In the leaf of rice (Oryza sativa L.) cultivar Yunnan purple rice,the anthocyanins with an obvious absorption peak at 530nm were distributed in the cells of upper and lower epidermis,bulliform tissue and bristle. The ...In the leaf of rice (Oryza sativa L.) cultivar Yunnan purple rice,the anthocyanins with an obvious absorption peak at 530nm were distributed in the cells of upper and lower epidermis,bulliform tissue and bristle. The maximal photosynthetic oxygen evolution rate and chlorophyll content in flag leaves were 28% and 23%,respectively,more than the common green leaf rice cultivar Chijiaoru-anzhan. Higher chlorophyll content is probably one of the physiological adaptations for enhancing light harvesting capacity of the antenna in photosystems in this cyanic leaves species. Upon the photooxidation of leaf segments mediated by methyl viologen in weak light for 3 days,the distinct bleaching of anthocyanins in purple rice was associated with the reduction of scavenging ability to DPPH· free radical ability and the increase in membrane leakage rate. But almost no changes in contents of flavonoids and total phenolics were observed. Chlorophyll fluorescence parameters Fv/Fo,qP and φPSⅡ decreased with the increase in NPQ and DES of xanthophylls cycle after photooxidation treatment. Green rice leaves showed more decrease in DPPH· scavenging rate and more increase in cell membrane leakage rate but showed a trace of anthocyanins during photooxidation. It is sug-gested that anthocyanin may be a beneficial and primary antioxidant in sun cyanic rice leaves against oxidative stress induced by environmental adversity. And photooxidation could induce different changing patterns of anthocyanins between the tested purple and green rice leaves.展开更多
Redox flow batteries(RFBs)are promising candidates to establish a grid-scale energy storage system for intermittent energy sources.While the current technology of vanadium RFBs has been widely exploited across the wor...Redox flow batteries(RFBs)are promising candidates to establish a grid-scale energy storage system for intermittent energy sources.While the current technology of vanadium RFBs has been widely exploited across the world,the rise in the price of vanadium and its limited volumetric energy density have necessitated the development of new kinds of redox active molecules.Organic molecules can be used as new and economical redox couples in RFBs to address these issues.In addition,the redox organic species also provide ample advantages to increase the voltage and solubility,provide multiple numbers of electron transfer,and ensure electrochemical/chemical stability by molecular engineering through simple synthetic methods.This review focuses on the recent developments in aqueous organic RFBs,including the molecular design and the corresponding cycling performance as these organic redox molecules are employed as either the negolyte or posolyte.Various strategies for tuning the electrochemical/chemical characteristics of organic molecules have improved their solubility,redox potential cycling stability,and crossover issue across a separating membrane.We also put forward new strategies using nanotechnology and our perspective for the future development of this rapidly growing field.展开更多
Abstract： A new compound 1-ethyl-1＇-（4-vinylbenzyl）-4, 4＇-bipyridinium chloride and iodide has been synthesized. The cyclic voltammogram and impedance spectra indicated that a layer of viologen＇s electrochromic ...Abstract： A new compound 1-ethyl-1＇-（4-vinylbenzyl）-4, 4＇-bipyridinium chloride and iodide has been synthesized. The cyclic voltammogram and impedance spectra indicated that a layer of viologen＇s electrochromic （EC） film could be deposited on conductive ITO glass working electrode With polyelectrolyte as ionic conduction layer, solid EC devices based on this compound have been assembled and their thickness was about 2.35 mm. When different voltages were added, they showed blue or violet red color. After optimization, its response time was less than 50 ms, the number of redox circulation was over 107 and the color of coloration states could be kept for 3 days. This kind of EC device can meet the demand of electronic ink.展开更多
Flexible electronics play a key role in the development of human society and our daily activities.Currently they are expected to revolutionize personal health management.However,it remains challenging to fabricate sma...Flexible electronics play a key role in the development of human society and our daily activities.Currently they are expected to revolutionize personal health management.However,it remains challenging to fabricate smart sensors with high robustness,reliability,and visible readout.Herein,high-performance electrochromic(EC),electro-fluorochromic(EFC),and double-network ionogels with excellent transmissivity,high mechanical robustness,and ultrastable reversibility are prepared by combination of thienoviologen-containing ionic liquids with poly(ethyl acrylate)elastomer.The ionogels exhibit good mechanical properties(1000%stretchability and 3.2 kJ m^(−2) fracture energy).The ionogel-based EC devices have a significantly simplified device fabrication process as well as superior cycling stability in which 88%of the contract ratio is maintained at 88%at 500 cycles,even after being stored for 2 years under ambient atmosphere(relative humidity:30%∼40%,25°C).The conductivity of ionogels showed a fast and reproducible response to strain,and the conductivity decreased with increased strain.By virtue of the EC and EFC properties of the thienoviologen component,the EC and EFC efficiency decreased with the increased strain loaded on the ionogels,and almost no EC or EFC phenomena were observed when the strain was above 300%.This feasible strategy provides an opportunity for the development of visible strain sensors to monitor the body’s movements through color and fluorescence emission.展开更多
The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical(PEC)H2 production devices.Coupling TiO_(2) with p-type semiconducto...The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical(PEC)H2 production devices.Coupling TiO_(2) with p-type semiconductors to construct heterojunction structures is one of the most widely used strategies to facilitate charge separation and transportation.However,the band position of TiO_(2) could not perfectly match with all p-type semiconductors.Here,taking antimony selenide(Sb_(2)Se_(3))as an example,a rational strategy was developed by introducing a viologen electron transfer mediator(ETM)containing polymeric film(poly-1,1′-dially-[4,4′-bipyridine]-1,1′-diium,denoted as PV^(2+))at the interface between Sb_(2)Se_(3) and TiO_(2) to regulate the energy band alignment,which could inhibit the recombination of photogenerated charge carriers of interfaces.With Pt as a catalyst,the constructed Sb_(2)Se_(3)/PV^(2+)/TiO_(2)/Pt photocathode showed a superior PEC hydrogen generation activity with a photocurrent density of−18.6 mA cm^(-2) vs.a reversible hydrogen electrode(RHE)and a half-cell solar-to-hydrogen efficiency(HC-STH)of 1.54%at 0.17 V vs.RHE,which was much better than that of the related Sb_(2)Se_(3)/TiO_(2)/Pt photocathode without PV^(2+)(−9.8 mA cm^(-2),0.51%at 0.10 V vs.RHE).展开更多
The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)...The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)-based Cu-viologen complex H_(4)[Cu_(2)~ⅠCl_(2)(Hbcbpy)_(4)] [α-Mo_(8)O_(26)] [β-Mo8O_(26)]·H_(2)O(BHU-2,Hbcbpy=1-(4-carboxybenzyl)-4,4'-bipyridinium) was synthesized and characterized by single-crystal X-ray diffraction(XRD),infrared radiation spectra,powder X-ray diffraction(PXRD) and X-ray photoelectron spectroscopy(XPS) spectra.The structural characteristic of BHU-2 is the presence of two types of octamolybdate clusters [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)and a new binuclear Cu~Ⅰ-Hbcbpy complex linked by Cl-bridges[Cu_(2)ⅠCl_(2)(Hbcbpy)_(4)]^(4+).BHU-2 as a heterogeneous catalyst exhibits excellent activities to the oxidation desulfurization and photocatalytic hydrogen production.At room temperature,BHU-2 can catalyze 96% conversion of methyl phenyl sulfide with 98% selectivity,and the process obeys the pseudo-first-order reaction kinetic with the half-life of9.6 min.The notorious 2-chloroethyl ethyl sulfide can achieve 99% conversion with 98% selectivity within only1 min at the presence of BHU-2,and the turnover frequency(TOF) is up to 7400 h^(-1).BHU-2 also exhibits high catalytic activity for the oxidation of other aromatic and aliphatic thioethers within short time at room temperature.Furthermore,BHU-2 shows a high catalytic activity for visible-light-driven hydrogen evolution with an H_(2) evolution rate of 1677.85 μmol·g^(-1)·h^(-1) within 10 h.Moreover,the catalytic activities do not decrease evidently after three cycles,revealing the prominent structural stability and recyclability.展开更多
The commercialization of lithium-sulfur(Li-S)batteries has been hindered by the shuttle effect and sluggish redox kinetics of lithium polysulfides(LiPSs).Herein,we reported a viologen-ba sed ionic conjugated mesoporou...The commercialization of lithium-sulfur(Li-S)batteries has been hindered by the shuttle effect and sluggish redox kinetics of lithium polysulfides(LiPSs).Herein,we reported a viologen-ba sed ionic conjugated mesoporous polymer(TpV-Cl),which acts as the cathode host for modifying Li-S batteries.The viologen component serves as a reversible electron conveyer,leading to a comprehensive enhancement in the adsorption of polysulfides and improved conversion rate of polysulfides during the electrochemical process.As a result,the S@TpV-PS cathode exhibits outstanding cycling performance,achieving 300 cycles at2.0 C(1 C=1675 mA g^(-1))with low decay rate of 0.032%per cycle.Even at a high sulfur loading of 4.0 mg cm^(-2),S@TpV-PS shows excellent cycling stability with a Coulombic efficiency of up to 98%.These results highlight the significant potential of S@TpV-PS in developing high-performance Li-S batteries.展开更多
A new iodiplumbate/organic hybrid constructed from asymmetric viologen and polyiodides,（PBPY-H2）2[PbI4（I3）2]（1, PBPY = N-（propionate）-4,4？-bipyridinium）, has been synthesized via solvothermal reaction and str...A new iodiplumbate/organic hybrid constructed from asymmetric viologen and polyiodides,（PBPY-H2）2[PbI4（I3）2]（1, PBPY = N-（propionate）-4,4？-bipyridinium）, has been synthesized via solvothermal reaction and structurally determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic system, space group P21/c with Mr = 1936.72, a = 11.622（2）, b = 14.839（3）, c = 13.372（2）A^°, β = 109.447（3）°, V = 2174.6（7）A^°^3, Z = 2, Dc = 2.958 g/cm^3, F（000） = 1712, μ（Mo Kα） = 11.011 mm^–1, the final R = 0.0389 and wR = 0.0854 for 3866 observed reflections with I 〉 2σ（I）. [Pb I4（I3）2]^4-mononuclear cluster of 1 features a seldom example of coordinated I-3 donors for the lead center. Intermolecular hydrogen bonds between [Pb I4＋4（I3）2]^4-clusters and（PBPY-H）2^4＋ dimmers contribute to the formation of a 2-D layer. Its absorption spectrum was investigated, and lower energy band gap of 1.42 eV was explained by DFT calculation. Interestingly, 1 exhibits photocatalytic activity for the degradation of rhodamine B.展开更多
Developing efficient photosensitizers for C-P bond construction is highly important and remains a challenge due to the urgently needed for the synthesis of modified nucleosides,nucleotides,and other phosphine-containi...Developing efficient photosensitizers for C-P bond construction is highly important and remains a challenge due to the urgently needed for the synthesis of modified nucleosides,nucleotides,and other phosphine-containing ligands.Herein,two pyrene-tethered bismoviologen derivatives(Py-BiV^(2+))were designed and synthesized for visible-light-induced C-P bonds formation.The photochemical and electrochemical properties of Py-BiV^(2+)were studied systemically,certifying fine-tunable opto-electronic properties through the number of pyrene groups(4,n=1;6,n=2).The prepared Py-BiV^(2+)showed strong light absorption,while retaining good redox features and chromic response features that were inherent to viologens.4 exhibited accelerated photoinduced electron transfer in the presence of the electron donor(pyrene)and the generated 4(radical cation)showed higher stability.Accordingly,Py-BiV^(2+)directly served as photosensitizers for the first time in the visible-light-induced C(sp^(3))-P and C(sp^(2))-P bonds formation.As expected,these novel viologen derivatives exhibited good catalytic performance and good substrate expansibility under ambient conditions.展开更多
Redox-flow batteries(RFBs)are a promising energy storage technology with remarkable scalability and safety for storing vast amounts of renewable energy and mitigating outputfluctuations of renewable power grids.We demon...Redox-flow batteries(RFBs)are a promising energy storage technology with remarkable scalability and safety for storing vast amounts of renewable energy and mitigating outputfluctuations of renewable power grids.We demonstrate a neutral pH aqueous RFB using a custom-designed 1’,1’’’,1’’’’’-(benzene-1,3,5-triyltris(methylene))tris(1-(3-(trimethyl ammonio)propyl)-[4’’,4’’’-bipyridine]-1,1’-diium)nonachloride(BTTMPB)as a 3 e-storage anolyte.The custom design with the high polarization in charge density has led to the excellent water solubility of 4.0 M in H_(2)O(321.6 A h L^(-1))and 2.4 M in 2.0 M NaCl(192.9 A h L^(-1)).The density functional theory(DFT)calculations and electrochemical experiments have shown 3 e-storage response of BTTMPB with a diffusion coefficient of 3.1×10^(-6)cm^(2) s^(-1)and rate con-stant of 1.6×10^(-2)cm s^(-1) for thefirst reduction process.The synthesized anolyte was paired with(Ferrocenylmethyl)trimethylammonium chloride(FcNCl)as catholyte enabling a 0.92 V aqueous RFB with 125.9 W h L^(-1)theoretical energy density.The aqueous RFB has an excellent cycling performance from 10-30 m A cm^(-2),energy efficiency up to 80%,capacity retention of 99.96%per cycle at 20 m A cm^(-2),and a high demonstrated energy density of 29.1 W h L^(-1).展开更多
基金supported by the National Natural Science Foundation of China(Grant No.30270125)Guangdong Natural Science Foundation(Grant No.04002309)Project of CAS Knowledge Innovation Program(Grant No.KSCX2-SW-130).
文摘In the leaf of rice (Oryza sativa L.) cultivar Yunnan purple rice,the anthocyanins with an obvious absorption peak at 530nm were distributed in the cells of upper and lower epidermis,bulliform tissue and bristle. The maximal photosynthetic oxygen evolution rate and chlorophyll content in flag leaves were 28% and 23%,respectively,more than the common green leaf rice cultivar Chijiaoru-anzhan. Higher chlorophyll content is probably one of the physiological adaptations for enhancing light harvesting capacity of the antenna in photosystems in this cyanic leaves species. Upon the photooxidation of leaf segments mediated by methyl viologen in weak light for 3 days,the distinct bleaching of anthocyanins in purple rice was associated with the reduction of scavenging ability to DPPH· free radical ability and the increase in membrane leakage rate. But almost no changes in contents of flavonoids and total phenolics were observed. Chlorophyll fluorescence parameters Fv/Fo,qP and φPSⅡ decreased with the increase in NPQ and DES of xanthophylls cycle after photooxidation treatment. Green rice leaves showed more decrease in DPPH· scavenging rate and more increase in cell membrane leakage rate but showed a trace of anthocyanins during photooxidation. It is sug-gested that anthocyanin may be a beneficial and primary antioxidant in sun cyanic rice leaves against oxidative stress induced by environmental adversity. And photooxidation could induce different changing patterns of anthocyanins between the tested purple and green rice leaves.
文摘Redox flow batteries(RFBs)are promising candidates to establish a grid-scale energy storage system for intermittent energy sources.While the current technology of vanadium RFBs has been widely exploited across the world,the rise in the price of vanadium and its limited volumetric energy density have necessitated the development of new kinds of redox active molecules.Organic molecules can be used as new and economical redox couples in RFBs to address these issues.In addition,the redox organic species also provide ample advantages to increase the voltage and solubility,provide multiple numbers of electron transfer,and ensure electrochemical/chemical stability by molecular engineering through simple synthetic methods.This review focuses on the recent developments in aqueous organic RFBs,including the molecular design and the corresponding cycling performance as these organic redox molecules are employed as either the negolyte or posolyte.Various strategies for tuning the electrochemical/chemical characteristics of organic molecules have improved their solubility,redox potential cycling stability,and crossover issue across a separating membrane.We also put forward new strategies using nanotechnology and our perspective for the future development of this rapidly growing field.
基金This work was financially supported by the Chongqing Natural Science Foundation of China （CSTC, 2005BB4109）.
文摘Abstract： A new compound 1-ethyl-1＇-（4-vinylbenzyl）-4, 4＇-bipyridinium chloride and iodide has been synthesized. The cyclic voltammogram and impedance spectra indicated that a layer of viologen＇s electrochromic （EC） film could be deposited on conductive ITO glass working electrode With polyelectrolyte as ionic conduction layer, solid EC devices based on this compound have been assembled and their thickness was about 2.35 mm. When different voltages were added, they showed blue or violet red color. After optimization, its response time was less than 50 ms, the number of redox circulation was over 107 and the color of coloration states could be kept for 3 days. This kind of EC device can meet the demand of electronic ink.
基金research was made possible as a result of generous grants from the National Key Research and Development Program of China(grant no.2021YFB3200700)the Natural Science Foundation of China(grant nos.22175138,21875180,and 52203240)+4 种基金the Independent Innovation Capability Improvement Project of Xi’an Jiaotong University(grant no.PY3A066)the China National Postdoctoral Program for Innovative Talents(grant no.BX2021231)the Fundamental Research Funds for the Central Universities(grant no.sxjh032021099)the China Postdoctoral Science Foundation(grant no.2021M692545)the Natural Science Foundation of Shaanxi Province(grant no.2021JQ-043).
文摘Flexible electronics play a key role in the development of human society and our daily activities.Currently they are expected to revolutionize personal health management.However,it remains challenging to fabricate smart sensors with high robustness,reliability,and visible readout.Herein,high-performance electrochromic(EC),electro-fluorochromic(EFC),and double-network ionogels with excellent transmissivity,high mechanical robustness,and ultrastable reversibility are prepared by combination of thienoviologen-containing ionic liquids with poly(ethyl acrylate)elastomer.The ionogels exhibit good mechanical properties(1000%stretchability and 3.2 kJ m^(−2) fracture energy).The ionogel-based EC devices have a significantly simplified device fabrication process as well as superior cycling stability in which 88%of the contract ratio is maintained at 88%at 500 cycles,even after being stored for 2 years under ambient atmosphere(relative humidity:30%∼40%,25°C).The conductivity of ionogels showed a fast and reproducible response to strain,and the conductivity decreased with increased strain.By virtue of the EC and EFC properties of the thienoviologen component,the EC and EFC efficiency decreased with the increased strain loaded on the ionogels,and almost no EC or EFC phenomena were observed when the strain was above 300%.This feasible strategy provides an opportunity for the development of visible strain sensors to monitor the body’s movements through color and fluorescence emission.
基金conducted by the Fundamental Research Center of Artificial Photosynthesis(FReCAP)financially supported by the National Natural Science Foundation of China(NSFC)(22172011 and 22088102)+2 种基金the K&A Wallenberg Foundation(KAW 2016.0072)Key Laboratory of Bio-based Chemicals of Liaoning Province of ChinaZhejiang Province Selected Funding for Postdoctoral Research Projects(ZJ2021001)for financial support.
文摘The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical(PEC)H2 production devices.Coupling TiO_(2) with p-type semiconductors to construct heterojunction structures is one of the most widely used strategies to facilitate charge separation and transportation.However,the band position of TiO_(2) could not perfectly match with all p-type semiconductors.Here,taking antimony selenide(Sb_(2)Se_(3))as an example,a rational strategy was developed by introducing a viologen electron transfer mediator(ETM)containing polymeric film(poly-1,1′-dially-[4,4′-bipyridine]-1,1′-diium,denoted as PV^(2+))at the interface between Sb_(2)Se_(3) and TiO_(2) to regulate the energy band alignment,which could inhibit the recombination of photogenerated charge carriers of interfaces.With Pt as a catalyst,the constructed Sb_(2)Se_(3)/PV^(2+)/TiO_(2)/Pt photocathode showed a superior PEC hydrogen generation activity with a photocurrent density of−18.6 mA cm^(-2) vs.a reversible hydrogen electrode(RHE)and a half-cell solar-to-hydrogen efficiency(HC-STH)of 1.54%at 0.17 V vs.RHE,which was much better than that of the related Sb_(2)Se_(3)/TiO_(2)/Pt photocathode without PV^(2+)(−9.8 mA cm^(-2),0.51%at 0.10 V vs.RHE).
基金financially supported by the National Natural Science Foundation of China (Nos.22271021,21901018 and 21971024)the Natural Science Foundation of Liaoning Province (No.2022-MS-373)Liaoning Revitalization Talents Program (No.XLYC1902011)。
文摘The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)-based Cu-viologen complex H_(4)[Cu_(2)~ⅠCl_(2)(Hbcbpy)_(4)] [α-Mo_(8)O_(26)] [β-Mo8O_(26)]·H_(2)O(BHU-2,Hbcbpy=1-(4-carboxybenzyl)-4,4'-bipyridinium) was synthesized and characterized by single-crystal X-ray diffraction(XRD),infrared radiation spectra,powder X-ray diffraction(PXRD) and X-ray photoelectron spectroscopy(XPS) spectra.The structural characteristic of BHU-2 is the presence of two types of octamolybdate clusters [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)and a new binuclear Cu~Ⅰ-Hbcbpy complex linked by Cl-bridges[Cu_(2)ⅠCl_(2)(Hbcbpy)_(4)]^(4+).BHU-2 as a heterogeneous catalyst exhibits excellent activities to the oxidation desulfurization and photocatalytic hydrogen production.At room temperature,BHU-2 can catalyze 96% conversion of methyl phenyl sulfide with 98% selectivity,and the process obeys the pseudo-first-order reaction kinetic with the half-life of9.6 min.The notorious 2-chloroethyl ethyl sulfide can achieve 99% conversion with 98% selectivity within only1 min at the presence of BHU-2,and the turnover frequency(TOF) is up to 7400 h^(-1).BHU-2 also exhibits high catalytic activity for the oxidation of other aromatic and aliphatic thioethers within short time at room temperature.Furthermore,BHU-2 shows a high catalytic activity for visible-light-driven hydrogen evolution with an H_(2) evolution rate of 1677.85 μmol·g^(-1)·h^(-1) within 10 h.Moreover,the catalytic activities do not decrease evidently after three cycles,revealing the prominent structural stability and recyclability.
基金supported by the National Natural Science Foundation of China(21825106,92061201,22205210,and 22171248)the Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(234000510007)+1 种基金the Natural Science Foundation of Henan Province(222300420289)Zhengzhou University。
文摘The commercialization of lithium-sulfur(Li-S)batteries has been hindered by the shuttle effect and sluggish redox kinetics of lithium polysulfides(LiPSs).Herein,we reported a viologen-ba sed ionic conjugated mesoporous polymer(TpV-Cl),which acts as the cathode host for modifying Li-S batteries.The viologen component serves as a reversible electron conveyer,leading to a comprehensive enhancement in the adsorption of polysulfides and improved conversion rate of polysulfides during the electrochemical process.As a result,the S@TpV-PS cathode exhibits outstanding cycling performance,achieving 300 cycles at2.0 C(1 C=1675 mA g^(-1))with low decay rate of 0.032%per cycle.Even at a high sulfur loading of 4.0 mg cm^(-2),S@TpV-PS shows excellent cycling stability with a Coulombic efficiency of up to 98%.These results highlight the significant potential of S@TpV-PS in developing high-performance Li-S batteries.
基金Project supported by the National Natural Science Foundation of China(21271043,21771038)Qishan Scholars Program of Fuzhou University(No.XQS-1403)
文摘A new iodiplumbate/organic hybrid constructed from asymmetric viologen and polyiodides,（PBPY-H2）2[PbI4（I3）2]（1, PBPY = N-（propionate）-4,4？-bipyridinium）, has been synthesized via solvothermal reaction and structurally determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic system, space group P21/c with Mr = 1936.72, a = 11.622（2）, b = 14.839（3）, c = 13.372（2）A^°, β = 109.447（3）°, V = 2174.6（7）A^°^3, Z = 2, Dc = 2.958 g/cm^3, F（000） = 1712, μ（Mo Kα） = 11.011 mm^–1, the final R = 0.0389 and wR = 0.0854 for 3866 observed reflections with I 〉 2σ（I）. [Pb I4（I3）2]^4-mononuclear cluster of 1 features a seldom example of coordinated I-3 donors for the lead center. Intermolecular hydrogen bonds between [Pb I4＋4（I3）2]^4-clusters and（PBPY-H）2^4＋ dimmers contribute to the formation of a 2-D layer. Its absorption spectrum was investigated, and lower energy band gap of 1.42 eV was explained by DFT calculation. Interestingly, 1 exhibits photocatalytic activity for the degradation of rhodamine B.
基金supported by the Natural Science Foundation of China(Nos.22175138,21875180)the Key Research and Development Program of Shaanxi(No.2021GXLH-Z023)the Independent Innovation Capability Improvement Project of Xi’an Jiaotong University(No.PY3A066)。
文摘Developing efficient photosensitizers for C-P bond construction is highly important and remains a challenge due to the urgently needed for the synthesis of modified nucleosides,nucleotides,and other phosphine-containing ligands.Herein,two pyrene-tethered bismoviologen derivatives(Py-BiV^(2+))were designed and synthesized for visible-light-induced C-P bonds formation.The photochemical and electrochemical properties of Py-BiV^(2+)were studied systemically,certifying fine-tunable opto-electronic properties through the number of pyrene groups(4,n=1;6,n=2).The prepared Py-BiV^(2+)showed strong light absorption,while retaining good redox features and chromic response features that were inherent to viologens.4 exhibited accelerated photoinduced electron transfer in the presence of the electron donor(pyrene)and the generated 4(radical cation)showed higher stability.Accordingly,Py-BiV^(2+)directly served as photosensitizers for the first time in the visible-light-induced C(sp^(3))-P and C(sp^(2))-P bonds formation.As expected,these novel viologen derivatives exhibited good catalytic performance and good substrate expansibility under ambient conditions.
基金the Department of Science and Technology(DST),Ministry of Science and Technology,Government of India,for sponsoring this study under project no.DST/TMD/MES/2k18/02CSIR,Gov.of India,for the Senior Research Fellowship。
文摘Redox-flow batteries(RFBs)are a promising energy storage technology with remarkable scalability and safety for storing vast amounts of renewable energy and mitigating outputfluctuations of renewable power grids.We demonstrate a neutral pH aqueous RFB using a custom-designed 1’,1’’’,1’’’’’-(benzene-1,3,5-triyltris(methylene))tris(1-(3-(trimethyl ammonio)propyl)-[4’’,4’’’-bipyridine]-1,1’-diium)nonachloride(BTTMPB)as a 3 e-storage anolyte.The custom design with the high polarization in charge density has led to the excellent water solubility of 4.0 M in H_(2)O(321.6 A h L^(-1))and 2.4 M in 2.0 M NaCl(192.9 A h L^(-1)).The density functional theory(DFT)calculations and electrochemical experiments have shown 3 e-storage response of BTTMPB with a diffusion coefficient of 3.1×10^(-6)cm^(2) s^(-1)and rate con-stant of 1.6×10^(-2)cm s^(-1) for thefirst reduction process.The synthesized anolyte was paired with(Ferrocenylmethyl)trimethylammonium chloride(FcNCl)as catholyte enabling a 0.92 V aqueous RFB with 125.9 W h L^(-1)theoretical energy density.The aqueous RFB has an excellent cycling performance from 10-30 m A cm^(-2),energy efficiency up to 80%,capacity retention of 99.96%per cycle at 20 m A cm^(-2),and a high demonstrated energy density of 29.1 W h L^(-1).
