Multi-metal porous crystalline materials(MPCM),integrating the functions of both multi-metal centres and porous crystalline materials(e.g.,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)),are an ex...Multi-metal porous crystalline materials(MPCM),integrating the functions of both multi-metal centres and porous crystalline materials(e.g.,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)),are an extended class of porous materials that have attracted much attention for a broad range of applications.Owing to the advantages of these materials,they generally display high porosity,multimetal active sites,well-tuned functions,and pre-designable structures,etc.,serving as desired platforms for the study of structure-property relationships.In view of the clean and sustainable target,a series of MPCM have been explored as electrocatalysts for electrocatalytic reactions like hydrogen evolution reaction,oxygen evolution reaction and electrocatalytic CO_(2)reduction reaction.Concerning the progress achieved for MPCM in electrocatalytic field during past years,this review will provide a brief introduction on the recent breakthrough of MPCM based electrocatalysts including their synthesis methods,structure design,component/morphology tuning,electrocatalytic property and structure-property relationship,etc.Besides,it will also conclude the current challenges and present perspectives for the MPCM based electrocatalysts,which might promote the development of porous crystalline materials in electrocatalysis and hope to provide new insights for scientists in related fields.展开更多
Cellulose is one of the most abundant natural polymers in the nature,which has many attractive advantages,such as renewability,biodegradability,and biocompatibility.However,due to the strong hydrogen bond network and ...Cellulose is one of the most abundant natural polymers in the nature,which has many attractive advantages,such as renewability,biodegradability,and biocompatibility.However,due to the strong hydrogen bond network and hierarchical structure,cellulose is extremely difficult to be dissolved and processed.More recently,a class of novel eco-friendly solvents,ionic liquids,have been found to be able to efficiently dissolve cellulose,providing a versatile platform for cellulose processing and functionalization.Herein,we highlight recent advances in efficiently fabricating functional cellulose derivatives via the homogeneous chemical modification and developing all-biomass materials via controlling the dissolution-regeneration process in ionic liquids.The effective and environmentally-friendly utilization of cellulose not only reduces dependence on fossil resources but also protects the environment.展开更多
Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three...Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO_(2)RR into CH_(4). Notably, they all exhibit higher FE (hollow sphere, 68.2%;nanosheet, 64.2% and nanofiber, 71.0%, -0.9 V) than COF-366-Cu (43.0%, -0.9 V) after morphology control. Noteworthy, the FE of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from -0.9 V to -1.1 V and the achieved FECH_(4) + C_(2)H_(4) (82.8%, -0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO_(2)RR to CH_(4).展开更多
Objective:To investigate the relationship of serum folic acid and vitamin B12 contents with maternal endothelial injury and placental ischemia hypoxia in patients with preeclampsia. Methods:A total of 76 puerperae wit...Objective:To investigate the relationship of serum folic acid and vitamin B12 contents with maternal endothelial injury and placental ischemia hypoxia in patients with preeclampsia. Methods:A total of 76 puerperae with preeclampsia who gave birth in this hospital between March 2016 and October 2017 were selected as the preeclampsia group, and 100 healthy puerperae who gave birth in this hospital during the same period were selected as the normal control group. The differences in serum contents of folic acid, vitamin B12, endothelial injury indexes and oxidative stress indexes were compared between the two groups 24 h before delivery. Pearson test was used to assess the intrinsic relationship of serum folic acid and vitamin B12 contents with the disease severity in puerperae with preeclampsia.Results:Serum folic acid and vitamin B12 contents of preeclampsia group were lower than those of control group;endothelial injury markers sEng, sFlt-1, ET-1 and TM contents were higher than those of control group whereas ADM content was lower than that of control group;oxidative stress indexes AOPPs and LHP contents were higher than those of normal control group whereas T-AOC content was lower than that of control group. The Pearson test showed that serum folic acid and vitamin B12 contents in puerperae with preeclampsia were directly correlated with vascular endothelial injury and placental ischemia hypoxia.Conclusion: There is folic acid and vitamin B12 deficiency in patients with preeclampsia, and it can aggravate the vascular endothelial injury and placental ischemia hypoxia.展开更多
Objective:To study the changes of miR-26b expression in the preeclampsia placenta and its downstream target genes.Methods: Preeclampsia placenta tissue and healthy placenta tissue from puerperae who gave birth in Peop...Objective:To study the changes of miR-26b expression in the preeclampsia placenta and its downstream target genes.Methods: Preeclampsia placenta tissue and healthy placenta tissue from puerperae who gave birth in People's Hospital of Songzi between August 2014 and February 2017 were collected, miRNA was extracted to determine miR-26b expression, and protein was extracted to detect he expression of cell invasion molecules MEST, LAMA4, uPA, HtrA4 and CTSB as well as angiogenesis molecules VEGF, ANG1, ANG2 and PLGF. Results: miR-26b expression in preeclampsia placenta tissue was significantly higher than that in healthy placenta tissue whereas MEST, LAMA4, uPA, HtrA4, CTSB, VEGF, ANG1, ANG2 and PLGF protein expression were significantly lower than those in healthy placenta tissue;MEST, LAMA4, uPA, HtrA4, CTSB, VEGF, ANG1, ANG2 and PLGF protein expression in preeclampsia placenta tissue with high miR-26b expression were significantly lower than those in preeclampsia placenta tissues with low miR-26 expression.Conclusion: miR-26b is highly expressed in the preeclampsia placenta tissue and the target genes are cell invasion molecules and angiogenesis molecules.展开更多
Erratum to Nano Research Energy,2025,DOI:10.26599/NRE.2025.9120205 https://doi.org/10.26599/NRE.2025.9120205 In the article,the Acknowledgements part in the maintext of this article was unfortunately mispresented due ...Erratum to Nano Research Energy,2025,DOI:10.26599/NRE.2025.9120205 https://doi.org/10.26599/NRE.2025.9120205 In the article,the Acknowledgements part in the maintext of this article was unfortunately mispresented due to the publisher’s negligence.Instead of Acknowledgements This work was financially supported by the National Key Research and Development Program of China(2022YFA1505700),the National Natural Science Foundation of China(52102216),the Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power,the Key Laboratory of Applied Surface and Colloid Chemistry(Shaanxi Normal University),Ministry of Education(2025067).展开更多
Inspired by high-entropy materials,it is a worthwhile direction to develop multi-metal integrated catalysts to study their synergistic catalytic effects in catalysis field.However,achieving this in porous crystalline ...Inspired by high-entropy materials,it is a worthwhile direction to develop multi-metal integrated catalysts to study their synergistic catalytic effects in catalysis field.However,achieving this in porous crystalline materials like covelent organic frameworks(COFs)for backend catalysis reactions remains scarce and challenging to date.Herein,a series of multimetal-variate COFs(i.e.,Quint-MMV-COF,Tetra-MMV-COF and Tri-n-MMV-COF(n=1,2 and 3))have been prepared that can be applied in indirect electrocatalysis.These MMV-COFs with advantages of multi-metal sites,porous structures and appropriate work function can serve as solid-phase redox mediators for the catalytic production of liquid-phase S-S bond products and gas-phase H_(2)product.Interestingly,the optimal Quint-MMV-COF presents excellent electrocatalytic efficiency for S-S bond products(yields up to 99%)and H_(2)(~1.62 mmol·g^(-1)·h^(-1))and can be readily recycled for 6 cycles.At the same time,1.52 g product with a yield of~92%can be obtained in the amplification reaction,showing much potential in industrial production.Validated by theoretical calculations,the synergistic effect of multi-metal sites can result in appropriate work function to boost the electron transfer and intermediate adsorption/conversion to achieve excellent overall S-S coupling efficiency.展开更多
The lower electricity consumption(EC)and higher value-added products are much desired yet still challenging for the development of CO_(2) coupling electrocatalytic systems.Herein,we give insight into the inherent natu...The lower electricity consumption(EC)and higher value-added products are much desired yet still challenging for the development of CO_(2) coupling electrocatalytic systems.Herein,we give insight into the inherent nature of the retrenchment of EC by exploring the photo-assisted co-electrolysis of methanol and CO_(2) system using a kind of hydroxyl-rich covalent organic frameworks(Dha-COF-Co)with well-tuned pore structure and morphology.Specifically,the hydroxyl induced hydrogen bond interaction in Dha-COF-Co enables to simultaneously regulate the pore microenvironment and nanoribbon morphology of COFs for performance boosting.Notably,the obtained Dha-COF-Co nanoribbon exhibits an overall EC retrenchment of~41.2%(highest in porous crystalline materials to date)when replacing the anodic OER with MOR in the photo-electrocatalytic MOR-CO_(2)RR coupling system,as well as superior FEHCOOH(anode,~100%)and FE_(CO)(cathode,>95%)at 1.8 V.Combined theoretical calculations with various characterizations,the vital role of hydroxyl group in both microenvironment and morphology tuning that can facilitate the CO_(2)RR and MOR kinetics to retrench the EC has been intensively discussed.展开更多
Electrochemical CO2 reduction reaction(CO2RR)to formate is economically viable considering the energy input and market value.Through learning nature,a series of chloroplast-like porous bismuth-based core–shell(CPBC)m...Electrochemical CO2 reduction reaction(CO2RR)to formate is economically viable considering the energy input and market value.Through learning nature,a series of chloroplast-like porous bismuth-based core–shell(CPBC)materials have been designed.In these materials,the porous carbon can enrich and transfer CO2 to the core–shell Bi@Bi2O3 in CO2 reduction process,during which Bi2O3 layer can be transformed into activated metastable layer to efficiently convert CO2 into formate and Bi can provide abundant electrons.Based on this,superior performances for most of important parameters in CO2 RR can be achieved and best of them,CPBC-1 presents remarkable Faradaic efficiency(FEformate>94%)over a wide potential range(-0.65 to-1.0 V)with high catalysis durability(>72 h).Noteworthy,its maximum energy efficiency is as high as 76.7%at-0.7 V,the highest one in reported bismuth-based materials.This work opens novel perspectives in designing nature-inspired CO2RR electrocatalysts.展开更多
The design of selective and efficient covalent organic frameworks(COFs)based electrocatalysts with tunable morphology for efficient CO_(2) reduction reaction(CO_(2)RR)to CH_(4) is highly desirable.Here,two kinds of an...The design of selective and efficient covalent organic frameworks(COFs)based electrocatalysts with tunable morphology for efficient CO_(2) reduction reaction(CO_(2)RR)to CH_(4) is highly desirable.Here,two kinds of anthraquinone-based COFs(i.e.,AAn-COF and OH-AAn-COF)with tunable 1D superstructures(e.g.,nanofibers(NF)and hollow tubes(HT))have been produced via Schiff-base condensation reaction.Interestingly,a rarely reported nanosheet-based self-template mechanism and a nanosheet-crimping mechanism have been demonstrated for the production of COF-based nanofibers and hollow tubes,respectively.Besides,the obtained COF-based superstructures can be post-modified with transition metals for efficient CO_(2)RR.Specifically,AAn-COF-Cu(NF)and OH-AAn-COF-Cu(HT)exhibit superior faradaic-efficiency with CH_(4)(FECH_(4))of 77%(-128.1 mA cm^(-2),-0.9 V)and 61%(-99.5 mA cm^(-2),-1.0 V)in a flow-cell,respectively.Noteworthy,the achieved FECH_(4) of AAn-COF-Cu(NF)(77%)is the highest one among reported crystalline COFs.This work provides a general methodology in exploring morphology-controlled COFs for electrocatalytic CO_(2)RR.展开更多
Polyester plastics such as poly(ethylene terephthal-ate)(PET)are utilized commonly in everyday life,yet only a small portion of these plastics are recycled,and typically,the recycling procedures face energy or polluti...Polyester plastics such as poly(ethylene terephthal-ate)(PET)are utilized commonly in everyday life,yet only a small portion of these plastics are recycled,and typically,the recycling procedures face energy or pollution problems.展开更多
The conversion of the biomass into eco-friendly fuels and chemicals has been exten-sively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society.Lignin,as a kind of promising...The conversion of the biomass into eco-friendly fuels and chemicals has been exten-sively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society.Lignin,as a kind of promising biomass energy,has been certified to produce the high-valued chemicals and fuels.Numerous efforts have been made to develop various catalysts for lignin catalytic conversion.Both metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)belong to very important heterogeneous porous catalysts due to their regular porous struc-tures,high specific surface area,and precisely tailored diversities.In the review,thefirst part focused on the catalytic conversion of lignin,lignin model compounds,and lignin derivatives using the pristine MOFs,functional MOF composites,and MOF-derived materials.The second part summarized the catalytic conversion of lignin model compounds using pristine COFs and functional COF composites.The review here mainly concentrated on the design of the materials,screening of catalytic conditions,and explorations of the corresponded mechanisms.Specifically,(1)we summarized the MOF-and COF-based materials for the effects on the catalytic trans-formation of lignin-related substances;(2)we emphasized the catalytic mechanism of C–C and C–O bonds cleavage together with the structure–activity relationships;(3)we in-depth realized the relationship between the chemical/electronic/structural properties of the MOF-and COF-based catalysts and their catalytic performance for lignin-related substances.Finally,the challenges and future perspectives were also discussed on the catalytic conversion of lignin-related substances by MOF-and COF-based catalysts.展开更多
A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphe...A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphen-pockets have been implanted into phthalocyanine(Pc)-based COFs through the elaborate design of structural struts;the produced NiPc-DFP-M COFs(M=Ni and Co)possess the advantages of controllable bimetallic centers with different coordination environments,outstanding light sensitivity,and built-in electric-field effects that can be successfully applied in light-assisted CO_(2)electroreduction.Notably,the optimal heterometallic NiPc-DFP-Co COF presents a∼100%Faradic efficiency for CO formation(FECO)in a wide potential range of−0.7 to−1.1 V and∼70%energy efficiency(−0.7 V)under light-irradiation,which is superior to mono-and homometallic COFs and under dark conditions.The high performance can be ascribed to the synergistic effect of the NiPc and Co-salphen pockets that can largely reduce the rate-determining energy-barrier and enhance the electron density to boost the light-assisted activity as supported by density functional theory calculations.A series of bimetallic Pc-based NiPc-DFP-M COF(M=Ni and Co)with integrated salphen-pockets and NiPc units have been synthesized and successfully applied in efficient light-assisted CO_(2)electroreduction.展开更多
Well-defined crystalline coordination compound catalysts have showcased distinct advantages in the regulation of the species and selectivity of electrocatalytic CO_(2)reduction products.However,the systematic study of...Well-defined crystalline coordination compound catalysts have showcased distinct advantages in the regulation of the species and selectivity of electrocatalytic CO_(2)reduction products.However,the systematic study of the crystal-facet effect of crystalline coordination compounds on the performance of electrocatalytic CO_(2)reduction has not yet been reported.Herein,a stable hexanuclear copper cluster(Cu6)catalyst model system is designed and synthesized.By effectively regulating the growth size(micro-nano size)and morphology of the Cu6 single crystal,Cu6(P)with the main(100)facet,Cu6(H)with the main(100)and(001)facets,and Cu6(S)with the main(001)facet are obtained.From Cu6(P)via Cu6(H)to Cu6(S),there is a shift from the predominantly exposed(100)facet(involving two non-adjacent active Cu sites)to the(001)facet(involving three adjacent active Cu sites),which directly affects the adsorption direction of the key*CO intermediate and the potential of C-C coupling,thus enabling effective regulation of the selectivity of C1(CO and CH4)and C2(C2H4)reduction products.This work provides an essential molecular model system and a novel design perspective for the systematic study of the crystalfacet effect of coordination compounds on the species and selectivity of CO_(2)reduction reaction products.展开更多
Intracranial aneurysms have a high prevalence in the population and are associated with high rates of disability and mortality after rupture.It is essential to assess the rupture risk of unruptured intracranial aneury...Intracranial aneurysms have a high prevalence in the population and are associated with high rates of disability and mortality after rupture.It is essential to assess the rupture risk of unruptured intracranial aneurysms by selecting appropriate morphological parameters.However,there is still a need for consistent evidence-based medicine to provide a clinical reference.Therefore,the expert group has jointly written this consensus based on literature review and clinical experience,aiming to provide a standardized reference for predicting the development of intracranial aneurysms and evaluating their rupture risk factors.展开更多
基金supported by the National Key R&D Program of China(No.2023YFA1507204)the National Natural Science Foundation of China(Nos.22171139,22225109,22309054,22071109,22371080,21775048)+2 种基金Natural Science Foundation of Guangdong Province(No.2023B1515020076)China Postdoctoral Science Foundation(No.2023M731154)China National Postdoctoral Program for Innovative Talents(No.BX20220116)。
文摘Multi-metal porous crystalline materials(MPCM),integrating the functions of both multi-metal centres and porous crystalline materials(e.g.,metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)),are an extended class of porous materials that have attracted much attention for a broad range of applications.Owing to the advantages of these materials,they generally display high porosity,multimetal active sites,well-tuned functions,and pre-designable structures,etc.,serving as desired platforms for the study of structure-property relationships.In view of the clean and sustainable target,a series of MPCM have been explored as electrocatalysts for electrocatalytic reactions like hydrogen evolution reaction,oxygen evolution reaction and electrocatalytic CO_(2)reduction reaction.Concerning the progress achieved for MPCM in electrocatalytic field during past years,this review will provide a brief introduction on the recent breakthrough of MPCM based electrocatalysts including their synthesis methods,structure design,component/morphology tuning,electrocatalytic property and structure-property relationship,etc.Besides,it will also conclude the current challenges and present perspectives for the MPCM based electrocatalysts,which might promote the development of porous crystalline materials in electrocatalysis and hope to provide new insights for scientists in related fields.
基金the Youth Innovation Promotion Association CAS(No.2018040)the National Natural Science Foundation of China(Nos.U2004211 and 52173292).
文摘Cellulose is one of the most abundant natural polymers in the nature,which has many attractive advantages,such as renewability,biodegradability,and biocompatibility.However,due to the strong hydrogen bond network and hierarchical structure,cellulose is extremely difficult to be dissolved and processed.More recently,a class of novel eco-friendly solvents,ionic liquids,have been found to be able to efficiently dissolve cellulose,providing a versatile platform for cellulose processing and functionalization.Herein,we highlight recent advances in efficiently fabricating functional cellulose derivatives via the homogeneous chemical modification and developing all-biomass materials via controlling the dissolution-regeneration process in ionic liquids.The effective and environmentally-friendly utilization of cellulose not only reduces dependence on fossil resources but also protects the environment.
基金financially supported by the National Natural Science Foundation of China (NSFC, Nos. 21871141, 21871142,21901122, 22071109 and 92061101)the Natural Science Research of Jiangsu Higher Education Institutions of China (No.19KJB150011)+1 种基金Project funded by China Postdoctoral Science Foundation (Nos. 2018M630572 and 2019M651873)Priority Academic Program Development of Jiangsu Higher Education Institutions and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials。
文摘Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO_(2)RR into CH_(4). Notably, they all exhibit higher FE (hollow sphere, 68.2%;nanosheet, 64.2% and nanofiber, 71.0%, -0.9 V) than COF-366-Cu (43.0%, -0.9 V) after morphology control. Noteworthy, the FE of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from -0.9 V to -1.1 V and the achieved FECH_(4) + C_(2)H_(4) (82.8%, -0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO_(2)RR to CH_(4).
文摘Objective:To investigate the relationship of serum folic acid and vitamin B12 contents with maternal endothelial injury and placental ischemia hypoxia in patients with preeclampsia. Methods:A total of 76 puerperae with preeclampsia who gave birth in this hospital between March 2016 and October 2017 were selected as the preeclampsia group, and 100 healthy puerperae who gave birth in this hospital during the same period were selected as the normal control group. The differences in serum contents of folic acid, vitamin B12, endothelial injury indexes and oxidative stress indexes were compared between the two groups 24 h before delivery. Pearson test was used to assess the intrinsic relationship of serum folic acid and vitamin B12 contents with the disease severity in puerperae with preeclampsia.Results:Serum folic acid and vitamin B12 contents of preeclampsia group were lower than those of control group;endothelial injury markers sEng, sFlt-1, ET-1 and TM contents were higher than those of control group whereas ADM content was lower than that of control group;oxidative stress indexes AOPPs and LHP contents were higher than those of normal control group whereas T-AOC content was lower than that of control group. The Pearson test showed that serum folic acid and vitamin B12 contents in puerperae with preeclampsia were directly correlated with vascular endothelial injury and placental ischemia hypoxia.Conclusion: There is folic acid and vitamin B12 deficiency in patients with preeclampsia, and it can aggravate the vascular endothelial injury and placental ischemia hypoxia.
文摘Objective:To study the changes of miR-26b expression in the preeclampsia placenta and its downstream target genes.Methods: Preeclampsia placenta tissue and healthy placenta tissue from puerperae who gave birth in People's Hospital of Songzi between August 2014 and February 2017 were collected, miRNA was extracted to determine miR-26b expression, and protein was extracted to detect he expression of cell invasion molecules MEST, LAMA4, uPA, HtrA4 and CTSB as well as angiogenesis molecules VEGF, ANG1, ANG2 and PLGF. Results: miR-26b expression in preeclampsia placenta tissue was significantly higher than that in healthy placenta tissue whereas MEST, LAMA4, uPA, HtrA4, CTSB, VEGF, ANG1, ANG2 and PLGF protein expression were significantly lower than those in healthy placenta tissue;MEST, LAMA4, uPA, HtrA4, CTSB, VEGF, ANG1, ANG2 and PLGF protein expression in preeclampsia placenta tissue with high miR-26b expression were significantly lower than those in preeclampsia placenta tissues with low miR-26 expression.Conclusion: miR-26b is highly expressed in the preeclampsia placenta tissue and the target genes are cell invasion molecules and angiogenesis molecules.
文摘Erratum to Nano Research Energy,2025,DOI:10.26599/NRE.2025.9120205 https://doi.org/10.26599/NRE.2025.9120205 In the article,the Acknowledgements part in the maintext of this article was unfortunately mispresented due to the publisher’s negligence.Instead of Acknowledgements This work was financially supported by the National Key Research and Development Program of China(2022YFA1505700),the National Natural Science Foundation of China(52102216),the Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power,the Key Laboratory of Applied Surface and Colloid Chemistry(Shaanxi Normal University),Ministry of Education(2025067).
基金supported by the National Key Research and Development Program of China(2022YFA1505700)the National Natural Science Foundation of China(52102216)+3 种基金the Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power,the Key Laboratory of Applied Surface and Colloid Chemistry(Shaanxi Normal University),Ministry of Education(2025067)the Anhui Key Laboratory of Nanomaterials and Nanotechnology,the Major Science and Technology Projects in Anhui Province(202305a12020006)the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2025-22)the Hubei Key Laboratory of Photoelectronic Conversion Materials and Devices,Hubei Normal University,the Fujian Normal University and the Innovation Training Program for College Students(cxxl-2025137,cxxl-2025131,2025019300A,20250193008).
文摘Inspired by high-entropy materials,it is a worthwhile direction to develop multi-metal integrated catalysts to study their synergistic catalytic effects in catalysis field.However,achieving this in porous crystalline materials like covelent organic frameworks(COFs)for backend catalysis reactions remains scarce and challenging to date.Herein,a series of multimetal-variate COFs(i.e.,Quint-MMV-COF,Tetra-MMV-COF and Tri-n-MMV-COF(n=1,2 and 3))have been prepared that can be applied in indirect electrocatalysis.These MMV-COFs with advantages of multi-metal sites,porous structures and appropriate work function can serve as solid-phase redox mediators for the catalytic production of liquid-phase S-S bond products and gas-phase H_(2)product.Interestingly,the optimal Quint-MMV-COF presents excellent electrocatalytic efficiency for S-S bond products(yields up to 99%)and H_(2)(~1.62 mmol·g^(-1)·h^(-1))and can be readily recycled for 6 cycles.At the same time,1.52 g product with a yield of~92%can be obtained in the amplification reaction,showing much potential in industrial production.Validated by theoretical calculations,the synergistic effect of multi-metal sites can result in appropriate work function to boost the electron transfer and intermediate adsorption/conversion to achieve excellent overall S-S coupling efficiency.
基金supported by the National Key R&D Program of China(No.2023YFA1507204).The National Natural Science Foundation of China(Nos.22225109,22309054,22171139,22071109,22371080,22201084)China Postdoctoral Science Foundation(Nos.2023M731154,2023M731155,and 2023T160236)+2 种基金China National Postdoctoral Program for Innovative Talents(No.BX20220116)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515013220)Natural Science Foundation of Guangdong Province(No.2023B1515020076).
文摘The lower electricity consumption(EC)and higher value-added products are much desired yet still challenging for the development of CO_(2) coupling electrocatalytic systems.Herein,we give insight into the inherent nature of the retrenchment of EC by exploring the photo-assisted co-electrolysis of methanol and CO_(2) system using a kind of hydroxyl-rich covalent organic frameworks(Dha-COF-Co)with well-tuned pore structure and morphology.Specifically,the hydroxyl induced hydrogen bond interaction in Dha-COF-Co enables to simultaneously regulate the pore microenvironment and nanoribbon morphology of COFs for performance boosting.Notably,the obtained Dha-COF-Co nanoribbon exhibits an overall EC retrenchment of~41.2%(highest in porous crystalline materials to date)when replacing the anodic OER with MOR in the photo-electrocatalytic MOR-CO_(2)RR coupling system,as well as superior FEHCOOH(anode,~100%)and FE_(CO)(cathode,>95%)at 1.8 V.Combined theoretical calculations with various characterizations,the vital role of hydroxyl group in both microenvironment and morphology tuning that can facilitate the CO_(2)RR and MOR kinetics to retrench the EC has been intensively discussed.
基金financially supported by the National Natural Science Foundation of China(21622104,21871142 and 21901122)the Natural Science Foundation of Jiangsu Province of China(BK20171032)+3 种基金the Natural Science Research of Jiangsu Higher Education Institutions of China(17KJB150025 and 19KJB150011)Projects funded by China Postdoctoral Science Foundation(2018 M630572 and 2019 M651873)Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials。
文摘Electrochemical CO2 reduction reaction(CO2RR)to formate is economically viable considering the energy input and market value.Through learning nature,a series of chloroplast-like porous bismuth-based core–shell(CPBC)materials have been designed.In these materials,the porous carbon can enrich and transfer CO2 to the core–shell Bi@Bi2O3 in CO2 reduction process,during which Bi2O3 layer can be transformed into activated metastable layer to efficiently convert CO2 into formate and Bi can provide abundant electrons.Based on this,superior performances for most of important parameters in CO2 RR can be achieved and best of them,CPBC-1 presents remarkable Faradaic efficiency(FEformate>94%)over a wide potential range(-0.65 to-1.0 V)with high catalysis durability(>72 h).Noteworthy,its maximum energy efficiency is as high as 76.7%at-0.7 V,the highest one in reported bismuth-based materials.This work opens novel perspectives in designing nature-inspired CO2RR electrocatalysts.
基金supported by the National Natural Science Foundation of China(21871141,21871142,21901122,22071109 and 92061101)the Natural Science Research of Jiangsu Higher Education Institutions of China(19KJB150011)+3 种基金China Postdoctoral Science Foundation(2018M630572 and 2019M651873)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX201171)Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘The design of selective and efficient covalent organic frameworks(COFs)based electrocatalysts with tunable morphology for efficient CO_(2) reduction reaction(CO_(2)RR)to CH_(4) is highly desirable.Here,two kinds of anthraquinone-based COFs(i.e.,AAn-COF and OH-AAn-COF)with tunable 1D superstructures(e.g.,nanofibers(NF)and hollow tubes(HT))have been produced via Schiff-base condensation reaction.Interestingly,a rarely reported nanosheet-based self-template mechanism and a nanosheet-crimping mechanism have been demonstrated for the production of COF-based nanofibers and hollow tubes,respectively.Besides,the obtained COF-based superstructures can be post-modified with transition metals for efficient CO_(2)RR.Specifically,AAn-COF-Cu(NF)and OH-AAn-COF-Cu(HT)exhibit superior faradaic-efficiency with CH_(4)(FECH_(4))of 77%(-128.1 mA cm^(-2),-0.9 V)and 61%(-99.5 mA cm^(-2),-1.0 V)in a flow-cell,respectively.Noteworthy,the achieved FECH_(4) of AAn-COF-Cu(NF)(77%)is the highest one among reported crystalline COFs.This work provides a general methodology in exploring morphology-controlled COFs for electrocatalytic CO_(2)RR.
基金This work was supported financially by National Nature Science Foundation of China(NSFC)(nos.21622104,21701085,21871125,21871141,21871142,and 21901122)The National Science Foundation(NSF)of Jiangsu Province of China(no.BK20171032)+2 种基金the Natural Science Research of Jiangsu Higher Education Institutions of China(nos.17KJB150025 and 19KJB150011)Project funded by China Postdoctoral Science Foundation(nos.2018M630572 and 2019M651873)Priority Academ-ic Program Development of Jiangsu Higher Education Institutions and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘Polyester plastics such as poly(ethylene terephthal-ate)(PET)are utilized commonly in everyday life,yet only a small portion of these plastics are recycled,and typically,the recycling procedures face energy or pollution problems.
基金National Natural Science Foundation of China,Grant/Award Numbers:22101089,22225109,22175094,21871141,21871142,22071109,92061101Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110836Open Fund of Energy and Materials Chemistry Joint Laboratory of SCNU and TINCI,Grant/Award Number:SCNU-TINCI-202204。
文摘The conversion of the biomass into eco-friendly fuels and chemicals has been exten-sively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society.Lignin,as a kind of promising biomass energy,has been certified to produce the high-valued chemicals and fuels.Numerous efforts have been made to develop various catalysts for lignin catalytic conversion.Both metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)belong to very important heterogeneous porous catalysts due to their regular porous struc-tures,high specific surface area,and precisely tailored diversities.In the review,thefirst part focused on the catalytic conversion of lignin,lignin model compounds,and lignin derivatives using the pristine MOFs,functional MOF composites,and MOF-derived materials.The second part summarized the catalytic conversion of lignin model compounds using pristine COFs and functional COF composites.The review here mainly concentrated on the design of the materials,screening of catalytic conditions,and explorations of the corresponded mechanisms.Specifically,(1)we summarized the MOF-and COF-based materials for the effects on the catalytic trans-formation of lignin-related substances;(2)we emphasized the catalytic mechanism of C–C and C–O bonds cleavage together with the structure–activity relationships;(3)we in-depth realized the relationship between the chemical/electronic/structural properties of the MOF-and COF-based catalysts and their catalytic performance for lignin-related substances.Finally,the challenges and future perspectives were also discussed on the catalytic conversion of lignin-related substances by MOF-and COF-based catalysts.
基金supported by National Natural Science Foundation of China(grant nos.21871141,21871142,22071109,21901122,22225109,22171139).
文摘A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphen-pockets have been implanted into phthalocyanine(Pc)-based COFs through the elaborate design of structural struts;the produced NiPc-DFP-M COFs(M=Ni and Co)possess the advantages of controllable bimetallic centers with different coordination environments,outstanding light sensitivity,and built-in electric-field effects that can be successfully applied in light-assisted CO_(2)electroreduction.Notably,the optimal heterometallic NiPc-DFP-Co COF presents a∼100%Faradic efficiency for CO formation(FECO)in a wide potential range of−0.7 to−1.1 V and∼70%energy efficiency(−0.7 V)under light-irradiation,which is superior to mono-and homometallic COFs and under dark conditions.The high performance can be ascribed to the synergistic effect of the NiPc and Co-salphen pockets that can largely reduce the rate-determining energy-barrier and enhance the electron density to boost the light-assisted activity as supported by density functional theory calculations.A series of bimetallic Pc-based NiPc-DFP-M COF(M=Ni and Co)with integrated salphen-pockets and NiPc units have been synthesized and successfully applied in efficient light-assisted CO_(2)electroreduction.
基金financially supported by the NSFC(grant nos.92061101,21871141,and 22225109)the Excellent Youth Foundation of Jiangsu Natural Science Foundation(grant no.BK20211593)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_1546)Priority Academic Program Development of Jiangsu Higher Education Institutions,and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘Well-defined crystalline coordination compound catalysts have showcased distinct advantages in the regulation of the species and selectivity of electrocatalytic CO_(2)reduction products.However,the systematic study of the crystal-facet effect of crystalline coordination compounds on the performance of electrocatalytic CO_(2)reduction has not yet been reported.Herein,a stable hexanuclear copper cluster(Cu6)catalyst model system is designed and synthesized.By effectively regulating the growth size(micro-nano size)and morphology of the Cu6 single crystal,Cu6(P)with the main(100)facet,Cu6(H)with the main(100)and(001)facets,and Cu6(S)with the main(001)facet are obtained.From Cu6(P)via Cu6(H)to Cu6(S),there is a shift from the predominantly exposed(100)facet(involving two non-adjacent active Cu sites)to the(001)facet(involving three adjacent active Cu sites),which directly affects the adsorption direction of the key*CO intermediate and the potential of C-C coupling,thus enabling effective regulation of the selectivity of C1(CO and CH4)and C2(C2H4)reduction products.This work provides an essential molecular model system and a novel design perspective for the systematic study of the crystalfacet effect of coordination compounds on the species and selectivity of CO_(2)reduction reaction products.
基金supported by the Project of“Key Research&Development(R&D)Plan of Zhejiang Province”[NO.2019C03034].
文摘Intracranial aneurysms have a high prevalence in the population and are associated with high rates of disability and mortality after rupture.It is essential to assess the rupture risk of unruptured intracranial aneurysms by selecting appropriate morphological parameters.However,there is still a need for consistent evidence-based medicine to provide a clinical reference.Therefore,the expert group has jointly written this consensus based on literature review and clinical experience,aiming to provide a standardized reference for predicting the development of intracranial aneurysms and evaluating their rupture risk factors.
