Photocatalytic disinfection is an eco-friendly strategy for countering bacterial pollution in aquatic environments.Numerous strategies have been devised to facilitate the generation of reactive oxygen species(ROS)with...Photocatalytic disinfection is an eco-friendly strategy for countering bacterial pollution in aquatic environments.Numerous strategies have been devised to facilitate the generation of reactive oxygen species(ROS)within photocatalysts,ultimately leading to the eradication of bacteria.However,the significance of the physical morphology of photocatalysts in the context of sterilization is frequently obscured,and the progress in the development of physical-chemical synergistic sterilization photocatalysts has been relatively limited.Herein,graphitic carbon nitride(g-C_(3)N_(4))is chemically protonated to expose more sharp edges.PL fluorescence and EIS results indicate that the protonation can accelerate photogenerated carrier separation and enhance ROS production.Meanwhile,the sharp edges on the protonated g-C_(3)N_(4)facilitate the physical disruption of cell walls for further promoting oxidative damage.Protonated C_(3)N_(4)demonstrated superior bactericidal performance than that of pristine g-C_(3)N_(4),effectively eliminating Escherichia coli within 40 minutes under irradiation.This work highlights the significance of incorporating physical and chemical synergies in photocatalyst design to enhance the disinfection efficiency of photocatalysis.展开更多
New layered perovskites, KSr2Nb3O10 and two new protonated niobates HSr2 Nb3O10·1.2H2O and HSr2Nb3O10,were synthesized by solid state reaction and ion-exchange reaction. These new compounds -were characterized by...New layered perovskites, KSr2Nb3O10 and two new protonated niobates HSr2 Nb3O10·1.2H2O and HSr2Nb3O10,were synthesized by solid state reaction and ion-exchange reaction. These new compounds -were characterized by EPMA, AAS, XRD, IR, DTA and so on. The structure may be described as treble perovskite sheets [Sr2Nb3O10]- interleaved with K+ ,H3O + or H+. These new compounds are new members of the Dion-Jacob-sonseries with n=3 for the general formula M[An-1 NbnO3n+1], and their indexed X-ray powder diffraction data were first reported in the paper.展开更多
Formation and dissociation mechanisms of C-C＋ base pairs in acidic and alkaline environments are investigated, employing ab initio quantum chemical calculations. Our calculations suggest that, in an acidic environmen...Formation and dissociation mechanisms of C-C＋ base pairs in acidic and alkaline environments are investigated, employing ab initio quantum chemical calculations. Our calculations suggest that, in an acidic environment, a cytosine monomer is first protonated and then dimerized with an unprotonated cytosine monomer to form a C-C＋ base pair; in an alkaline environment, a protonated cytosine dimer is first unprotonated and then dissociated into two cytosine monomers. In addition, the force for detaching a C-C＋ base pair was found to be inversely proportional to the distance between the two cytosine monomers. These results provide a microscopic mechanism to qualitatively explain the experimentally observed reversible formation and dissociation of i-motifs.展开更多
Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base(RPSB).Microbial rhodopsins absorb light through chro...Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base(RPSB).Microbial rhodopsins absorb light through chromophore and play a fundamental role in optogenetics.Numerous microbial rhodopsins have been discovered,contributing to diverse functions and colors.Solid-state NMR spectroscopy has been instrumental in elucidating the conformation of chromophores and the three-dimensional structure of microbial rhodopsins.This review focuses on the 15N chemical shift values of RPSB and summarizes recent progress in the field.We displayed the correlation between the 15N isotropic chemical shift values of RPSB and the maximum absorption wavelength of rhodopsin using solid-state NMR spectroscopy.展开更多
A modified method for preparation and purification of Schiff base and protonated Schiff base from 9-cis-retinal has been suggested. Reaction took place in chloroform phase and purification was conducted by using water...A modified method for preparation and purification of Schiff base and protonated Schiff base from 9-cis-retinal has been suggested. Reaction took place in chloroform phase and purification was conducted by using water to remove the excess solvent, base and acid.展开更多
Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to real...Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.展开更多
Infrared multiple photon dissociation （IRMPD） spectroscopic and theoretical studies of protonated homodimers of amino acids generated by electrospray ionization in the gas phase have been reviewed. Results show that...Infrared multiple photon dissociation （IRMPD） spectroscopic and theoretical studies of protonated homodimers of amino acids generated by electrospray ionization in the gas phase have been reviewed. Results show that proton affinity （PA） may be applied as a probe to predict their structural type： salt- bridged or charge-solvated. Proline can be viewed as a reference. For an amino acid with a PA value higher than that of proline, the most stable conformation of its protonated homodimer tends to prefer salt- bridged conformation; otherwise, charge-solvated conformation is expected to be the most stable. However, side chain effects may cause the inaccuracy in structural determination due to the strong interactions with the charge, which makes the charge-solvated structure more stable even for species with high PA values. Temperature effect on distribution of different isomers is also very important. In lots of cases, the coexistence of multiple isomers is general, which makes the explanation of an overall IRMPD spectrum difficult. So a statistical view on the distribution of optimized isomers is very helpful.展开更多
The low energy collisioninduced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact a...The low energy collisioninduced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact and chemical ionization conditions. It was found that this compound shows an unusual reactivity towards protonation. Two possible sites of protonation have been proposed to explain the corresponding fragmentation processes, one is that the protonation takes place on the oxygen atom of hydroxyl group, resulting in the loss of water and the other is the formation of an intermediary protonbound complex in the fragmentation process, giving rise to the fragment ions of m/z 133 and m/z 135. The results show both cases are coexistence in the fragmentations of protonated N-hydroxyphthalimide, and the unimolecular fragmentation pathways are available.展开更多
Density functional calculations are used to determine structural and electronic properties of P4,P4O6,P4O10,P20O30 and P20O50 clusters and their protonated derivatives.These oxygen-rich phosphorus oxides are predicted...Density functional calculations are used to determine structural and electronic properties of P4,P4O6,P4O10,P20O30 and P20O50 clusters and their protonated derivatives.These oxygen-rich phosphorus oxides are predicted to have relatively high stabilities with respect to their components P4 and O2,and their unsaturated P and end-on O atoms as the proton acceptor can accommodate multiple protons to generate highly positively charged cationic clusters,such as P20O30H1010＋.Calculations indicate that P4O6 and P20O30 have higher reactivity toward the proton capture than the P4,P4O10 and P20O50 clusters,and the most stable protonated clusters among these different series of cationic clusters are P4H2……2＋,P4O6H2^2＋,P4O10H3^3＋,P20O30H4^4＋ and P20O50H4^4＋,respectively.The cage skeleton of the phosphorus oxide clusters shows high stability for the consecutive protonation,and the unsymmetrical stretching of the skeletal P-O bond and the wagging mode of P-H coupled with the P-O bond stretching have strong adsorptions.These computational findings are useful for further experimental and theoretical studies of novel phosphorus oxide clusters and their highly positively charged derivatives.展开更多
A novel photocatalyst with protonated carbon nitride(p-C_(3)N_(4))loaded with IrO_(2)quantum dots(QDs)was fabricated via a facile hydrothermal method.Structure characterization studies(XRD,STEM,XPS,UV–vis spectra and...A novel photocatalyst with protonated carbon nitride(p-C_(3)N_(4))loaded with IrO_(2)quantum dots(QDs)was fabricated via a facile hydrothermal method.Structure characterization studies(XRD,STEM,XPS,UV–vis spectra and PL spectra)revealed that the IrO_(2)QDs with an average diameter of ca.展开更多
Covalent organic frameworks(COFs)are emerging as promising photocatalysts owing to their tailorable structures,exceptional crystallinity,and robustness.However,the photocatalytic performance of COFs is limited by fast...Covalent organic frameworks(COFs)are emerging as promising photocatalysts owing to their tailorable structures,exceptional crystallinity,and robustness.However,the photocatalytic performance of COFs is limited by fast charge recombination and inefficient charge migration.Herein,a novel post-synthetic partial protonation strategy is proposed to construct COFs with asymmetric unprotonated/protonated homojunctions,which endow them with an enlarged molecular dipole moment,thereby generating a strong built-in electric field that significantly enhances the charge separation and transport efficiencies in COFs.In addition,the protonation process extends the light absorption range and improves the hydrophilicity of COFs.The photocatalytic hydrogen evolution rate of the partially protonated TPE-COF and ETTBA-COF is enhanced by 88-and 175-fold relative to their pristine counterparts,4.3 and 2.48 times those of fully protonated counterparts,respectively.Our results clearly demonstrate the pivotal role of the asymmetric unprotonated/protonated homojunctions within COFs in the photocatalytic hydrogen evolution.This post-synthetic partial protonation strategy provides a novel paradigm for establishing internal electric fields within COFs.展开更多
In this work, we demonstrated the successful construction of metal-free zero- dimensional/two-dimensional carbon nanodot （CND）-hybridized protonatedg=C3N4 （pCN） （CND/pCN） heterojunction photocatalysts b; means o...In this work, we demonstrated the successful construction of metal-free zero- dimensional/two-dimensional carbon nanodot （CND）-hybridized protonatedg=C3N4 （pCN） （CND/pCN） heterojunction photocatalysts b; means of electrostatic attraction. We experimentally found that CNDs with an average diameter of 4.4 nm were uniformly distributed on the surface of pCN using electron microscopy analysis. The CND/pCN-3 sample with a CND content of 3 wt.% showed thehighest catalytic activity in the CO2 photoreduction process under visible and simulated solar light. This process results in the evolution of CH4 and CO. Thetotal amounts of CH4 and CO generated by the CND/pCN-3 photocatalyst after 10 h of visible-light activity were found to be 29.23 and 58.82 molgcatalyst-1, respectively. These values were 3.6 and 2.28 times higher, respectively, than thearn＊ounts generated when using pCN alone. The corresponding apparent quantum efficiency （AQE） was calculated to be 0.076%. Furthermore, the CND/pCN-3 sample demonstrated high stability and durability after four consecutive photoreaction cycles, with no significant decrease in the catalytic activity.展开更多
This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the correspo...This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.展开更多
Proton exchange membrane fuel cells(PEMFCs)are considered as a promising renewable power source.However,the massive commercial application of PEMFCs has been greatly hindered by their high expense and less-satisfied p...Proton exchange membrane fuel cells(PEMFCs)are considered as a promising renewable power source.However,the massive commercial application of PEMFCs has been greatly hindered by their high expense and less-satisfied performance mainly due to the sluggish oxygen reduction reaction(ORR)kinetics even on state-of-the-art Pt catalyst.Octahedral PtNi nanoparticles(oct-PtNi NPs)with excellent ORR activity in a half-cell have been widely studied,while their performance in membrane electrode assembly(MEA)has much less reported.Herein,we investigated the MEA performance using the carbon supported oct-PtNi NPs(oct-PtNi/C)as the cathode catalyst.Under the mild acid washing condition,the surface Ni atoms of oct-PtNi/C were largely removed,and the performance of the MEA using the acid-leaching oct-PtNi/C(PNC-A)as the cathode catalyst was greatly improved.The maximum power density of the MEA reached 1.0 W·cm^(-2) with the cath-ode Pt loading of 0.2 mg·cm^(-2),which is 15%higher than that using Pt/C as the catalyst.After 30k cycles in the accelerated degradation test(ADT),the MEA using PNC-A as the catalyst showed a performance retention of 82%,higher than that of Pt/C(74%).The results reported here verify the possibility of using PNC-A as an advanced cathode catalyst in PEMFCs,thus enhancing the performance of PEMFCs while lowering the amount of expensive Pt.展开更多
Ordered thin organic films deposited on solid substrates by the Langmuir-Blodgett(LB) technique have attracted much attention because of their possibility of being applied tofunctional molecular device architectures, ...Ordered thin organic films deposited on solid substrates by the Langmuir-Blodgett(LB) technique have attracted much attention because of their possibility of being applied tofunctional molecular device architectures, such as electronic, nonlinear optical and bio-logical sensors. Very elegant work has been carried out by Kuhn and his展开更多
It has been investigated for a long time by many authors to mimic the vision pro-cess.The most important step is to synthesize pigments having similar function ofrhodopsin,for example,to combine ll-cis-retinal with op...It has been investigated for a long time by many authors to mimic the vision pro-cess.The most important step is to synthesize pigments having similar function ofrhodopsin,for example,to combine ll-cis-retinal with opsin to form rhodopsin.Sinceit is difficult to obtain the ll-cis-retinal,Hubbard et al.suggested an“isorhodopsin”from9-cis-retinal and amine to mimic the rhodopsin,and a photoisomerization effect can be ob-served in this system.However,there were no reports about the photoelectric response ofthis“isorhodopsin”.In this article,we measure the photoresponse of展开更多
Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and effic...Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].展开更多
An important feature of quantum chromodynamics(QCD)is that the strong force grows as the distance between partons increases,which confines partons into hadrons,commonly known as QCD confinement.Perturbative QCD(pQCD)d...An important feature of quantum chromodynamics(QCD)is that the strong force grows as the distance between partons increases,which confines partons into hadrons,commonly known as QCD confinement.Perturbative QCD(pQCD)does not work at large distance,such as the length scale of a hadron,which is the regime of non-perturbative QCD.The detailed QCD mechanisms through which confinement occurs from partons to hadrons(usually known as hadronization),and how it manifests itself in partonic structure of hadrons(usually known as parton distribution),remain unresolved puzzles of first-principle QCD calculations.展开更多
We successfully incorporated phenyl groups into a small-molecule quaternary ammonium cross-linker and synthesized cross-linked polybenzimidazole membranes via a one-step cross-linking process.Compared with conventiona...We successfully incorporated phenyl groups into a small-molecule quaternary ammonium cross-linker and synthesized cross-linked polybenzimidazole membranes via a one-step cross-linking process.Compared with conventional quaternary ammonium-crosslinked benzimidazole membranes,the introduction of phenyl groups significantly increases the free volume within the membrane.After phosphoric acid doping,the benzimidazole membrane with larger free volume retains more phosphoric acid compared to conventional quaternary ammonium-crosslinked membranes,forming an extensive hydrogen-bonding network that effectively enhances its anhydrous proton conductivity.The anhydrous proton conductivity reaches 91 mS·cm^(-1)at 160℃,substantially higher than that of conventional quaternary ammonium-crosslinked membranes with the same mass fraction.Benefiting from the improved conductivity,the membrane electrode assembly exhibits reduced ohmic polarization,achieving a peak power density of 792 mW·cm^(-2)at 160℃.展开更多
In this paper,we review recent highlights in heavy-ion collisions and proton–proton collisions at top energies from STAR experiment at the Relativistic Heavy Ion Collider(RHIC) with key contributions from Chinese gro...In this paper,we review recent highlights in heavy-ion collisions and proton–proton collisions at top energies from STAR experiment at the Relativistic Heavy Ion Collider(RHIC) with key contributions from Chinese groups,including the quark–gluon plasma bulk properties,electromagnetic probes,heavy flavor and jets,antimatter hyper-nucleus,nuclear structure,global polarization,and nucleon spin structure.These data serve as important ingredients in the physics of quantum chromodynamics.展开更多
基金supported by the National Natural Science Foundation of China(No.2021YFC3200603)the Special Research Assistant Program,Chinese Academy of Sciences.
文摘Photocatalytic disinfection is an eco-friendly strategy for countering bacterial pollution in aquatic environments.Numerous strategies have been devised to facilitate the generation of reactive oxygen species(ROS)within photocatalysts,ultimately leading to the eradication of bacteria.However,the significance of the physical morphology of photocatalysts in the context of sterilization is frequently obscured,and the progress in the development of physical-chemical synergistic sterilization photocatalysts has been relatively limited.Herein,graphitic carbon nitride(g-C_(3)N_(4))is chemically protonated to expose more sharp edges.PL fluorescence and EIS results indicate that the protonation can accelerate photogenerated carrier separation and enhance ROS production.Meanwhile,the sharp edges on the protonated g-C_(3)N_(4)facilitate the physical disruption of cell walls for further promoting oxidative damage.Protonated C_(3)N_(4)demonstrated superior bactericidal performance than that of pristine g-C_(3)N_(4),effectively eliminating Escherichia coli within 40 minutes under irradiation.This work highlights the significance of incorporating physical and chemical synergies in photocatalyst design to enhance the disinfection efficiency of photocatalysis.
基金Funded by Natural Science Foundation of China (No. 50002007), Major Program of Chinese Education Ministry and Open Foundation of State Key Lab. of Advanced Tech. for Materials Syn-thesis and Processing.
文摘New layered perovskites, KSr2Nb3O10 and two new protonated niobates HSr2 Nb3O10·1.2H2O and HSr2Nb3O10,were synthesized by solid state reaction and ion-exchange reaction. These new compounds -were characterized by EPMA, AAS, XRD, IR, DTA and so on. The structure may be described as treble perovskite sheets [Sr2Nb3O10]- interleaved with K+ ,H3O + or H+. These new compounds are new members of the Dion-Jacob-sonseries with n=3 for the general formula M[An-1 NbnO3n+1], and their indexed X-ray powder diffraction data were first reported in the paper.
基金Project supported by the National Basic Research Program of China (973 Program,Grant No.2013CB932804)the National Natural Science Foundation of China (Grant Nos.91227115 and 11121403)the Hundred Talent Program of the Chinese Academy of Sciences (CAS)
文摘Formation and dissociation mechanisms of C-C＋ base pairs in acidic and alkaline environments are investigated, employing ab initio quantum chemical calculations. Our calculations suggest that, in an acidic environment, a cytosine monomer is first protonated and then dimerized with an unprotonated cytosine monomer to form a C-C＋ base pair; in an alkaline environment, a protonated cytosine dimer is first unprotonated and then dissociated into two cytosine monomers. In addition, the force for detaching a C-C＋ base pair was found to be inversely proportional to the distance between the two cytosine monomers. These results provide a microscopic mechanism to qualitatively explain the experimentally observed reversible formation and dissociation of i-motifs.
基金supported in part by JSPS KAKENHI Grant Numbers in Japan(JP21H05229 to I.K.)JST CREST(JPMJCR21B2)The authors also thank Nobuko Yamaguchi for the financial support.
文摘Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base(RPSB).Microbial rhodopsins absorb light through chromophore and play a fundamental role in optogenetics.Numerous microbial rhodopsins have been discovered,contributing to diverse functions and colors.Solid-state NMR spectroscopy has been instrumental in elucidating the conformation of chromophores and the three-dimensional structure of microbial rhodopsins.This review focuses on the 15N chemical shift values of RPSB and summarizes recent progress in the field.We displayed the correlation between the 15N isotropic chemical shift values of RPSB and the maximum absorption wavelength of rhodopsin using solid-state NMR spectroscopy.
文摘A modified method for preparation and purification of Schiff base and protonated Schiff base from 9-cis-retinal has been suggested. Reaction took place in chloroform phase and purification was conducted by using water to remove the excess solvent, base and acid.
文摘Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.
基金supported by the National Natural Science Foundation of China(Nos.21475065,21627801 and 11704280)
文摘Infrared multiple photon dissociation （IRMPD） spectroscopic and theoretical studies of protonated homodimers of amino acids generated by electrospray ionization in the gas phase have been reviewed. Results show that proton affinity （PA） may be applied as a probe to predict their structural type： salt- bridged or charge-solvated. Proline can be viewed as a reference. For an amino acid with a PA value higher than that of proline, the most stable conformation of its protonated homodimer tends to prefer salt- bridged conformation; otherwise, charge-solvated conformation is expected to be the most stable. However, side chain effects may cause the inaccuracy in structural determination due to the strong interactions with the charge, which makes the charge-solvated structure more stable even for species with high PA values. Temperature effect on distribution of different isomers is also very important. In lots of cases, the coexistence of multiple isomers is general, which makes the explanation of an overall IRMPD spectrum difficult. So a statistical view on the distribution of optimized isomers is very helpful.
文摘The low energy collisioninduced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact and chemical ionization conditions. It was found that this compound shows an unusual reactivity towards protonation. Two possible sites of protonation have been proposed to explain the corresponding fragmentation processes, one is that the protonation takes place on the oxygen atom of hydroxyl group, resulting in the loss of water and the other is the formation of an intermediary protonbound complex in the fragmentation process, giving rise to the fragment ions of m/z 133 and m/z 135. The results show both cases are coexistence in the fragmentations of protonated N-hydroxyphthalimide, and the unimolecular fragmentation pathways are available.
基金Supported by the National Natural Science Foundation of China (21133007 and 20873105)the Ministry of Science and Technology (2011CB808504 and 2012CB214902)
文摘Density functional calculations are used to determine structural and electronic properties of P4,P4O6,P4O10,P20O30 and P20O50 clusters and their protonated derivatives.These oxygen-rich phosphorus oxides are predicted to have relatively high stabilities with respect to their components P4 and O2,and their unsaturated P and end-on O atoms as the proton acceptor can accommodate multiple protons to generate highly positively charged cationic clusters,such as P20O30H1010＋.Calculations indicate that P4O6 and P20O30 have higher reactivity toward the proton capture than the P4,P4O10 and P20O50 clusters,and the most stable protonated clusters among these different series of cationic clusters are P4H2……2＋,P4O6H2^2＋,P4O10H3^3＋,P20O30H4^4＋ and P20O50H4^4＋,respectively.The cage skeleton of the phosphorus oxide clusters shows high stability for the consecutive protonation,and the unsymmetrical stretching of the skeletal P-O bond and the wagging mode of P-H coupled with the P-O bond stretching have strong adsorptions.These computational findings are useful for further experimental and theoretical studies of novel phosphorus oxide clusters and their highly positively charged derivatives.
基金supported by the Science and Technology Program of Guangzhou,China(No.201803030019)the Key Laboratory of Renewable Energy,Chinese Academy Sciences Foundation(No.Y707j71001).We thank the support from the Analysis and Testing Center of Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences.
文摘A novel photocatalyst with protonated carbon nitride(p-C_(3)N_(4))loaded with IrO_(2)quantum dots(QDs)was fabricated via a facile hydrothermal method.Structure characterization studies(XRD,STEM,XPS,UV–vis spectra and PL spectra)revealed that the IrO_(2)QDs with an average diameter of ca.
基金supported by the Science and Technology Project of Jiangsu Province(BZ2022056,BK20210356)the National Natural Science Foundation of China(22205109,21975128)the Fundamental Research Funds for the Central Universities(30922010812)。
文摘Covalent organic frameworks(COFs)are emerging as promising photocatalysts owing to their tailorable structures,exceptional crystallinity,and robustness.However,the photocatalytic performance of COFs is limited by fast charge recombination and inefficient charge migration.Herein,a novel post-synthetic partial protonation strategy is proposed to construct COFs with asymmetric unprotonated/protonated homojunctions,which endow them with an enlarged molecular dipole moment,thereby generating a strong built-in electric field that significantly enhances the charge separation and transport efficiencies in COFs.In addition,the protonation process extends the light absorption range and improves the hydrophilicity of COFs.The photocatalytic hydrogen evolution rate of the partially protonated TPE-COF and ETTBA-COF is enhanced by 88-and 175-fold relative to their pristine counterparts,4.3 and 2.48 times those of fully protonated counterparts,respectively.Our results clearly demonstrate the pivotal role of the asymmetric unprotonated/protonated homojunctions within COFs in the photocatalytic hydrogen evolution.This post-synthetic partial protonation strategy provides a novel paradigm for establishing internal electric fields within COFs.
文摘In this work, we demonstrated the successful construction of metal-free zero- dimensional/two-dimensional carbon nanodot （CND）-hybridized protonatedg=C3N4 （pCN） （CND/pCN） heterojunction photocatalysts b; means of electrostatic attraction. We experimentally found that CNDs with an average diameter of 4.4 nm were uniformly distributed on the surface of pCN using electron microscopy analysis. The CND/pCN-3 sample with a CND content of 3 wt.% showed thehighest catalytic activity in the CO2 photoreduction process under visible and simulated solar light. This process results in the evolution of CH4 and CO. Thetotal amounts of CH4 and CO generated by the CND/pCN-3 photocatalyst after 10 h of visible-light activity were found to be 29.23 and 58.82 molgcatalyst-1, respectively. These values were 3.6 and 2.28 times higher, respectively, than thearn＊ounts generated when using pCN alone. The corresponding apparent quantum efficiency （AQE） was calculated to be 0.076%. Furthermore, the CND/pCN-3 sample demonstrated high stability and durability after four consecutive photoreaction cycles, with no significant decrease in the catalytic activity.
文摘This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.
基金supported by grants from the Natural Science Foundation of China(22362031 and 21805121)the Science and Technology Project of Yunnan Province(2019FD137)。
文摘Proton exchange membrane fuel cells(PEMFCs)are considered as a promising renewable power source.However,the massive commercial application of PEMFCs has been greatly hindered by their high expense and less-satisfied performance mainly due to the sluggish oxygen reduction reaction(ORR)kinetics even on state-of-the-art Pt catalyst.Octahedral PtNi nanoparticles(oct-PtNi NPs)with excellent ORR activity in a half-cell have been widely studied,while their performance in membrane electrode assembly(MEA)has much less reported.Herein,we investigated the MEA performance using the carbon supported oct-PtNi NPs(oct-PtNi/C)as the cathode catalyst.Under the mild acid washing condition,the surface Ni atoms of oct-PtNi/C were largely removed,and the performance of the MEA using the acid-leaching oct-PtNi/C(PNC-A)as the cathode catalyst was greatly improved.The maximum power density of the MEA reached 1.0 W·cm^(-2) with the cath-ode Pt loading of 0.2 mg·cm^(-2),which is 15%higher than that using Pt/C as the catalyst.After 30k cycles in the accelerated degradation test(ADT),the MEA using PNC-A as the catalyst showed a performance retention of 82%,higher than that of Pt/C(74%).The results reported here verify the possibility of using PNC-A as an advanced cathode catalyst in PEMFCs,thus enhancing the performance of PEMFCs while lowering the amount of expensive Pt.
基金Project supported by the National Natural Science Foundation of China.
文摘Ordered thin organic films deposited on solid substrates by the Langmuir-Blodgett(LB) technique have attracted much attention because of their possibility of being applied tofunctional molecular device architectures, such as electronic, nonlinear optical and bio-logical sensors. Very elegant work has been carried out by Kuhn and his
文摘It has been investigated for a long time by many authors to mimic the vision pro-cess.The most important step is to synthesize pigments having similar function ofrhodopsin,for example,to combine ll-cis-retinal with opsin to form rhodopsin.Sinceit is difficult to obtain the ll-cis-retinal,Hubbard et al.suggested an“isorhodopsin”from9-cis-retinal and amine to mimic the rhodopsin,and a photoisomerization effect can be ob-served in this system.However,there were no reports about the photoelectric response ofthis“isorhodopsin”.In this article,we measure the photoresponse of
文摘Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].
基金supported in part by the National Natural Science Foundation of China(No.12575145)the National Key Research and Development Program of China(No.2022YFA1604900)。
文摘An important feature of quantum chromodynamics(QCD)is that the strong force grows as the distance between partons increases,which confines partons into hadrons,commonly known as QCD confinement.Perturbative QCD(pQCD)does not work at large distance,such as the length scale of a hadron,which is the regime of non-perturbative QCD.The detailed QCD mechanisms through which confinement occurs from partons to hadrons(usually known as hadronization),and how it manifests itself in partonic structure of hadrons(usually known as parton distribution),remain unresolved puzzles of first-principle QCD calculations.
基金Funded in part by the National Key Research and Development Program of China(No.2023YFB4006302)。
文摘We successfully incorporated phenyl groups into a small-molecule quaternary ammonium cross-linker and synthesized cross-linked polybenzimidazole membranes via a one-step cross-linking process.Compared with conventional quaternary ammonium-crosslinked benzimidazole membranes,the introduction of phenyl groups significantly increases the free volume within the membrane.After phosphoric acid doping,the benzimidazole membrane with larger free volume retains more phosphoric acid compared to conventional quaternary ammonium-crosslinked membranes,forming an extensive hydrogen-bonding network that effectively enhances its anhydrous proton conductivity.The anhydrous proton conductivity reaches 91 mS·cm^(-1)at 160℃,substantially higher than that of conventional quaternary ammonium-crosslinked membranes with the same mass fraction.Benefiting from the improved conductivity,the membrane electrode assembly exhibits reduced ohmic polarization,achieving a peak power density of 792 mW·cm^(-2)at 160℃.
基金supported in part by the National Key Research and Development Program of China (Grant No.2022YFA1604900)the National Natural Science Foundation of China (Grant No.12575145)。
文摘In this paper,we review recent highlights in heavy-ion collisions and proton–proton collisions at top energies from STAR experiment at the Relativistic Heavy Ion Collider(RHIC) with key contributions from Chinese groups,including the quark–gluon plasma bulk properties,electromagnetic probes,heavy flavor and jets,antimatter hyper-nucleus,nuclear structure,global polarization,and nucleon spin structure.These data serve as important ingredients in the physics of quantum chromodynamics.
