The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and deba...The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.展开更多
Electrochemical reduction of nitrate,a common pollutant in aquatic environment,to valuable ammonia(NO3-RR) using renewably-sourced electricity has attracted widespread interests,with past efforts mainly focused on des...Electrochemical reduction of nitrate,a common pollutant in aquatic environment,to valuable ammonia(NO3-RR) using renewably-sourced electricity has attracted widespread interests,with past efforts mainly focused on designing electrocatalysts with high activity and selectivity.The detailed correlation between catalyst properties and NO3-RR kinetics,nevertheless,is still not fully understood.In this work,we modulate the surface oxygen species of Cu_(2)O via facet engineering,and systematically study the impact of these oxygen species on the NO_(3)^(-)RR activity.Combining advanced spectroscopic techniques,densi ty fu n ctional theory calculations and molecular dynamics simulations,we find that while oxygen vacancies on Cu_(2)O(111) surface promote the adsorption of reactants and reaction intermediates,hydroxyl groups effectively inhibit the side reaction of hydrogen evolution and facilitate the hydrogenation process of NO3-RR.These two effects work in concert to render Cu_(2)O(111) facet the highest NO3-RR activity relative to those from other facets.Our study provides critical insights into the synergistic effect of exposed facets and surface oxygen species on heterogeneous catalysis,and offers a generalizable,facet engineeringbased strategy for improving the performance of a variety of electrocatalysts important for renewable energy conversion.展开更多
The slow redox dynamics and dissolution of polysulfides in lithium-sulfur(Li-S)batteries result in poor rate performance and rapid decay of battery capacity,thus limiting their practical application.Ferroelectric bari...The slow redox dynamics and dissolution of polysulfides in lithium-sulfur(Li-S)batteries result in poor rate performance and rapid decay of battery capacity,thus limiting their practical application.Ferroelectric barium titanate(BT)nanoparticles have been reported to effectively improve the electrochemical performance of Li-S batteries due to the inherent self-polarization and high adsorption capacity of the BT nanoparticles towards polysulfides.Here in this paper,BT nanoparticles,behave as highly efficient electrocatalyst and demonstrate much higher redox dynamics towards the conversion reaction of polysulfides and Li2S than TiO2,as shown by both electrochemical measurements and density functional theory calculation.The coupling of the sulfur host of the hollow and graphitic carbon flakes(HGCF)and the BT nanoparticles(HGCF/S-BT)enable excellent electrochemical performance of Li-S batteries,delivering a0.047%capacity decay per cycle in 1000 cycles at 1 C,788 mAh g^-1 at 2 C and a reversible capacity of613 mAh g^-1 after 300 cycles at a current density of 0.5 C at a S loading of 3.4 mg cm^-2.HGCF/S-BT also shows great promise for practical application in flexible devices as demonstrated on the soft-packaged Li-S batteries.展开更多
The alkaline hydrogen evolution reaction(HER) on Pt-based catalysts is largely limited by the slow water dissociation kinetics. Pt-based single atom alloy catalysts(SAAC) with water dissociation sites have been demons...The alkaline hydrogen evolution reaction(HER) on Pt-based catalysts is largely limited by the slow water dissociation kinetics. Pt-based single atom alloy catalysts(SAAC) with water dissociation sites have been demonstrated as excellent alkaline HER catalysts. However, the regulation of their activity and stability at the atomic scale is still a great challenge. Herein, the kinetic and stability issues are successfully resolved via engineering the electronic structure of Pt-Co SAAC by Au-induced tensile strain. The atomic dispersion of Co into the Pt shell was confirmed by extended X-ray absorption fine structure and the electronic structure and catalytic HER performance was modulated by the tensile strain induced by the Pt shell thickness. An inverse volcano-type relation between HER activity and surface strain was found.Density functional theory(DFT) calculations reveal that the Au-induced tensile strain on Pt-Co shell can not only boost the adsorption and dissociation kinetics of water at Co site by upshifting the dband and promoting the electron transfer, but also downshift the d-band center of Pt in Pt-Co shell, leading to optimized H* adsorption/desorption. The champion catalyst provides an overpotential of only 14 m V at the current density of 10 mA cm^(-2). This work not only provides an effective strategy for the construction of single-atom alloy electrocatalysts for high performance toward alkaline HER but also sheds light on the understanding of the reaction mechanism at the atomic level.展开更多
The electrochemical performance of lithium-sulfur(Li-S)batteries is strongly hampered by the shuttle effect and slow redox kinetics of lithium polysulfides(Li PSs).Surface modified interlayer of a separator of Li-S ba...The electrochemical performance of lithium-sulfur(Li-S)batteries is strongly hampered by the shuttle effect and slow redox kinetics of lithium polysulfides(Li PSs).Surface modified interlayer of a separator of Li-S batteries is demonstrated to be an effective strategy to overcome this problem.Herein,cobalt nanoparticles confined in nitrogen co-doped porous carbon framework(Co-CN)were developed from pyrolysis of ZIF-67 and used as interlayer of PP separator for Li-S batteries,and were functionalized by four pyrrole derivatives,1-phenylpyrrole,1-methyl pyrrole,1-(p-toluenesulfonyl)pyrrole,and 1-pyrrole,respectively,which were screened in terms of the electron-withdrawing/donating ability of the substituent groups on the pyrrolic nitrogen.The impact of the molecular structure of pyrrole derivatives on the interaction with Li PSs and the electrochemical performance of Li-S batteries were explored by nuclear magnetic resonance and theoretical calculation.It is uncovered that 1-phenylpyrrole shows the highest enhancement of redox kinetics of Li PSs,attributing to the optimal interaction with Co nanoparticles and Li PSs.Therefore,1-phenylpyrrole modified Co-CN interlayer enables the best electrochemical performance for the Li-S batteries,delivering a specific capacity of 562 m Ah g^(-1)at 5 C and a capacity of 538,526,and 449 m Ah g^(-1)after 500 cycles at 1,2,and 3 C,respectively.At a high sulfur loading of 5.5 mg cm^(-2),it achieves a capacity of 440 m Ah g^(-1)after 500 cycles at 1 C.This work reveals the interaction mechanism among Li PSs,Co nanoparticles and the molecular modifiers in improving the electrochemical performance of Li-S batteries.展开更多
Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochem...Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochemical performance of SIBs,remains at its infancy.Here in this paper,ZnSe@C nanoparticles were prepared from ZIF-8 and the SEI layers on these electrodes with and without reduced graphene oxide(rGO)layers were examined in details by X-ray photoelectron spectroscopies at varied charged/discharged states.It is observed that fast and complicated electrolyte decomposition reactions on ZnSe@C leads to quite thick SEI film and intercalation of solvated sodium ions through such thick SEI film results in slow ion diffusion kinetics and unstable electrode structure.However,the presence of rGO could efficiently suppress the decomposition of electrolyte,thus thin and stable SEI film was formed.ZnSe@C electrodes wrapped by rGO demonstrates enhanced interfacial charge transfer kinetics and high electrochemical performance,a capacity retention of 96.4%,after 1000 cycles at 5 A/g.This study might offer a simple avenue for the designing high performance anode materials through manipulation of SEI film.展开更多
The photovoltaic performance of perovskite sloar cells(PSCs)is strongly dependent on the crystallinity,morphorlogy and defects of perovskite films.In the present work,a novel strategy was developed to fabricate the hi...The photovoltaic performance of perovskite sloar cells(PSCs)is strongly dependent on the crystallinity,morphorlogy and defects of perovskite films.In the present work,a novel strategy was developed to fabricate the high quality CsPbI3 inorganic perovskite by tuning the growth dynamics of CsPbI3 by pretreatment of fresh CsPbI3 films with phenylethylamine iodide(PEAI).The PEAI can mediate the phase transformation from 1D(DMAPbI3)(DMA:dimethylammonium)to 3D CsPbI3 all-inorganic perovskite films via the PEA2CsPb2I7 of 2D perovskite intermediate phase,resulting in highly crystalline CsPbI3 perovskite films with remarkably enlarged grains and reduced defects.The as-achieved highly crystalline CsPbI3 inorganic perovskite not only exhibited improved phase stability but also significant reduced defects.The perovskite solar cells based on these CsPbI3 thin films exhibited a champion efficiency of 17.08%,much higher than those prepared through posttreatment or direct addition of PEAI into CsPbI3 precursor solution.This work not only developed an effective strategy to prepare high crystalline CsPbI3 film and highly efficient CsPbI3-based all-inorganic PSCs,but also unraveled the mediation mechanism of CsPbI3by pre-treatment of PEAI,shedding light for further development of high perfomance perovskite-based optoelectronics.展开更多
基金supported by the National Natural Science Foundation of China(U2032151,22272059)。
文摘The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.
基金supported by the Guangdong Provincial Natural Science Foundation,China(2021A1515012330)the National Natural Science Foundation of China(11975102)+2 种基金the State Key Laboratory of Pulp and Paper Engineering(2022PY03)the Guangdong Pearl River Talent Program,China(2017GC010281)supported by ME2 project under contract from the National Natural Science Foundation of China(11227902)。
文摘Electrochemical reduction of nitrate,a common pollutant in aquatic environment,to valuable ammonia(NO3-RR) using renewably-sourced electricity has attracted widespread interests,with past efforts mainly focused on designing electrocatalysts with high activity and selectivity.The detailed correlation between catalyst properties and NO3-RR kinetics,nevertheless,is still not fully understood.In this work,we modulate the surface oxygen species of Cu_(2)O via facet engineering,and systematically study the impact of these oxygen species on the NO_(3)^(-)RR activity.Combining advanced spectroscopic techniques,densi ty fu n ctional theory calculations and molecular dynamics simulations,we find that while oxygen vacancies on Cu_(2)O(111) surface promote the adsorption of reactants and reaction intermediates,hydroxyl groups effectively inhibit the side reaction of hydrogen evolution and facilitate the hydrogenation process of NO3-RR.These two effects work in concert to render Cu_(2)O(111) facet the highest NO3-RR activity relative to those from other facets.Our study provides critical insights into the synergistic effect of exposed facets and surface oxygen species on heterogeneous catalysis,and offers a generalizable,facet engineeringbased strategy for improving the performance of a variety of electrocatalysts important for renewable energy conversion.
基金supported by the Fundamental Research Funds for Central Universities(SCUT No.2019ZD22)Guangdong Innovative and Entrepreneurial Research Team Program(No.2016ZT06N569)。
文摘The slow redox dynamics and dissolution of polysulfides in lithium-sulfur(Li-S)batteries result in poor rate performance and rapid decay of battery capacity,thus limiting their practical application.Ferroelectric barium titanate(BT)nanoparticles have been reported to effectively improve the electrochemical performance of Li-S batteries due to the inherent self-polarization and high adsorption capacity of the BT nanoparticles towards polysulfides.Here in this paper,BT nanoparticles,behave as highly efficient electrocatalyst and demonstrate much higher redox dynamics towards the conversion reaction of polysulfides and Li2S than TiO2,as shown by both electrochemical measurements and density functional theory calculation.The coupling of the sulfur host of the hollow and graphitic carbon flakes(HGCF)and the BT nanoparticles(HGCF/S-BT)enable excellent electrochemical performance of Li-S batteries,delivering a0.047%capacity decay per cycle in 1000 cycles at 1 C,788 mAh g^-1 at 2 C and a reversible capacity of613 mAh g^-1 after 300 cycles at a current density of 0.5 C at a S loading of 3.4 mg cm^-2.HGCF/S-BT also shows great promise for practical application in flexible devices as demonstrated on the soft-packaged Li-S batteries.
基金supported by the National Natural Science Foundation of China (U2032151)the National Key R&D Program of China (2018YFB1502600)+1 种基金the Basic Research and Applied Basic Research Foundation of Guangzhou (B3210580)the Natural Science Foundation of Guangdong Province (B6211050)。
文摘The alkaline hydrogen evolution reaction(HER) on Pt-based catalysts is largely limited by the slow water dissociation kinetics. Pt-based single atom alloy catalysts(SAAC) with water dissociation sites have been demonstrated as excellent alkaline HER catalysts. However, the regulation of their activity and stability at the atomic scale is still a great challenge. Herein, the kinetic and stability issues are successfully resolved via engineering the electronic structure of Pt-Co SAAC by Au-induced tensile strain. The atomic dispersion of Co into the Pt shell was confirmed by extended X-ray absorption fine structure and the electronic structure and catalytic HER performance was modulated by the tensile strain induced by the Pt shell thickness. An inverse volcano-type relation between HER activity and surface strain was found.Density functional theory(DFT) calculations reveal that the Au-induced tensile strain on Pt-Co shell can not only boost the adsorption and dissociation kinetics of water at Co site by upshifting the dband and promoting the electron transfer, but also downshift the d-band center of Pt in Pt-Co shell, leading to optimized H* adsorption/desorption. The champion catalyst provides an overpotential of only 14 m V at the current density of 10 mA cm^(-2). This work not only provides an effective strategy for the construction of single-atom alloy electrocatalysts for high performance toward alkaline HER but also sheds light on the understanding of the reaction mechanism at the atomic level.
基金supported by the National Key Research and Development Program of China(Grant No.2017YFA0206703)the National Natural Science Foundation of China(Grant No.U2032151)。
文摘The electrochemical performance of lithium-sulfur(Li-S)batteries is strongly hampered by the shuttle effect and slow redox kinetics of lithium polysulfides(Li PSs).Surface modified interlayer of a separator of Li-S batteries is demonstrated to be an effective strategy to overcome this problem.Herein,cobalt nanoparticles confined in nitrogen co-doped porous carbon framework(Co-CN)were developed from pyrolysis of ZIF-67 and used as interlayer of PP separator for Li-S batteries,and were functionalized by four pyrrole derivatives,1-phenylpyrrole,1-methyl pyrrole,1-(p-toluenesulfonyl)pyrrole,and 1-pyrrole,respectively,which were screened in terms of the electron-withdrawing/donating ability of the substituent groups on the pyrrolic nitrogen.The impact of the molecular structure of pyrrole derivatives on the interaction with Li PSs and the electrochemical performance of Li-S batteries were explored by nuclear magnetic resonance and theoretical calculation.It is uncovered that 1-phenylpyrrole shows the highest enhancement of redox kinetics of Li PSs,attributing to the optimal interaction with Co nanoparticles and Li PSs.Therefore,1-phenylpyrrole modified Co-CN interlayer enables the best electrochemical performance for the Li-S batteries,delivering a specific capacity of 562 m Ah g^(-1)at 5 C and a capacity of 538,526,and 449 m Ah g^(-1)after 500 cycles at 1,2,and 3 C,respectively.At a high sulfur loading of 5.5 mg cm^(-2),it achieves a capacity of 440 m Ah g^(-1)after 500 cycles at 1 C.This work reveals the interaction mechanism among Li PSs,Co nanoparticles and the molecular modifiers in improving the electrochemical performance of Li-S batteries.
基金supported by the Fundamental Research Funds for Central Universities(SCUT Grant No.2019ZD22)the Guangdong Innovative and Entrepreneurial Research Team Program(No.2016ZT06N569)。
文摘Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochemical performance of SIBs,remains at its infancy.Here in this paper,ZnSe@C nanoparticles were prepared from ZIF-8 and the SEI layers on these electrodes with and without reduced graphene oxide(rGO)layers were examined in details by X-ray photoelectron spectroscopies at varied charged/discharged states.It is observed that fast and complicated electrolyte decomposition reactions on ZnSe@C leads to quite thick SEI film and intercalation of solvated sodium ions through such thick SEI film results in slow ion diffusion kinetics and unstable electrode structure.However,the presence of rGO could efficiently suppress the decomposition of electrolyte,thus thin and stable SEI film was formed.ZnSe@C electrodes wrapped by rGO demonstrates enhanced interfacial charge transfer kinetics and high electrochemical performance,a capacity retention of 96.4%,after 1000 cycles at 5 A/g.This study might offer a simple avenue for the designing high performance anode materials through manipulation of SEI film.
基金supported by the National Natural Science Foundation of China(No.51602106)。
文摘The photovoltaic performance of perovskite sloar cells(PSCs)is strongly dependent on the crystallinity,morphorlogy and defects of perovskite films.In the present work,a novel strategy was developed to fabricate the high quality CsPbI3 inorganic perovskite by tuning the growth dynamics of CsPbI3 by pretreatment of fresh CsPbI3 films with phenylethylamine iodide(PEAI).The PEAI can mediate the phase transformation from 1D(DMAPbI3)(DMA:dimethylammonium)to 3D CsPbI3 all-inorganic perovskite films via the PEA2CsPb2I7 of 2D perovskite intermediate phase,resulting in highly crystalline CsPbI3 perovskite films with remarkably enlarged grains and reduced defects.The as-achieved highly crystalline CsPbI3 inorganic perovskite not only exhibited improved phase stability but also significant reduced defects.The perovskite solar cells based on these CsPbI3 thin films exhibited a champion efficiency of 17.08%,much higher than those prepared through posttreatment or direct addition of PEAI into CsPbI3 precursor solution.This work not only developed an effective strategy to prepare high crystalline CsPbI3 film and highly efficient CsPbI3-based all-inorganic PSCs,but also unraveled the mediation mechanism of CsPbI3by pre-treatment of PEAI,shedding light for further development of high perfomance perovskite-based optoelectronics.