Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production.However,developing effective and stable non‐noble‐metal electrocatalysts which work well at high current densities demand...Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production.However,developing effective and stable non‐noble‐metal electrocatalysts which work well at high current densities demanded by industry still remain great challenge.Herein,taking advantage of the highly tunable metal‐organic framework(MOF)templates,nitrogen doped binary transition metal phosphides electrocatalysts(N‐CoP_(x)/Ni_(2)P)with three‐dimensional(3D)conductive network structure were successfully synthesized.The 3D open porous channels could expose more catalytically active sites;nitrogen doping and the synergistic effect between CoP and Ni_(2)P can increase the electron density of Co atoms at active sites,further optimizing the Gibbs free energy of hydrogen(ΔGH*)and water(ΔG_(H_(2)O*)).As a result,the obtained N‐CoP_(x)/Ni_(2)P catalyst exhibits extraordinary electrocatalytic activity in a wide pH range.Especially,it requires an extremely low overpotential of 152 mV to deliver a high current density of 650 mA cm^(–2) in alkaline media.This work may shed some light on the rational design of cheap electrocatalysts and electrode materials that work well at high current densities.展开更多
The prototypical E2 elimination and SN2 sub-stitution reactions between microsolvated fluoride and ethyl bromide show unexpected dynamic behaviors in mechanistic evolution driven by solvation and collision activation....The prototypical E2 elimination and SN2 sub-stitution reactions between microsolvated fluoride and ethyl bromide show unexpected dynamic behaviors in mechanistic evolution driven by solvation and collision activation.Considering the steric effects,the gas-phase selectivity favors an E2 pathway barely dependent on collision energies.Remarkably,base solvation steers the reaction in an effective way toward substitution at a near-thermal energy,whereas the governing high-energy events retain elimination.Chemical dynamics simulations reproduce exper-imental findings and uncover a crucial solute-solvent coupling in determining such competing processes.Interestingly,collision activation can tune the underlying atomistic dynamics essentially in the reactant entrance channel and cause a mechanism shift.These features for the ubiquitous competing E2/SN2 dynamics remain quite unknown,providing unique insight into reaction selectivity for complex chemical networks.展开更多
Measurement of the cross-sections of the ^(79)Br(n,2n)^(78)Br,^(81)Br(n,p)^(81)mSe,^(81)Br(n,α)^(78)As,and ^(79)Br(n,α)^(76)As reactions was performed at specific neutron energies,precisely,13.5±0.2,14.1±0...Measurement of the cross-sections of the ^(79)Br(n,2n)^(78)Br,^(81)Br(n,p)^(81)mSe,^(81)Br(n,α)^(78)As,and ^(79)Br(n,α)^(76)As reactions was performed at specific neutron energies,precisely,13.5±0.2,14.1±0.2,14.4±0.2,and 14.8±0.2 MeV,relative to the standard ^(93)Nb(n,2n)^(92)mNb and ^(27)Al(n,α)^(24)Na reference reactions using offlineγ-ray spectrometry and neutron activation.Monoenergetic neutrons were generated at the China Academy of Engineering Physics via a ^(3)H(d,n)^(4)He reaction using the K-400 Neutron Generator equipped with a solid ^(3)H-Ti based target.The activity of the reaction produce was obtained using a high-purity germanium detector.The cross-sections of the(n,2n),(n,p),and(n,α)reactions on the bromine isotopes were measured in the 13–15 MeV neutron energy range.The covariance analysis approach was employed for a thorough inspection of any uncertainties within the measured cross-section data.A discussion and comparison of the observed outcome were carried out with previously published data,especially with the results of the JENDL-4.0,JEFF-3.3,TENDL-2019,and ENDF/B-VIII.0 data libraries,along with the theoretical excitation function curve derived by employing the TALYS-1.95 program.Improved cross-section restrictions for the investigated processes in the 13–15 MeV neutron energy range will be obtained using the current findings,which will help to raise the caliber of associated databases.Furthermore,the parameters of relevant nuclear reaction models can be verified using this data.展开更多
Cross-section data of the^(185)Re(n,2n)^(184)mRe,^(185)Re(n,2n)^(184)gRe,^(185)Re(n,α)182m1+m2+gTa,^(187)Re(n,2n)^(186)g,(m)Re,^(187)Re(n,α)^(184)Ta,and^(187)Re(n,p)^(187)W reactions were measured at four neutron en...Cross-section data of the^(185)Re(n,2n)^(184)mRe,^(185)Re(n,2n)^(184)gRe,^(185)Re(n,α)182m1+m2+gTa,^(187)Re(n,2n)^(186)g,(m)Re,^(187)Re(n,α)^(184)Ta,and^(187)Re(n,p)^(187)W reactions were measured at four neutron energies,namely 13.5,14.1,14.4,and 14.8 MeV,by means of the activation technique,relative to the reference cross-section values of the 93Nb(n,2n)92mNb reaction.The neutrons were generated from the T(d,n)4He reaction at the K-400 Neutron Generator at China Academy of Engineering Physics.The inducedγactivities were measured using a high-resolutionγ-ray spectrometer equipped with a coaxial high-purity germanium detector.The excitation functions of the six above-mentioned nuclear reactions at neutron energies from the threshold to 20 MeV were calculated by adopting the nuclear theoretical model program system Talys-1.9 with the relevant parameters properly adjusted.The measured cross sections were analyzed and compared with previous experiments conducted by other researchers,and with the evaluated data of BROND-3.1,ENDF/B-VIII.0,JEFF-3.3,and the theoretical values based on Talys-1.9.The new measured results agree with those of previous experiments and the theoretical excitation curve at the corresponding energies.The theoretical excitation curves based on Talys-1.9 generally match most of experimental data well.展开更多
The reaction cross-sections of ^(124)Xe(n,2n)^(123)Xe,^(126)Xe(n,2n)^(125)Xe,^(128)Xe(n,2n)^(127)Xe,^(130)Xe(n,2n)^(129)mXe,^(132)Xe(n,2n)^(131)mXe,^(130)Xe(n,p)^(130)I,^(131)Xe(n,p)^(131)I,and ^(132)Xe(n,p)^(132)I we...The reaction cross-sections of ^(124)Xe(n,2n)^(123)Xe,^(126)Xe(n,2n)^(125)Xe,^(128)Xe(n,2n)^(127)Xe,^(130)Xe(n,2n)^(129)mXe,^(132)Xe(n,2n)^(131)mXe,^(130)Xe(n,p)^(130)I,^(131)Xe(n,p)^(131)I,and ^(132)Xe(n,p)^(132)I were measured at the 13.5,13.8,14.1,14.4,and 14.8 MeV neutron energies.The monoenergetic neutrons were generated via the ^(3)H(d,n)^(4)He reaction at the China Academy of Engineering Physics using the K-400 Neutron Generator with a solid ^(3)H-Ti target.A high-purity germanium detector was employed to measure the activities of the product.The reactions ^(93)Nb(n,2n)^(92m)Nb and ^(27)Al(n,α)^(24)Na were adopted for neutron flux calibration.The cross sections of the(n,2n)and(n,p)reactions of the xenon isotopes were obtained within the 13-15 MeV neutron energy range.These cross-sections were then compared with the IAEA-exchange format(EXFOR)database-derived experimental data,together with the evaluation results of the CENDL-3,ENDF/B-Ⅷ.0,JENDL-4.0,RUSFOND,and JEFF-3.3 data libraries,as well as the theoretical excitation function obtained using the TALYS-1.95 code.The cross-sections of the reactions(except for the ^(124)Xe(n,2n)^(123)Xe and ^(132)Xe(n,p)^(132)I)at 13.5,13.8,and 14.1 MeV are reported for the first time in this study.The obtained results are beneficial in providing better cross-section constraints for the reactions in the 13-15 MeV region,thus improving the quality of the corresponding database.Meanwhile,these data can also be used for the verification of relevant nuclear reaction model parameters.展开更多
The cross sections of the^(121)Sb(n,2n)^(120)Sb^(m) and ^(123)Sb(n,2n)^(122)Sb reactions were measured at 12.50,15.79 and 18.87 MeV neutron energies relative to the standard ^(27)Al(n,α)^(24)Na monitor reaction using...The cross sections of the^(121)Sb(n,2n)^(120)Sb^(m) and ^(123)Sb(n,2n)^(122)Sb reactions were measured at 12.50,15.79 and 18.87 MeV neutron energies relative to the standard ^(27)Al(n,α)^(24)Na monitor reaction using neutron activation and offline γ-ray spectrometry.Irradiation of the samples was performed at the BARC-TIFR Pelletron Linac Facility,Mumbai,India.The quasi-monoenergetic neutrons were generated via the ^(7)Li(p,n)reaction.Statistical model calculations were performed by nuclear reaction codes TALYS(ver.1.9)and EMPIRE(ver.3.2.2)using various input parameters and nuclear level density models.The cross sections of the ground and the isomeric state as well as the isomeric cross section ratio were studied theoretically from reaction threshold to 26 MeV energies.The effect of pre-equilibrium emission is also discussed in detail using different theoretical models.The present measured cross sections were discussed and compared with the reported experimental data and evaluation data of the JEFF-3.3,ENDF/B-VIII.0,JENDL/AD-2017 and TENDL-2019 libraries.A detailed analysis of the uncertainties in the measured cross section data was performed using the covariance analysis method.Furthermore,a systematic study of the(n,2n)reaction cross section for^(121)Sb and^(123)Sb isotopes was also performed within 14-15 MeV neutron energies using various systematic formulae.This work helps to overcome discrepancies in Sb data and illustrate a better understanding of pre-equilibrium emission in the(n,2n)reaction channel.展开更多
Ubiquitous competition of stereospecific E2 elimination versus SN2 substitution is of central importance in chemical synthesis.Herein,we uncover how the nature of the leaving group affects the intrinsic competing dyna...Ubiquitous competition of stereospecific E2 elimination versus SN2 substitution is of central importance in chemical synthesis.Herein,we uncover how the nature of the leaving group affects the intrinsic competing dynamics that remains largely unknown as opposed to its role in reactivity.Results are presented for a prototype case of fluoride anion reacting with ethyl chloride,compared to reacting with ethyl iodide.Chemical dynamics simulations reproduce scattering signatures observed in experiments and reveal that the direct stripping/rebound mechanisms characterize the E2/S_(N)2 reactions,in line with their dynamic fingerprints identified.Quite similar structures and energetics are found for the Cl^(−)and I^(−)leaving halides,whereas the competing dynamics show markedly distinct features.A halogen-bonding attraction is found to be crucial that modifies the interaction potential in the entrance channel and essentially tunes the underlying atomistic behaviors causing a mechanistic shift.This work highlights the dynamical effects induced by a leaving group on the proceedings of baseinduced elimination and nucleophilic substitution,providing a unique insight into the reaction selectivity for complex chemical networks and environments.展开更多
文摘Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production.However,developing effective and stable non‐noble‐metal electrocatalysts which work well at high current densities demanded by industry still remain great challenge.Herein,taking advantage of the highly tunable metal‐organic framework(MOF)templates,nitrogen doped binary transition metal phosphides electrocatalysts(N‐CoP_(x)/Ni_(2)P)with three‐dimensional(3D)conductive network structure were successfully synthesized.The 3D open porous channels could expose more catalytically active sites;nitrogen doping and the synergistic effect between CoP and Ni_(2)P can increase the electron density of Co atoms at active sites,further optimizing the Gibbs free energy of hydrogen(ΔGH*)and water(ΔG_(H_(2)O*)).As a result,the obtained N‐CoP_(x)/Ni_(2)P catalyst exhibits extraordinary electrocatalytic activity in a wide pH range.Especially,it requires an extremely low overpotential of 152 mV to deliver a high current density of 650 mA cm^(–2) in alkaline media.This work may shed some light on the rational design of cheap electrocatalysts and electrode materials that work well at high current densities.
基金supported by the State Key Lab of Urban Water Resource and Environment of Harbin Institute of Technology(No.ES202303)the National Natural Science Foundation of China(No.22203039).
文摘The prototypical E2 elimination and SN2 sub-stitution reactions between microsolvated fluoride and ethyl bromide show unexpected dynamic behaviors in mechanistic evolution driven by solvation and collision activation.Considering the steric effects,the gas-phase selectivity favors an E2 pathway barely dependent on collision energies.Remarkably,base solvation steers the reaction in an effective way toward substitution at a near-thermal energy,whereas the governing high-energy events retain elimination.Chemical dynamics simulations reproduce exper-imental findings and uncover a crucial solute-solvent coupling in determining such competing processes.Interestingly,collision activation can tune the underlying atomistic dynamics essentially in the reactant entrance channel and cause a mechanism shift.These features for the ubiquitous competing E2/SN2 dynamics remain quite unknown,providing unique insight into reaction selectivity for complex chemical networks.
基金Supported by the National Natural Science Foundation of China(12165006,11875016).
文摘Measurement of the cross-sections of the ^(79)Br(n,2n)^(78)Br,^(81)Br(n,p)^(81)mSe,^(81)Br(n,α)^(78)As,and ^(79)Br(n,α)^(76)As reactions was performed at specific neutron energies,precisely,13.5±0.2,14.1±0.2,14.4±0.2,and 14.8±0.2 MeV,relative to the standard ^(93)Nb(n,2n)^(92)mNb and ^(27)Al(n,α)^(24)Na reference reactions using offlineγ-ray spectrometry and neutron activation.Monoenergetic neutrons were generated at the China Academy of Engineering Physics via a ^(3)H(d,n)^(4)He reaction using the K-400 Neutron Generator equipped with a solid ^(3)H-Ti based target.The activity of the reaction produce was obtained using a high-purity germanium detector.The cross-sections of the(n,2n),(n,p),and(n,α)reactions on the bromine isotopes were measured in the 13–15 MeV neutron energy range.The covariance analysis approach was employed for a thorough inspection of any uncertainties within the measured cross-section data.A discussion and comparison of the observed outcome were carried out with previously published data,especially with the results of the JENDL-4.0,JEFF-3.3,TENDL-2019,and ENDF/B-VIII.0 data libraries,along with the theoretical excitation function curve derived by employing the TALYS-1.95 program.Improved cross-section restrictions for the investigated processes in the 13–15 MeV neutron energy range will be obtained using the current findings,which will help to raise the caliber of associated databases.Furthermore,the parameters of relevant nuclear reaction models can be verified using this data.
基金Supported by National Natural Science Foundation of China(11605099,11575090)。
文摘Cross-section data of the^(185)Re(n,2n)^(184)mRe,^(185)Re(n,2n)^(184)gRe,^(185)Re(n,α)182m1+m2+gTa,^(187)Re(n,2n)^(186)g,(m)Re,^(187)Re(n,α)^(184)Ta,and^(187)Re(n,p)^(187)W reactions were measured at four neutron energies,namely 13.5,14.1,14.4,and 14.8 MeV,by means of the activation technique,relative to the reference cross-section values of the 93Nb(n,2n)92mNb reaction.The neutrons were generated from the T(d,n)4He reaction at the K-400 Neutron Generator at China Academy of Engineering Physics.The inducedγactivities were measured using a high-resolutionγ-ray spectrometer equipped with a coaxial high-purity germanium detector.The excitation functions of the six above-mentioned nuclear reactions at neutron energies from the threshold to 20 MeV were calculated by adopting the nuclear theoretical model program system Talys-1.9 with the relevant parameters properly adjusted.The measured cross sections were analyzed and compared with previous experiments conducted by other researchers,and with the evaluated data of BROND-3.1,ENDF/B-VIII.0,JEFF-3.3,and the theoretical values based on Talys-1.9.The new measured results agree with those of previous experiments and the theoretical excitation curve at the corresponding energies.The theoretical excitation curves based on Talys-1.9 generally match most of experimental data well.
基金Supported by the National Natural Science Foundation of China(11875016,12165006)。
文摘The reaction cross-sections of ^(124)Xe(n,2n)^(123)Xe,^(126)Xe(n,2n)^(125)Xe,^(128)Xe(n,2n)^(127)Xe,^(130)Xe(n,2n)^(129)mXe,^(132)Xe(n,2n)^(131)mXe,^(130)Xe(n,p)^(130)I,^(131)Xe(n,p)^(131)I,and ^(132)Xe(n,p)^(132)I were measured at the 13.5,13.8,14.1,14.4,and 14.8 MeV neutron energies.The monoenergetic neutrons were generated via the ^(3)H(d,n)^(4)He reaction at the China Academy of Engineering Physics using the K-400 Neutron Generator with a solid ^(3)H-Ti target.A high-purity germanium detector was employed to measure the activities of the product.The reactions ^(93)Nb(n,2n)^(92m)Nb and ^(27)Al(n,α)^(24)Na were adopted for neutron flux calibration.The cross sections of the(n,2n)and(n,p)reactions of the xenon isotopes were obtained within the 13-15 MeV neutron energy range.These cross-sections were then compared with the IAEA-exchange format(EXFOR)database-derived experimental data,together with the evaluation results of the CENDL-3,ENDF/B-Ⅷ.0,JENDL-4.0,RUSFOND,and JEFF-3.3 data libraries,as well as the theoretical excitation function obtained using the TALYS-1.95 code.The cross-sections of the reactions(except for the ^(124)Xe(n,2n)^(123)Xe and ^(132)Xe(n,p)^(132)I)at 13.5,13.8,and 14.1 MeV are reported for the first time in this study.The obtained results are beneficial in providing better cross-section constraints for the reactions in the 13-15 MeV region,thus improving the quality of the corresponding database.Meanwhile,these data can also be used for the verification of relevant nuclear reaction model parameters.
基金IUAC New Delhi financial assistance through a research project (IUAC/XIII.7/UFR-60321)
文摘The cross sections of the^(121)Sb(n,2n)^(120)Sb^(m) and ^(123)Sb(n,2n)^(122)Sb reactions were measured at 12.50,15.79 and 18.87 MeV neutron energies relative to the standard ^(27)Al(n,α)^(24)Na monitor reaction using neutron activation and offline γ-ray spectrometry.Irradiation of the samples was performed at the BARC-TIFR Pelletron Linac Facility,Mumbai,India.The quasi-monoenergetic neutrons were generated via the ^(7)Li(p,n)reaction.Statistical model calculations were performed by nuclear reaction codes TALYS(ver.1.9)and EMPIRE(ver.3.2.2)using various input parameters and nuclear level density models.The cross sections of the ground and the isomeric state as well as the isomeric cross section ratio were studied theoretically from reaction threshold to 26 MeV energies.The effect of pre-equilibrium emission is also discussed in detail using different theoretical models.The present measured cross sections were discussed and compared with the reported experimental data and evaluation data of the JEFF-3.3,ENDF/B-VIII.0,JENDL/AD-2017 and TENDL-2019 libraries.A detailed analysis of the uncertainties in the measured cross section data was performed using the covariance analysis method.Furthermore,a systematic study of the(n,2n)reaction cross section for^(121)Sb and^(123)Sb isotopes was also performed within 14-15 MeV neutron energies using various systematic formulae.This work helps to overcome discrepancies in Sb data and illustrate a better understanding of pre-equilibrium emission in the(n,2n)reaction channel.
基金supported by the State Key Lab of Urban Water Resource and Environment of the Harbin Institute of Technology(No.ES202303)。
文摘Ubiquitous competition of stereospecific E2 elimination versus SN2 substitution is of central importance in chemical synthesis.Herein,we uncover how the nature of the leaving group affects the intrinsic competing dynamics that remains largely unknown as opposed to its role in reactivity.Results are presented for a prototype case of fluoride anion reacting with ethyl chloride,compared to reacting with ethyl iodide.Chemical dynamics simulations reproduce scattering signatures observed in experiments and reveal that the direct stripping/rebound mechanisms characterize the E2/S_(N)2 reactions,in line with their dynamic fingerprints identified.Quite similar structures and energetics are found for the Cl^(−)and I^(−)leaving halides,whereas the competing dynamics show markedly distinct features.A halogen-bonding attraction is found to be crucial that modifies the interaction potential in the entrance channel and essentially tunes the underlying atomistic behaviors causing a mechanistic shift.This work highlights the dynamical effects induced by a leaving group on the proceedings of baseinduced elimination and nucleophilic substitution,providing a unique insight into the reaction selectivity for complex chemical networks and environments.
