The canonical and locatized molecutar orbiters of [NCCuS_2NoS_2]^(2-) cluster were calculated by means of CNDO quantum chemistry method. Then the energy and properties of corresponding chemicat bonds were discussed, e...The canonical and locatized molecutar orbiters of [NCCuS_2NoS_2]^(2-) cluster were calculated by means of CNDO quantum chemistry method. Then the energy and properties of corresponding chemicat bonds were discussed, especially, Cu-Sb-No three center conjugated π bonds and No-St-No conjugated π bonds were accounted for.展开更多
Spin-unrestricted localized INDO method was used to calculate the electronic structure of rare earth cluster Sc(Sc_6Cl_(12)Co).Based on the analysis of the composition of the molecular orbitals and bond orders,it was ...Spin-unrestricted localized INDO method was used to calculate the electronic structure of rare earth cluster Sc(Sc_6Cl_(12)Co).Based on the analysis of the composition of the molecular orbitals and bond orders,it was pointed out that the interstitial transition metal atom Co in the octahedral Sc skeleton forms strong covalent bond with six Sc atoms and the bonding of Sc- Cl is mainly ionic in character.There are nine valence molecular orbitals in the cluster.展开更多
The localized molecular orbitals for typical bowl-shaped circulenes are obtained by the use of INDO-LMO method. It is found that these bowl-shaped circulenes with strained π-electron systems are still aromatic and th...The localized molecular orbitals for typical bowl-shaped circulenes are obtained by the use of INDO-LMO method. It is found that these bowl-shaped circulenes with strained π-electron systems are still aromatic and the rim π-bonds with larger localization form reactive regions for formation of buckminsterfullerene.展开更多
Single-atom catalysts (SACs) have emerged as a transformative class of materials in heterogeneous catalysis owing to their atomically dispersed metal centers, maximal atom utilization, and well-defined coordination en...Single-atom catalysts (SACs) have emerged as a transformative class of materials in heterogeneous catalysis owing to their atomically dispersed metal centers, maximal atom utilization, and well-defined coordination environments. In the energy sector, SACs have shown exceptional performance in electrocatalytic reactions such as the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and carbon dioxide reduction (CO_(2)RR), where their tunable local electronic structures facilitate high activity and selectivity under mild conditions. Meanwhile, in the environmental domain, SACs are increasingly explored for advanced oxidation processes (AOPs), particularly in water purification applications, due to their ability to generate reactive species from green oxidants like hydrogen peroxide or peroxymonosulfate (PMS). Among various AOP strategies, PMS-based Fenton-like reactions have gained attention due to the high oxidation potential and stability of PMS in a wide pH range.展开更多
Optimizing the catalytic activity and stability of molybdenum disulfide (MoS_(2)) towards alkaline hydrogen evolution reaction (HER) is significant for sustaining green hydrogen. A moderate localized electronic struct...Optimizing the catalytic activity and stability of molybdenum disulfide (MoS_(2)) towards alkaline hydrogen evolution reaction (HER) is significant for sustaining green hydrogen. A moderate localized electronic structure of active sites plays a crucial role in determining the activity and stability of the catalysts, yet how to construct such localized electronic structure still remains indeterminacy. Enlightened by theoretical prediction, herein, the introduction of both single-atom Re and the adjacent S vacancy in MoS_(2) (denoted as Re-MoS_(2)-Vs) exhibits collaborative effect on regulating the localized electronic structure of active sites (viz. Re-(S, Vs)-Mo). Such regulated electronic structure helps to decrease the energy barrier of the water dissociation and optimize hydrogen adsorption energy for enhancing alkaline HER performance. Most importantly, Mo-S bonds in the above local Re-(S, Vs)-Mo configurations are also strengthened for preventing the leaching of Mo and S atoms and then ensuring the long-time stability. Consequently, the deliberately designed Re-MoS_(2)-Vs with a Re coordination number of ~ 5.0 is experimentally verified to exhibit a comparable electrocatalytic performance and robust operational stability over 120 h. This strategy provides a promising guidance for modulating the electronic structure of MoS_(2) based catalysts via double-tuning atomic-scale local configuration for HER applications.展开更多
Structurally ordered intermetallic borides are a large family of inorganic solids with rich bonding schemes,and huge compositional and structural diversity.The family members possess high flexibility to modulate the l...Structurally ordered intermetallic borides are a large family of inorganic solids with rich bonding schemes,and huge compositional and structural diversity.The family members possess high flexibility to modulate the local electronic structures and surface adsorption properties,providing great opportunities for the development of advanced catalysts with superior activity and stability.In this review,we summarize the structural features of intermetallic borides,with emphasis on the covalent linkage patterns of boron atoms in them,and the research methods for understanding their electronic structures.We also present the recent developments in the synthesis of phase-pure,well-defined intermetallic borides,most of which are suitable for catalytic studies.We further highlight the theoretical and experimental advances in the emerging boride-catalyzed reactions and the important roles of boron in tuning electrocatalytic performances.Finally,we propose the remaining challenges and future developments of boride synthesis and catalytic applications.展开更多
With practical electrocatalytic hydrogen production frequently involving the splitting of water in various pH media,there is an urgent need but still a technical challenge to develop low-cost,highly active,and stable ...With practical electrocatalytic hydrogen production frequently involving the splitting of water in various pH media,there is an urgent need but still a technical challenge to develop low-cost,highly active,and stable electrocatalysts for pH-universal hydrogen evolution reaction(HER).We report herein the adoption of a hydrothermal reaction combined with a post gas-phase doping strategy to fabricate P-doped NiCo_(2)Se_(4) hollow nanoneedle arrays on carbon fiber paper(i.e.,P-NiCo_(2)Se_(4)/CFP).Notably,the optimal arrays(P8.71-NiCo_(2)Se_(4)/CFP)can afford an outstanding pH-universal HER performance,with an overpotential as low as 33,57,and 69 mV at 10 mA·cm^(−2) and corresponding Tafel slopes down to 52,61,and 72 mV·dec^(−1) in acidic,alkaline,and neutral media,respectively,outperforming most state-of-the-art nonprecious catalysts and even the commercial Pt/C catalyst in both neutral and alkaline media at large current densities.Impressively,P_(8.71-)NiCo_(2)Se_(4)/CFP also displays good durability toward long-time stability testing in harsh acidic and alkaline electrolytes.Experimental and theoretical studies further reveal that the doping of P atoms into NiCo_(2)Se_(4) can simultaneously optimize its H*adsorption/desorption energy,water adsorption energy,and water dissociation energy by adjusting the local electronic states of various active sites,thus accelerating the rate-determining step of HER in different pH media to endow P-NiCo_(2)Se_(4) with an outstanding pH-universal HER performance.This work provides atomic-level insights into the roles of active sites in various electrolysis environments,thereby shedding new light on the rational design of highly efficient pH-universal nonprecious catalysts for HER and beyond.展开更多
The local electronic structure of a transition metal can be adjusted by changing the metal octahedral linking mode in order to control its electrocatalytic activity.Perovskite(corner-sharing octahedra)and layered hydr...The local electronic structure of a transition metal can be adjusted by changing the metal octahedral linking mode in order to control its electrocatalytic activity.Perovskite(corner-sharing octahedra)and layered hydroxide(edge-sharing octahedra)structures have previously been studied as OER electrocatalysts.However,catalysts with face-sharing octahedra have still rarely been studied to date.In this work,a nickel–cobalt phosphite including local structural motifs with face-sharing octahedra has been studied as a model electrocatalyst for OER.展开更多
Improving the catalytic activity of non-noble metal single atom catalysts(SACs)has attracted considerable attention in materials science.Although optimizing the local electronic structure of single atom can greatly im...Improving the catalytic activity of non-noble metal single atom catalysts(SACs)has attracted considerable attention in materials science.Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity,it often involves in-plane modulation and requires high temperatures.Herein,we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co-S bond anchored onto graphitic carbon nitride(C_(3)N_(4))at room temperature(RT).Each Co atom is bonded to four N atoms and one S atom(Co-(N,S)/C_(3)N_(4)).Owing to the greater electronegativity of S in the Co-S bond,the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level.Consequently,when employed for the photocatalytic hydrogen evolution reaction,the adsorption energy of intermediate hydrogen(H*)on the Co atoms is remarkably low.In the presence of the Co-(N,S)/C_(3)N_(4)SACs,the hydrogen evolution rates reach up to 10 mmol/(g·h),which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C_(3)N_(4)and noble platinum nanoparticles(PtNPs)/C_(3)N_(4)catalysts,respectively.Attributed to the tailorable axial Co-S bond in the SAC,the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions.This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic applications.展开更多
文摘The canonical and locatized molecutar orbiters of [NCCuS_2NoS_2]^(2-) cluster were calculated by means of CNDO quantum chemistry method. Then the energy and properties of corresponding chemicat bonds were discussed, especially, Cu-Sb-No three center conjugated π bonds and No-St-No conjugated π bonds were accounted for.
文摘Spin-unrestricted localized INDO method was used to calculate the electronic structure of rare earth cluster Sc(Sc_6Cl_(12)Co).Based on the analysis of the composition of the molecular orbitals and bond orders,it was pointed out that the interstitial transition metal atom Co in the octahedral Sc skeleton forms strong covalent bond with six Sc atoms and the bonding of Sc- Cl is mainly ionic in character.There are nine valence molecular orbitals in the cluster.
文摘The localized molecular orbitals for typical bowl-shaped circulenes are obtained by the use of INDO-LMO method. It is found that these bowl-shaped circulenes with strained π-electron systems are still aromatic and the rim π-bonds with larger localization form reactive regions for formation of buckminsterfullerene.
文摘Single-atom catalysts (SACs) have emerged as a transformative class of materials in heterogeneous catalysis owing to their atomically dispersed metal centers, maximal atom utilization, and well-defined coordination environments. In the energy sector, SACs have shown exceptional performance in electrocatalytic reactions such as the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and carbon dioxide reduction (CO_(2)RR), where their tunable local electronic structures facilitate high activity and selectivity under mild conditions. Meanwhile, in the environmental domain, SACs are increasingly explored for advanced oxidation processes (AOPs), particularly in water purification applications, due to their ability to generate reactive species from green oxidants like hydrogen peroxide or peroxymonosulfate (PMS). Among various AOP strategies, PMS-based Fenton-like reactions have gained attention due to the high oxidation potential and stability of PMS in a wide pH range.
基金supported by the National Natural Science Foundation of China(No.22209193)Natural Science Foundation of Shandong Province(Nos.ZR2020ZD10 and ZR2021QB111)+1 种基金the Taishan Scholars Program of Shandong Province(No.tstq20221151)the Innovation Funds of Shandong Energy Institute(No.SEI I202140).
文摘Optimizing the catalytic activity and stability of molybdenum disulfide (MoS_(2)) towards alkaline hydrogen evolution reaction (HER) is significant for sustaining green hydrogen. A moderate localized electronic structure of active sites plays a crucial role in determining the activity and stability of the catalysts, yet how to construct such localized electronic structure still remains indeterminacy. Enlightened by theoretical prediction, herein, the introduction of both single-atom Re and the adjacent S vacancy in MoS_(2) (denoted as Re-MoS_(2)-Vs) exhibits collaborative effect on regulating the localized electronic structure of active sites (viz. Re-(S, Vs)-Mo). Such regulated electronic structure helps to decrease the energy barrier of the water dissociation and optimize hydrogen adsorption energy for enhancing alkaline HER performance. Most importantly, Mo-S bonds in the above local Re-(S, Vs)-Mo configurations are also strengthened for preventing the leaching of Mo and S atoms and then ensuring the long-time stability. Consequently, the deliberately designed Re-MoS_(2)-Vs with a Re coordination number of ~ 5.0 is experimentally verified to exhibit a comparable electrocatalytic performance and robust operational stability over 120 h. This strategy provides a promising guidance for modulating the electronic structure of MoS_(2) based catalysts via double-tuning atomic-scale local configuration for HER applications.
基金financial support from the National Natural Science Foundation of China(NSFC):Grant No.21922507 and 21771079the Fok Ying Tung Education Foundation:Grant No.161011+4 种基金financial support from the NSFC(Grant No.21901083)the Postdoctoral Innovative Talent Support Program(Grant No.BX20180120)the China Postdoctoral Science Foundation(Grant No.2018M641771)the National Natural Science Foundation of China(Grant No.21621001)the 111 Project(No.B17020)for financial support.
文摘Structurally ordered intermetallic borides are a large family of inorganic solids with rich bonding schemes,and huge compositional and structural diversity.The family members possess high flexibility to modulate the local electronic structures and surface adsorption properties,providing great opportunities for the development of advanced catalysts with superior activity and stability.In this review,we summarize the structural features of intermetallic borides,with emphasis on the covalent linkage patterns of boron atoms in them,and the research methods for understanding their electronic structures.We also present the recent developments in the synthesis of phase-pure,well-defined intermetallic borides,most of which are suitable for catalytic studies.We further highlight the theoretical and experimental advances in the emerging boride-catalyzed reactions and the important roles of boron in tuning electrocatalytic performances.Finally,we propose the remaining challenges and future developments of boride synthesis and catalytic applications.
基金supported by the National Natural Science Foundation of China(Nos.21872011 and 21273020).
文摘With practical electrocatalytic hydrogen production frequently involving the splitting of water in various pH media,there is an urgent need but still a technical challenge to develop low-cost,highly active,and stable electrocatalysts for pH-universal hydrogen evolution reaction(HER).We report herein the adoption of a hydrothermal reaction combined with a post gas-phase doping strategy to fabricate P-doped NiCo_(2)Se_(4) hollow nanoneedle arrays on carbon fiber paper(i.e.,P-NiCo_(2)Se_(4)/CFP).Notably,the optimal arrays(P8.71-NiCo_(2)Se_(4)/CFP)can afford an outstanding pH-universal HER performance,with an overpotential as low as 33,57,and 69 mV at 10 mA·cm^(−2) and corresponding Tafel slopes down to 52,61,and 72 mV·dec^(−1) in acidic,alkaline,and neutral media,respectively,outperforming most state-of-the-art nonprecious catalysts and even the commercial Pt/C catalyst in both neutral and alkaline media at large current densities.Impressively,P_(8.71-)NiCo_(2)Se_(4)/CFP also displays good durability toward long-time stability testing in harsh acidic and alkaline electrolytes.Experimental and theoretical studies further reveal that the doping of P atoms into NiCo_(2)Se_(4) can simultaneously optimize its H*adsorption/desorption energy,water adsorption energy,and water dissociation energy by adjusting the local electronic states of various active sites,thus accelerating the rate-determining step of HER in different pH media to endow P-NiCo_(2)Se_(4) with an outstanding pH-universal HER performance.This work provides atomic-level insights into the roles of active sites in various electrolysis environments,thereby shedding new light on the rational design of highly efficient pH-universal nonprecious catalysts for HER and beyond.
基金financially supported by the National Natural Science Foundation of China(No.51302282)the Natural Science Foundation of Shaanxi Province(No.201701D221055)+1 种基金the Natural Science Foundation of Zhejiang Province(No.LY19E010002)the State Key Laboratory of Special Functional Waterproof Materials(No.SKLW2018006).
文摘The local electronic structure of a transition metal can be adjusted by changing the metal octahedral linking mode in order to control its electrocatalytic activity.Perovskite(corner-sharing octahedra)and layered hydroxide(edge-sharing octahedra)structures have previously been studied as OER electrocatalysts.However,catalysts with face-sharing octahedra have still rarely been studied to date.In this work,a nickel–cobalt phosphite including local structural motifs with face-sharing octahedra has been studied as a model electrocatalyst for OER.
基金National Natural Science Foundation of China(No.22008251)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515010318)Shenzhen Science and Technology Program(No.JCYJ20220531095813031).
文摘Improving the catalytic activity of non-noble metal single atom catalysts(SACs)has attracted considerable attention in materials science.Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity,it often involves in-plane modulation and requires high temperatures.Herein,we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co-S bond anchored onto graphitic carbon nitride(C_(3)N_(4))at room temperature(RT).Each Co atom is bonded to four N atoms and one S atom(Co-(N,S)/C_(3)N_(4)).Owing to the greater electronegativity of S in the Co-S bond,the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level.Consequently,when employed for the photocatalytic hydrogen evolution reaction,the adsorption energy of intermediate hydrogen(H*)on the Co atoms is remarkably low.In the presence of the Co-(N,S)/C_(3)N_(4)SACs,the hydrogen evolution rates reach up to 10 mmol/(g·h),which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C_(3)N_(4)and noble platinum nanoparticles(PtNPs)/C_(3)N_(4)catalysts,respectively.Attributed to the tailorable axial Co-S bond in the SAC,the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions.This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic applications.
