Developing high-performance catalysts using traditional trial-and-error methods is generally time consuming and inefficient.Here,by combining machine learning techniques and first-principle calculations,we are able to...Developing high-performance catalysts using traditional trial-and-error methods is generally time consuming and inefficient.Here,by combining machine learning techniques and first-principle calculations,we are able to discover novel graphene-supported single-atom catalysts for nitrogen reduction reaction in a rapid way.Successfully,45 promising catalysts with highly efficient catalytic performance are screened out from 1626 candidates.Furthermore,based on the optimal feature sets,new catalytic descriptors are constructed via symbolic regression,which can be directly used to predict single-atom catalysts with good accuracy and good generalizability.This study not only provides dozens of promising catalysts and new descriptors for nitrogen reduction reaction but also offers a potential way for rapid screening of new electrocatalysts.展开更多
Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since ...Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since the mechanical exfoliation of graphene in 2004. Starting from graphene, 2D materials now have become a big family with numerous members and diverse categories. The unique structural features and physicochemical properties of 2D materials make them one class of the most appealing candidates for a wide range of potential applications. In particular, we have seen some major breakthroughs made in the field of 2D materials in last five years not only in developing novel synthetic methods and exploring new structures/properties but also in identifying innovative applications and pushing forward commercialisation. In this review, we provide a critical summary on the recent progress made in the field of 2D materials with a particular focus on last five years. After a brief backgroundintroduction, we first discuss the major synthetic methods for 2D materials, including the mechanical exfoliation, liquid exfoliation, vapor phase deposition, and wet-chemical synthesis as well as phase engineering of 2D materials belonging to the field of phase engineering of nanomaterials(PEN). We then introduce the superconducting/optical/magnetic properties and chirality of 2D materials along with newly emerging magic angle 2D superlattices. Following that, the promising applications of 2D materials in electronics, optoelectronics, catalysis, energy storage, solar cells, biomedicine, sensors, environments, etc. are described sequentially. Thereafter, we present the theoretic calculations and simulations of 2D materials. Finally, after concluding the current progress, we provide some personal discussions on the existing challenges and future outlooks in this rapidly developing field.展开更多
Effectively controlling the selectivity of C_(2) oxygenates is desirable for electrocatalytic CO_(2) reduction.Copper catalyst has been considered as the most potential for reducing CO_(2) to C_(2) products,but it sti...Effectively controlling the selectivity of C_(2) oxygenates is desirable for electrocatalytic CO_(2) reduction.Copper catalyst has been considered as the most potential for reducing CO_(2) to C_(2) products,but it still suffers from low C_(2) selectivity,high overpotential,and competitive hydrogen evolution reaction(HER).Here,we propose a design strategy to introduce a second metal that weakly binds to H and a functional ligand that provides hydrogen bonds and protons to achieve high selectivity of C_(2)oxygenates and effective suppression of HER on the Cu(100)surface simultaneously.Seven metals and eleven ligands are screened using first-principles calculations,which shows that Sn is the most efficient for inhibiting HER and cysteamine(CYS)ligand is the most significant in reducing the limiting potential of^(*)CO hydrogenation to^(*)CHO.In the post C-C coupling steps,a so-called“pulling effect”that transfers H in the CYS ligand as a viable proton donor to the C_(2)intermediate to form an H bond,can further stabilize the OH group and facilitate the selection of C_(2)products toward oxygenates.Therefore,this heterogeneous electrocatalyst can effectively reduce CO_(2)to ethanol and ethylene glycol with an ultra-low limiting potential of-0.43 V.This study provides a new strategy for effectively improving the selectivity of C_(2)oxygenates and inhibiting HER to achieve advanced electrocatalytic CO_(2)reduction.展开更多
Oxygen-containing species have been demonstrated to play a key role in facilitating electrocatalytic CO_(2) reduction(CO_(2)RR),particularly in enhancing the selectivity towards multi-carbon(C2+)products.However,the u...Oxygen-containing species have been demonstrated to play a key role in facilitating electrocatalytic CO_(2) reduction(CO_(2)RR),particularly in enhancing the selectivity towards multi-carbon(C2+)products.However,the underlying promotion mechanism is still under debate,which greatly limits the rational optimization of the catalytic performance of CO_(2)RR.Herein,taking CO_(2) and O_(2) co-electrolysis over Cu as the prototype,we successfully clarified how O_(2) boosts CO_(2)RR from a new perspective by employing comprehensive theoretical simulations.Our results demonstrated that O_(2) in feed gas can be rapidly reduced into^(*)OH,leading to the partial oxidation of Cu surface under reduction conditions.Surface^(*)OH accelerates the formation of quasi-specifically adsorbed K^(+)due to the electrostatic interaction between^(*)OH and K^(+)ions,which significantly increases the concentration of K^(+)near the Cu surface.These quasi-specifically adsorbed K+ions can not only lower the C-C coupling barriers but also promote the hydrogenation of CO_(2) to improve the CO yield rate,which are responsible for the remarkably enhanced efficiency of C^(2+)products.During the whole process,O_(2) co-electrolysis plays an indispensable role in stabilizing surface^(*)OH.This mechanism can be also adopted to understand the effect of high pH of electrolyte and residual O in oxide-derived Cu(OD-Cu)on the catalytic efficiency towards C^(2+)products.Therefore,our work provides new insights into strategies for improving C^(2+)products on the Cu-based catalysts,i.e.,maintaining partial oxidation of surface under reduction conditions.展开更多
MXenes have exhibited great potential as cost-effective electrocatalysts for hydrogen evolution reaction(HER). However, insight into the origin of activity is still missing. Herein, on the basis of a systematical inve...MXenes have exhibited great potential as cost-effective electrocatalysts for hydrogen evolution reaction(HER). However, insight into the origin of activity is still missing. Herein, on the basis of a systematical investigation of the HER performance of 20 MXenes(M_2NO_2 and M_2CO_2, M = Sc, Ti, V, Cr, Zr, Nb, Mo,Hf, Ta and W), a Fermi-abundance model is proposed to understand variation of the activity in different MXenes. It is found that the occupied p electronic states of surface O atoms play a decisive role in the HER activity of MXenes. More importantly, Ti_2NO_2 and Nb_2NO_2 are found to be promising HER electrocatalysts with the free energy for hydrogen adsorption close to zero. This work not only provides possible catalysts for HER, the developed Fermi-abundance model but also is applicable to other two-dimensional materials and may serve as a simple descriptor of the intrinsic HER activity.展开更多
Crystal phase can greatly affect the physicochemical properties and applications of nanomaterials.However,it stil remains a great challenge to synthesize nanostructures with the same composition and morphology but dif...Crystal phase can greatly affect the physicochemical properties and applications of nanomaterials.However,it stil remains a great challenge to synthesize nanostructures with the same composition and morphology but different phases in order to explore the phase-dependent properties and applications.Herein,we report the crystal phase-controlled synthesis of PtCu alloy shells on 4H Au nanoribbons(NRBs),referred to as 4H-Au NRBs,to form the 4H-Au@PtCu core-shell NRBs.By tuning the thickness of PtCu,4H-PtCu and face-centered cubic(cc)phase PICu(cc-PtCu)alloy shells are successtully grown on the 4H-Au NRB cores.This thickness-dependent phase-controlled growth strategy can also be used to grow PtCo alloys with 4H or fcc phase on 4H-Au NRBs.Significantly,when used as electrocatalysts for the ethanol oxidation reaction(EOR)in alkaline media,the 4H-Au@4H-PtCu NRBs show much better EOR performance than the 4H-Au@fcc-PtCu NRBs,and both of them possess superior performance compared to the commercial Pt black.Our study provides a strategy on phase-contolled synthesis of nanomaterials used for crystal phase-dependent applications.展开更多
基金S.Z.and S.L.contributed equally to this work.This work was supported by the Natural Science Foundation of China (22033002,21773027,and 22003009)the National Natural Science Foundation of Jiangsu(BK20180353)+1 种基金Postgraduate Research and Practice Innovation Program of Jiangsu Province (KYCX20_0075)the China Postdoctoral Science Foundation (Grant No.2020M681450),the Fundamental Research Funds for the Central Universities of China(2242021k10009)。
文摘Developing high-performance catalysts using traditional trial-and-error methods is generally time consuming and inefficient.Here,by combining machine learning techniques and first-principle calculations,we are able to discover novel graphene-supported single-atom catalysts for nitrogen reduction reaction in a rapid way.Successfully,45 promising catalysts with highly efficient catalytic performance are screened out from 1626 candidates.Furthermore,based on the optimal feature sets,new catalytic descriptors are constructed via symbolic regression,which can be directly used to predict single-atom catalysts with good accuracy and good generalizability.This study not only provides dozens of promising catalysts and new descriptors for nitrogen reduction reaction but also offers a potential way for rapid screening of new electrocatalysts.
文摘Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since the mechanical exfoliation of graphene in 2004. Starting from graphene, 2D materials now have become a big family with numerous members and diverse categories. The unique structural features and physicochemical properties of 2D materials make them one class of the most appealing candidates for a wide range of potential applications. In particular, we have seen some major breakthroughs made in the field of 2D materials in last five years not only in developing novel synthetic methods and exploring new structures/properties but also in identifying innovative applications and pushing forward commercialisation. In this review, we provide a critical summary on the recent progress made in the field of 2D materials with a particular focus on last five years. After a brief backgroundintroduction, we first discuss the major synthetic methods for 2D materials, including the mechanical exfoliation, liquid exfoliation, vapor phase deposition, and wet-chemical synthesis as well as phase engineering of 2D materials belonging to the field of phase engineering of nanomaterials(PEN). We then introduce the superconducting/optical/magnetic properties and chirality of 2D materials along with newly emerging magic angle 2D superlattices. Following that, the promising applications of 2D materials in electronics, optoelectronics, catalysis, energy storage, solar cells, biomedicine, sensors, environments, etc. are described sequentially. Thereafter, we present the theoretic calculations and simulations of 2D materials. Finally, after concluding the current progress, we provide some personal discussions on the existing challenges and future outlooks in this rapidly developing field.
基金supported by the National Natural Science Foundation of China(Grant No.22033002,21525311,21773027)the Scientific Research Foundation of Graduate School of Southeast University(YBPY1920)+1 种基金the China Postdoctoral Science Foundation(Grant No.2020M681450)the China Scholarship Council(CSC,201906090150)。
文摘Effectively controlling the selectivity of C_(2) oxygenates is desirable for electrocatalytic CO_(2) reduction.Copper catalyst has been considered as the most potential for reducing CO_(2) to C_(2) products,but it still suffers from low C_(2) selectivity,high overpotential,and competitive hydrogen evolution reaction(HER).Here,we propose a design strategy to introduce a second metal that weakly binds to H and a functional ligand that provides hydrogen bonds and protons to achieve high selectivity of C_(2)oxygenates and effective suppression of HER on the Cu(100)surface simultaneously.Seven metals and eleven ligands are screened using first-principles calculations,which shows that Sn is the most efficient for inhibiting HER and cysteamine(CYS)ligand is the most significant in reducing the limiting potential of^(*)CO hydrogenation to^(*)CHO.In the post C-C coupling steps,a so-called“pulling effect”that transfers H in the CYS ligand as a viable proton donor to the C_(2)intermediate to form an H bond,can further stabilize the OH group and facilitate the selection of C_(2)products toward oxygenates.Therefore,this heterogeneous electrocatalyst can effectively reduce CO_(2)to ethanol and ethylene glycol with an ultra-low limiting potential of-0.43 V.This study provides a new strategy for effectively improving the selectivity of C_(2)oxygenates and inhibiting HER to achieve advanced electrocatalytic CO_(2)reduction.
基金supported by the National Key Research and Development Program of China(2022YFA1503100 and 2021YFA1500700)the National Natural Science Foundation of China(22033002,92261112,and 22303011)+2 种基金the Basic Research Program of Jiangsu Province(BK20220800 and BK20222007)the Fundamental Research Funds for the Central Universities(2242023R40016)supported by the Big Data Computing Center of Southeast University and National Supercomputing Center of Tianjin.
文摘Oxygen-containing species have been demonstrated to play a key role in facilitating electrocatalytic CO_(2) reduction(CO_(2)RR),particularly in enhancing the selectivity towards multi-carbon(C2+)products.However,the underlying promotion mechanism is still under debate,which greatly limits the rational optimization of the catalytic performance of CO_(2)RR.Herein,taking CO_(2) and O_(2) co-electrolysis over Cu as the prototype,we successfully clarified how O_(2) boosts CO_(2)RR from a new perspective by employing comprehensive theoretical simulations.Our results demonstrated that O_(2) in feed gas can be rapidly reduced into^(*)OH,leading to the partial oxidation of Cu surface under reduction conditions.Surface^(*)OH accelerates the formation of quasi-specifically adsorbed K^(+)due to the electrostatic interaction between^(*)OH and K^(+)ions,which significantly increases the concentration of K^(+)near the Cu surface.These quasi-specifically adsorbed K+ions can not only lower the C-C coupling barriers but also promote the hydrogenation of CO_(2) to improve the CO yield rate,which are responsible for the remarkably enhanced efficiency of C^(2+)products.During the whole process,O_(2) co-electrolysis plays an indispensable role in stabilizing surface^(*)OH.This mechanism can be also adopted to understand the effect of high pH of electrolyte and residual O in oxide-derived Cu(OD-Cu)on the catalytic efficiency towards C^(2+)products.Therefore,our work provides new insights into strategies for improving C^(2+)products on the Cu-based catalysts,i.e.,maintaining partial oxidation of surface under reduction conditions.
基金supported by the National Natural Science Foundation for Distinguished Young Scholar (21525311)the National Key R&D Program of China (2017YFA0204800)+3 种基金the National Natural Science Foundation of China (21773027, 21703032)Jiangsu 333 Project (BRA2016353)the Scientific Research Foundation of Graduate School of Southeast University in Chinathe Fundamental Research Funds for the Central Universities of China
文摘MXenes have exhibited great potential as cost-effective electrocatalysts for hydrogen evolution reaction(HER). However, insight into the origin of activity is still missing. Herein, on the basis of a systematical investigation of the HER performance of 20 MXenes(M_2NO_2 and M_2CO_2, M = Sc, Ti, V, Cr, Zr, Nb, Mo,Hf, Ta and W), a Fermi-abundance model is proposed to understand variation of the activity in different MXenes. It is found that the occupied p electronic states of surface O atoms play a decisive role in the HER activity of MXenes. More importantly, Ti_2NO_2 and Nb_2NO_2 are found to be promising HER electrocatalysts with the free energy for hydrogen adsorption close to zero. This work not only provides possible catalysts for HER, the developed Fermi-abundance model but also is applicable to other two-dimensional materials and may serve as a simple descriptor of the intrinsic HER activity.
基金supported by the National Natural Science Foundation of China(22033002,21525311,21773027,21703032,and 21973011)the China Postdoctoral Science Foundation(2020M681450)。
基金MOE under AcRF Tier 2(Nos.MOE2016-T2-2-103 and MOE2017-T2-1-162)NTU under Start-Up Grant(No.M4081296.070.500000)in Singapore+2 种基金We would like to acknowledge the Facility for Analysis,Characterization,Testing and Simulation,Nanyang Technological University,Singapore,for use of their electron microscopy and X-ray facilities.Z.X.F.and H.Z.thank the financial support from ITC via Hong Kong Branch of National Precious Metals Material Engineering Research Center(NPMM)acknowledge the start-up grants(Nos.9380100,9610480 and 7200651)grants(Nos.9610478 and 1886921)in City University of Hong Kong.
文摘Crystal phase can greatly affect the physicochemical properties and applications of nanomaterials.However,it stil remains a great challenge to synthesize nanostructures with the same composition and morphology but different phases in order to explore the phase-dependent properties and applications.Herein,we report the crystal phase-controlled synthesis of PtCu alloy shells on 4H Au nanoribbons(NRBs),referred to as 4H-Au NRBs,to form the 4H-Au@PtCu core-shell NRBs.By tuning the thickness of PtCu,4H-PtCu and face-centered cubic(cc)phase PICu(cc-PtCu)alloy shells are successtully grown on the 4H-Au NRB cores.This thickness-dependent phase-controlled growth strategy can also be used to grow PtCo alloys with 4H or fcc phase on 4H-Au NRBs.Significantly,when used as electrocatalysts for the ethanol oxidation reaction(EOR)in alkaline media,the 4H-Au@4H-PtCu NRBs show much better EOR performance than the 4H-Au@fcc-PtCu NRBs,and both of them possess superior performance compared to the commercial Pt black.Our study provides a strategy on phase-contolled synthesis of nanomaterials used for crystal phase-dependent applications.
