine. Its structure was characterized by XPS, IR, UV, HPLC, DTA-TG and elemental analysis. The physico-mechanical and anticorrosive properties of the polymer were also investigated. The results show that the coating of PUBN can be hardened in 2 h at room temperature and its film has excellent physico-mechanical properties and good anticorrosive properties.展开更多
In this study,the hydrogel network was reinforced by covalent-like hydrogen bonding,and the strong binding ability of boron-nitrogen coordination served as the main driving force.Among them,acrylamide(AM)and 3-acrylam...In this study,the hydrogel network was reinforced by covalent-like hydrogen bonding,and the strong binding ability of boron-nitrogen coordination served as the main driving force.Among them,acrylamide(AM)and 3-acrylamidophenylboronic acid(AAPBA)were the main body,and the numerous hydroxyl groups in the trehalose(Treh)molecule and other polymer groups formed strong hydrogen bonding interactions to improve the mechanical properties of the PAM/PAAPBA/Treh(PAAT)hydrogel and ensured the simplicity of the synthesis process.The hydrogel possessed high strain at break(1239%),stress(64.7 kPa),low hysteresis(100%to 500%strain,corresponding to dissipation energy from 1.37 to 7.80 kJ/m^(3)),and outstanding cycling stability(retained more than 90%of maximum stress after 200 ten-sile cycles).By integrating carbon nanotubes(CNTs)into PAAT hydrogel(PAATC),the PAATC hydrogel with excellent strain response performance was successfully constructed.The PAATC conductive hydro-gel exhibited high sensitivity(gauge factor(GF)=10.58 and sensitivity(S)=0.304 kPa^(-1)),wide strain response range(0.5%-1000%),fast response time(450 ms),and short recovery time(350 ms),excellent fatigue resistance,and strain response stability.Furthermore,the PAATC-based triboelectric nanogener-ator(TENG)displayed outstanding energy harvesting performance,which shows its potential for appli-cation in self-powered electronic devices.展开更多
Photoelectron velocity map images of Cu(CO)_(3)^(-)have been experimentally recorded in the 700-1100 nm range.The infrared-inactive Cu^(-)C symmetric stretching modes for Cu(CO)_(3)(v_(2)≈367 cm^(-1))and Cu(CO)_(3)^(...Photoelectron velocity map images of Cu(CO)_(3)^(-)have been experimentally recorded in the 700-1100 nm range.The infrared-inactive Cu^(-)C symmetric stretching modes for Cu(CO)_(3)(v_(2)≈367 cm^(-1))and Cu(CO)_(3)^(-)(v_(2)≈408 cm^(-1)),as well as the electron affinity(1.03±0.11 eV)of Cu(CO)_(3),are accurately determined from high resolution photoelectron spectra.In combination with quantum chemical calculations and bonding analyses,the coordination bonds in both Cu(CO)_(3)^(-)are Cu(CO)_(3)are found to be due to back-donationπbonding type,formed via electron promotion from Cu’s 4s orbital to the 4p orbital,which is consequently donated to the unoccupied anti-bondingπ*orbitals of the carbonyl groups.The attachment of an additional electron to Cu(CO)_(3)strengthens the Cu^(-)CO coordination,making Cu(CO)_(3)^(-)more stable.The intramolecular interactions between the Cu/Cu^(-)and carbonyl groups are found to be primarily governed by electrostatic forces and orbital interactions.展开更多
Aromatic bond including metallic atom (Ni) is investigated by EHMO calculation.The NMR spectra and the mechanism for hydrolysis are discussed on the ground of results of computation.
基金supported by the National Natural Science Foundation of China(Nos.52231007,51872238,52074227,and 21806129)the Fundamental Research Funds for the Central Universities(Nos.3102018zy045,3102019AX11,and 5000220455)the Natural Science Basic Research Plan in Shaanxi Province of China(Nos.2017JQ5116 and 2020JM-118).
文摘The emergence of precision electronic devices and wearable electronic products urgently requires high-performance multifunctional electromagnetic wave(EMW)absorbers to meet the applicability and versatility in various applications.Herein,a dual-network(DN)gel was successfully prepared using acrylamide and sodium lignosulphonate as the basic units by simple chemical cross-linking and physical cross-linking methods.Specifically,the hydrogel forms two types of cross-linking networks through metal coordination and hydrogen bonding.Benefiting from the combined effects of dipole polarization and conductivity loss,the gel achieves an effective absorption bandwidth(EAB)of 6.74 GHz at a thickness of only 1.89 mm,demonstrating excellent EMW absorption performance.In addition,this unique structural configuration endows the EMW absorber with multifunctional features,such as remarkable tensile strength,good environmental compatibility,ultraviolet(UV)resistance,and excellent adhesion.Integrating multiple functional features into the EMW gels displays a broad application prospect in a variety of application scenarios.This research reveals the significance of DN structure design in the electromagnetic wave absorption(EWA)performance of gel-based materials,providing a substantial foundation for the multifunctional design of gel-based absorbers.
基金supported by the National Natural Science Foundation of China (Nos. 21631006 and 21771100)。
文摘Spiropyrans(SPs) are a well-known class of photochromic compounds and have found widespread application due to their unique properties. However, for many conventional SPs, high energy ultraviolet(UV)light is commonly essential to drive photoisomerization, leading to poor fatigue resistance. Moreover, the practical application of spiropyrans is hindered by their fast fading speed due to the instability of closed forms(SP) or open forms(MC). Herein, we disclose a novel strategy to address these challenges through introducing both electron-donating substituents to stabilize the SP and dynamic coordination bonds to stabilize the MC. The resulting new spiropyrans complexes exhibit negative photochromic properties, with fast visible light response, good stability of both SP and MC, and significantly improved fatigue resistance.
文摘Inspired by natural photosynthesis,fabricating high-performance S-scheme heterojunction is regarded as a successful tactic to address energy and environmental issues.Herein,NH_(2)-MIL-125(Ti)/Zn_(0.5)Cd_(0.5)S/NiS(NMT/ZCS/NiS)S-scheme heterojunction with interfacial coordination bonds is successfully synthesized through in-situ solvothermal strategy.Notably,the optimal NMT/ZCS/NiS S-scheme heterojunction exhibits comparable photocatalytic H_(2)evolution(PHE)rate of about 14876.7μmol h^(−1)g^(−1)with apparent quantum yield of 24.2%at 420 nm,which is significantly higher than that of recently reported MOFs-based photocatalysts.The interfacial coordination bonds(Zn–N,Cd–N,and Ni–N bonds)accelerate the separation and transfer of photogenerated charges,and the NiS as cocatalyst can provide more catalytically active sites,which synergistically improve the photocatalytic performance.Moreover,theoretical calculation results display that the construction of NMT/ZCS/NiS S-scheme heterojunction also optimize the binding energy of active site-adsorbed hydrogen atoms to enable fast adsorption and desorption.Photoassisted Kelvin probe force microscopy,in-situ irradiation X-ray photoelectron spectroscopy,femtosecond transient absorption spectroscopy,and theoretical calculations provide sufficient evidence of the S-scheme charge migration mechanism.This work offers unique viewpoints for simultaneously accelerating the charge dynamics and optimizing the binding strength between the active sites and hydrogen adsorbates over S-scheme heterojunction.
基金supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(RS-2024-00446825)supported by the Ministry of Trade,Industry and Energy(MOTIE)and the Korea Institute for Advancement of Technology(KIAT)through the International Cooperative R&D program(Project No.P0027664).
文摘The fundamental issues associated with Zn anodes prevent the commercialization of aqueous Zn ion batteries.To address this,a simple dip-coating method was used to coordinate a thin layer of branched polyethyleneimine(b-PEI)polymer onto the electrode surface.This process increases hydrophilicity and reduces interfacial resistance between the electrode and aqueous electrolyte.Consequently,electrolyte leaching from the hydrophilic polymer coating layer is prevented,charge distribution is uniform,and stable electrochemical performance is maintained over extended periods.In symmetric cell testing,the b-PEI@Zn anode exhibits a lifespan of over 1400 h(3 mA cm^(-2),1 mAh cm^(-2)).Furthermore,full-cell tests,the b-PEI@Zn anode demonstrates higher capacity(+26.05%)and improved stability(95.4%)compared to the bare Zn anode(0.5 A g−1).This study presents a practical surface modification strategy for Zn anodes and underscores the potential of innovative polymer-based electrode coatings for aqueous battery applications.
基金supported by the National Natural Science Foundation of China(No.22375123)the Shuguang Program of Shanghai Education Development Foundation,the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2022SXTD012)。
文摘Fluorinated fused azobenzene boron(FBAz)is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells(all-PSC).The B←N bridging units impart a fixed configuration and low-lying LUMO/HOMO energy.Three polymer acceptor materials(P2f,P3f and P5f)with different fluorine substitution positions by copolymerizing FBAz with indacenodithiophene(IDT),are synthesized and investigated to study the influence of fluorinated forms on the all-polymer solar cell performance.The FBAz units are synthesized in just three steps,facilitating the straightforward production of polymer acceptors P2f,P3f,and P5f.These acceptors exhibit strong light absorption in the visible to near-infrared range of 500-1000nm and possess suitable LUMO/HOMO energy levels of-3.99/-5.66 eV which are very complementary to that(E_(LUMO/HOMO)=-3.59/-5.20 eV)of the widely-used polymer donor poly[(ethylhexylthiophenyl)-benzodithiophene-(ethylhexyl)-thienothiophene](PTB7-Th).All-polymer solar cells(all-PSCs)with PTB7-Th as electron donor and P3f as electron acceptor exhibits highest power conversion efficiencies(PCE)2.70%.When PC_(61)BM is added as the third component,the device efficiency can reach 5.36%.These preliminary results indicate that FBAz is a promising strong electron acceptor for the development of n-type polymer semiconductors,especially in organic photovoltaics(OPVs).To the best of our knowledge,this is the first example demonstrating the unique photovoltaic properties of the N=N double bond as an acceptor material.
基金supported by the National Natural Science Fundation of China((51873103)Capacity Building Project of Some Local Colleges and Universities in Shanghai(17030501200)+1 种基金Talent Program of Shanghai University of Engineering Science(2017RC422017)Postgraduate Research and Innovation Project of Shanghai University of Engineering Science(0234-E3-0903-19-01367).
文摘Due to the special viscoelastic property, traditional rubber with high performance has been widely used in human life and production. However, it is challenging to improve the damping property without sacrificing the extensibility. In this work, a novel type of second-generation polyurethane dendrimer terminated with pyridine(G2-Py) was synthesized by using thiolactone chemistry and subsequently complexed with Zn ions. The structure and morphology of G2-Py were characterized. G2-Py-Zn2+was then mixed with chlorinated butyl rubber(CIIR) by a two-roll mill. A series of CIIR/G2-Py-Zn2+elastomers were obtained through vulcanization. CIIR/G2-Py-Zn2+elastomers could achieve high stretchability(a strain of ~1035%), high mechanical strength(a tensile stress of 7.64 MPa). This was benefitted from the friction between G2-Py and CIIR as well as variety of non-covalent bonds provided by G2-Py-Zn2+,which can dissipate energy to further improve the strength and extensibility. The coordination of Zn2+-pyridine was confirmed by Fourier transform infrared spectroscopy, stress relaxation and cycle tensile test. To further investigate the morphology and damping properties of the elastomers, scanning electron microscopy and dynamic mechanical analysis were performed. CIIR-5 showed the best damping performance with higher tan δ_(max) and wider effective damping temperatures. Therefore, this dendrimer modification technology provides wider applications for CIIR elastomers in daily life.
基金Project(51674305)supported by the National Natural Science Foundation of ChinaProject(2013WK2007)supported by the Key Project of Science and Technology of Hunan Province,ChinaProject(2015CX001)supported by the Innovation Stimulating Program of Central South University,China
文摘Synthesized struvite was innovatively applied to removing Cu（II） from aqueous solution. The Cu（II） adsorption behavior and relative mechanisms were studied and analyzed. The maximum Cu（II） adsorption under pH=4.0 and 318 K calculated from adsorption thermodynamic analysis was 145.1 mg/g. The sorption kinetics can be favorably described by pseudo-second order model. The activation energy （Ea） of 17.5 kJ/mol suggested that the adsorption process was a chemical adsorption. The calculated thermodynamic parameters indicated that the adsorption was a spontaneous and endothermic one. On the basis of characterization upon struvite before and after adsorption, it was found that the electrostatic attraction and coordination bonding supported the ion sorption on struvite surface, and the transformation of copper ion into copper hydroxide occurred on struvite surface and within its crevices.
基金financially supported by the 973 Program(No.2014CB643504)the National Natural Science Foundation of China(Nos.51373165,21574129 and 21404099)+1 种基金the“Thousand Talents Program”of China,the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB12010200)the State Key Laboratory of Supramolecular Structure and Materials in Jilin University(No.sklssm201608)
文摘B-N coordination bond can be used to develop polymer electron acceptors for efficient all-polymer solar cells （all-PSCs）. Here, we report a new alternating conjugated polymer containing two building blocks based on B-N unit. The polymer exhibits strong light absorption in the visible range, low-lying LUMO/HOMO energy levels and moderate electron mobility. The resulting all-PSC devices exhibit power conversion efficiencies of 1.50%-2.47%.
基金supported by the National Natural Science Foundation of China (Nos.21625403,21574129)Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB12010200)+2 种基金Jilin Scientific and Technological Development Program (No.20170519003JH)Youth Innovation Promotion Association of Chinese Academy of Sciences (No.2017265)Open Project (No.sklssm201803) of the State Key Laboratory of Supramolecular Structure and Materials in Jilin University of China
文摘Polymer electron acceptors for all-polymer solar cells （all-PSCs） are usually conjugated copolymers, which contain alternating electron-rich units and electron-deficient units. In this manuscript, we report a conjugated homopolymer （P-BNBP） based on an electron-deficient unit of double B,--N bridged bipyridine, which can be used as electron acceptor for all-polymer solar cells. P-BNBP shows low-lying LUMO energy level of -3.59eV, high absorption coefficient of 1.6 ×10^5Lmo1^-1 cm^-1 at 626nm and moderate electron mobility of 4.37 ×10^-6cm^2V^-1s^-1. AII-PSC devices exhibit power conversion efficiencies of 2.44%-3.04%. These results demonstrate that conjugated homopolymers are promising as electron acceptor materials for alI-PSCs.
基金supported by the National Natural Science Foundation of China(51125009,91434118,21401185,21521092)Hundred Talents Program of Chinese Academy of SciencesJilin Province Science and Technology Development Project(20170101092JC,20160520006JH)
文摘The chemical bonding nature of rare earth（RE） elements can be studied by a quantitative analysis of electron domain of an atom. The outer electrons of RE elements are within the valence shell 4f^（0-14）5d^（0-1）6s^2, which are involved in all chemical bonding features. We in this work found that the chemical bonding characteristics of 4f electrons are a kind of hybridizations, and classified them into three types of chemical bonding of 4f^（0-14）5d^（0-1）6s^2, furthermore, the coordination number ranging from 2 to 16 could thus be determined. We selected Y（NO_3）_3, La（NO_3）_3, Ce（NO_3）_3, YCl_3, LaCl_3, and CeCl_3 as examples to in-situ observe their IR spectra of chemical bonding behaviors of Y^（3＋）, La^（3＋） and Ce^（3＋） cations, which could show different chemical bonding modes of 4f and 5d electrons. In the present study, we obtained the direct criterion to confirm whether 4f electrons can participate in chemical bonding, that is, only when the coordination number of RE cations is larger than 9.
基金the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.NRF-2019R1G1A1099335)supported also by the Mid-Level Researcher National Project of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea(NRF-2020R1A2C2004192)supported partly by Basic Research Program through the National Research Foundation,Republic of Korea(NRF-2019R1FA1062702)。
文摘The unique interactions between hexadecanoic acid(HA)and albumin(ALB)molecules on the surface of the porous layer of AZ31 Mg alloy were exploited to fabricate a novel hybrid composite film with excellent electrochemical stability in a 3.5 wt.%Na Cl solution.Herein,the inorganic layer(IL)obtained by plasma electrolytic oxidation of AZ31 Mg alloy in an alkaline-phosphate-WO_(3)electrolyte was soaked in an organic solution composed of ALB and HA for 10 and 24 h at 60℃.Although albumin and HA may coexist on the same surface of IL,the higher reactivity of ALB molecules would prevent the formation of a thick layer of HA.The donor-acceptor complexes formed due to the unique interactions between ALB and/or HA and IL surface would reduce the area exposed to the corrosive species which in turn would efficiently protect the substrate from corrosion.The porous structure of the IL would provide preferable sites for the physical and chemical locking triggered by charge-transfer phenomena,leading to the inhomogeneous nucleation and crystal growth of a flowery flakes-like organic layer.DFT calculations were performed to reveal the primary bonding modes between the ALB,HA,and IL and to assess the mechanistic insights into the formation of such novel hybrid composites.
基金This work is supported by the National Science Foundation of China.
文摘Cardanol-aldehyde condensation polymer containing boron-nitrogen coordinate bond (CFBN) has been synthesized and characterized by IR, XPS, HPLC and DTA-TG. Its properties were also investigated. The results show that the coating film of CFBN has excellent physico-mechanical properties, good anticorrosive properties and stable at high temperature. (Author abstract) 8 Refs.
基金Supported by the National Natural Science Foundation of China(No.21201087 and 21671084)NSF of Jiangsu Province(BK20131244 and BK20130460)+1 种基金the Foundation of Jiangsu Educational Committee(16KJB430011)the Qing Lan Project of Jiangsu Province and Jiangsu Overseas Research&Training Program for University Prominent Young&Middle-aged Teacher and Presidents,Six talent peaks project in Jiangsu Province(2014-XCL-008)
文摘Two novel coordination polymers with molecular structures（2MI）＋[Zn（2MI）Cl3]-（1） and（2MI）＋NO3-（2） based on ligand 2-methylimidazole（2MI） were synthesized under solution method. Compound 1 crystallizes in the monoclinic system, space group Cc with a=7.489（2）, b=13.448（4）, c=13.983（4） , β=98.402（2）°, Z=4 and V=102.246（2） 3. Compound 2 crystallizes in the orthorhombic system, space group pnma with a=14.296（3）, b=6.3180（12）, c=7.3862（13） , β=90°, Z=4 and V=667.1（2） 3. Dielectric measurements show compounds 1 and 2 have reversible dielectric anomalous behaviors with variation frequencies at different temperature.
基金supported by the National Natural Science Foundation of China(Nos.21822507,21625403,21761132020)National Key Research and Development Program of China(No.2018YFE0100600)founded by MOST,Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2017265)。
文摘For organnoboron co mpounds,the substituents on boron atoms are very important because they not only impact on the molecular stability but also significantly modulate the electronic structu res and prope rties.In this manuscript,we synthesized two new B←N-co ntaining azaacenes with propynyl groups on boron atoms through one-step Grignard reaction.Replacing fluorine atoms by propynyl groups greatly impacts on the electronic energy levels,especially enhancing the HOMO levels,thus leading to the narrowed HOMO-LUMO bandgaps.These B←N-containing azaacenes exhibit the NIR light-absorption(λabs=706 nm for 2 a and 762 nm for 2 b)and fluorescence properties(λem=740 nm for 2 a and802 nm for 2 b),as well as multiple reversible redox behaviors,which are significantly different from the analogs with fluorine atoms.This study thus provides a functional substituent of boron atom,which may lead to new organoboron materials with fascinating properties.
基金This work was financially supported by the National Key Research and Development Program of China(No.2019YFA0705902)funded by MOSTthe National Natural Science Foundation of China(Nos.21875244 and 22135007).
文摘The development of new polymer acceptors strongly paves the power conversion efficiency(PCE)improvement of all polymer solar cells(all-PSCs).Herein,we develop a new polymer acceptor PBN26,which is the alternating copolymer of 2,2′-((2Z,2′Z)-((12,13-bis(2-octyldodecyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1 H-indene-2,1-diylidene))dimalononitrile and B←N bridged thienylthiazole(BNTT).The optimized all-PSCs device based on PBN26 exhibits a PCE of 15.09%,which is the highest value of the all-PSCs based on B←N-based polymer acceptors at present.Moreover,we also fabricate an all-PSC module with active area of 10 cm2 by blade coating,which exhibits a PCE of 8.78%.These results prove that polymer acceptors containing B←N units are promising for all-PSC device applications.
文摘Aiming to reduce the defects of perovskite film and improve carrier transport,an organic small molecule,benzo[d]isothiazol-3(2H)-one 1,1-dioxide(OBS),is introduced as an additive in the solution-processing of perovskite and prepare uniform perovskite films with a continuous distribution of OBS at grain boundaries.Fourier trans-form infrared spectroscopy and X-ray photoelectron spectroscopy are conducted to reveal the interactions of hydrogen bonding and coordina tion bonding between OBS and perovskite.Various characterizations(including X-ray diffraction,UV-vis spectroscopy,electrochemical impedance spectroscopy,etc.)are conducted to uncover the effect of OBS on device performance.Consequently,high efficiency of 23.26%is obtained for the OBS-treated device,while the control device shows only a companion efficiency of 21.60%.
基金This work is supported by the National Natural Science Foundation of China
文摘Urushiol polymer containing B-N bond (PUBN) was synthesized with urushiol-boron polymer and diethylene triamine. Its structure was characterized by XPS, IR, UV, HPLC, DTA-TG and elemental analysis. The physico-mechanical and anticorrosive properties of the polymer were also investigated. The results show that the coating of PUBN can be hardened in 2 h at room temperature and its film has excellent physico-mechanical properties and good anticorrosive properties.
基金the financial support from the National Natural Science Foundation of China (52002356)the China Postdoctoral Science Foundation (2020M672269)the National Key R&D program of China (2019YFA0706802)
文摘In this study,the hydrogel network was reinforced by covalent-like hydrogen bonding,and the strong binding ability of boron-nitrogen coordination served as the main driving force.Among them,acrylamide(AM)and 3-acrylamidophenylboronic acid(AAPBA)were the main body,and the numerous hydroxyl groups in the trehalose(Treh)molecule and other polymer groups formed strong hydrogen bonding interactions to improve the mechanical properties of the PAM/PAAPBA/Treh(PAAT)hydrogel and ensured the simplicity of the synthesis process.The hydrogel possessed high strain at break(1239%),stress(64.7 kPa),low hysteresis(100%to 500%strain,corresponding to dissipation energy from 1.37 to 7.80 kJ/m^(3)),and outstanding cycling stability(retained more than 90%of maximum stress after 200 ten-sile cycles).By integrating carbon nanotubes(CNTs)into PAAT hydrogel(PAATC),the PAATC hydrogel with excellent strain response performance was successfully constructed.The PAATC conductive hydro-gel exhibited high sensitivity(gauge factor(GF)=10.58 and sensitivity(S)=0.304 kPa^(-1)),wide strain response range(0.5%-1000%),fast response time(450 ms),and short recovery time(350 ms),excellent fatigue resistance,and strain response stability.Furthermore,the PAATC-based triboelectric nanogener-ator(TENG)displayed outstanding energy harvesting performance,which shows its potential for appli-cation in self-powered electronic devices.
基金supported by the National Natural Science Foundation of China(No.22173089 and No.22103075)the National Key R&D Program of Chi-na(No.2021YFA0716801)Innovation Program for Quantum Science and Technology(2021ZD0300301).
文摘Photoelectron velocity map images of Cu(CO)_(3)^(-)have been experimentally recorded in the 700-1100 nm range.The infrared-inactive Cu^(-)C symmetric stretching modes for Cu(CO)_(3)(v_(2)≈367 cm^(-1))and Cu(CO)_(3)^(-)(v_(2)≈408 cm^(-1)),as well as the electron affinity(1.03±0.11 eV)of Cu(CO)_(3),are accurately determined from high resolution photoelectron spectra.In combination with quantum chemical calculations and bonding analyses,the coordination bonds in both Cu(CO)_(3)^(-)are Cu(CO)_(3)are found to be due to back-donationπbonding type,formed via electron promotion from Cu’s 4s orbital to the 4p orbital,which is consequently donated to the unoccupied anti-bondingπ*orbitals of the carbonyl groups.The attachment of an additional electron to Cu(CO)_(3)strengthens the Cu^(-)CO coordination,making Cu(CO)_(3)^(-)more stable.The intramolecular interactions between the Cu/Cu^(-)and carbonyl groups are found to be primarily governed by electrostatic forces and orbital interactions.
文摘Aromatic bond including metallic atom (Ni) is investigated by EHMO calculation.The NMR spectra and the mechanism for hydrolysis are discussed on the ground of results of computation.
