The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving c...The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.展开更多
Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of...Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.展开更多
Dendritic mesoporous silica nanoparticles own three-dimensional center-radial channels and hierarchical pores,which endows themselves with super-high specific surface area,extremely large pore volumes,especially acces...Dendritic mesoporous silica nanoparticles own three-dimensional center-radial channels and hierarchical pores,which endows themselves with super-high specific surface area,extremely large pore volumes,especially accessible internal spaces,and so forth.Dissimilar guest species(such as organic groups or metal nanoparticles)could be readily decorated onto the interfaces of the channels and pores,realizing the functionalization of dendritic mesoporous silica nanoparticles for targeted applications.As adsorbents and catalysts,dendritic mesoporous silica nanoparticles-based materials have experienced nonignorable development in CO_(2)capture and catalytic conversion.This comprehensive review provides a critical survey on this pregnant subject,summarizing the designed construction of novel dendritic mesoporous silica nanoparticles-based materials,the involved chemical reactions(such as CO_(2)methanation,dry reforming of CH_(4)),the value-added chemicals from CO_(2)(such as cyclic carbonates,2-oxazolidinones,quinazoline-2,4(1H,3H)-diones),and so on.The adsorptive and catalytic performances have been compared with traditional silica mesoporous materials(such as SBA-15 or MCM-41),and the corresponding reaction mechanisms have been thoroughly revealed.It is sincerely expected that the in-depth discussion could give materials scientists certain inspiration to design brand-new dendritic mesoporous silica nanoparticles-based materials with superior capabilities towards CO_(2)capture,utilization,and storage.展开更多
Direct in vivo conversion of astrocytes into functional new neurons induced by neural transcription factors has been recognized as a potential new therapeutic intervention for neural injury and degenerative disorders....Direct in vivo conversion of astrocytes into functional new neurons induced by neural transcription factors has been recognized as a potential new therapeutic intervention for neural injury and degenerative disorders. However, a few recent studies have claimed that neural transcription factors cannot convert astrocytes into neurons, attributing the converted neurons to pre-existing neurons mis-expressing transgenes. In this study, we overexpressed three distinct neural transcription factors––NeuroD1, Ascl1, and Dlx2––in reactive astrocytes in mouse cortices subjected to stab injury, resulting in a series of significant changes in astrocyte properties. Initially, the three neural transcription factors were exclusively expressed in the nuclei of astrocytes. Over time, however, these astrocytes gradually adopted neuronal morphology, and the neural transcription factors was gradually observed in the nuclei of neuron-like cells instead of astrocytes. Furthermore,we noted that transcription factor-infected astrocytes showed a progressive decrease in the expression of astrocytic markers AQP4(astrocyte endfeet signal), CX43(gap junction signal), and S100β. Importantly, none of these changes could be attributed to transgene leakage into preexisting neurons. Therefore, our findings suggest that neural transcription factors such as NeuroD1, Ascl1, and Dlx2 can effectively convert reactive astrocytes into neurons in the adult mammalian brain.展开更多
Unraveling atomic-level active sites of layered photocatalyst towards lowconcentration CO_(2) conversion is still challenging.Herein,the yield and selectivity of photocatalytic CO_(2) reduction of the Aurivillius-rela...Unraveling atomic-level active sites of layered photocatalyst towards lowconcentration CO_(2) conversion is still challenging.Herein,the yield and selectivity of photocatalytic CO_(2) reduction of the Aurivillius-related oxide semiconductor Bi_(2)O_(2)SiO_(3) nanosheet(BOSO)were largely improved using a surface sulfidation strategy.The experiment and theoretical calculation confirmed that surface sulfidation of the Bi_(2)O_(2)SiO_(3) nanosheet(S-BOSO,6.28 nm)redistributed the charge-enriched Bi sites,extended the solar spectrum absorption to the whole visible range,and considerably enhanced the charge separation,in addition to creating new reaction active sites,as compared to pristine BOSO.Subsequently,surface sulfidation played a switchable role,wherein S-BOSO showed a very high CH_(3)OH generation rate(12.78μmol g^(-1) for 4 h,78.6%selectivity)from low-concentration CO_(2)(1000 ppm)under visible light irradiation,which outperforms most of the state-of-the-art photocatalysts under similar conditions.This study presents an atomic-level modification protocol for engineering reactive sites and charge behaviors to promote solar-to-energy conversion.展开更多
Hydrophobic treatment of the catalyst surfaces can suppress the competitive hydrogen evolution reaction(HER) during the nitrogen reduction reaction(NRR).In this work,the surface of Ti_(3)C_(2)Ti_(x) MXene is modified ...Hydrophobic treatment of the catalyst surfaces can suppress the competitive hydrogen evolution reaction(HER) during the nitrogen reduction reaction(NRR).In this work,the surface of Ti_(3)C_(2)Ti_(x) MXene is modified by cetyltrimethylammonium bromide(CTAB) and trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-trideca fluorooctyl) silane(FOTS) to increase the hydrophobicity of MXenes.The ammonia(NH_(3)) production rate and faradaic efficiency(FE) are improved from 37.62 to 54.01 μg h^(-1)mg_(cat)^(-1).and 5.5% to 18.1% at-0.7 V vs.RHE,respectively after surface modification.^(15)N isotopic labeling experiment confirms that nitrogen in produced ammonia originates from N_(2) in the electrolyte.The excellent NRR activity of surface hydrophobic MXenes is mainly due to surfactant molecules,which inhibit the entry of water molecules and the competitive HER,which have been verified by in situ FT-IR,DFT and molecular dynamics calculations.This strategy provides an ingenious method to design more active NRR electrocatalysts.展开更多
The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high e...The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high efficiency catalytic system with environmentally benign characteristic are important determinants.In this work,protic ionic liquids[TMG][2-OPy]were prepared via one-step neutralization between 1,1,3,3-tetramethylguanidine and 2-hydroxypyridine,applying to the domain of synthesizing quinzoline-2,4(1 H,3H)-diones from CO_(2)and 2-aminobenzontiles without any solvent or metal,achieving the yield of 97%at 90℃for 8 h under atmospheric.A series of substrates with good to acceptable yield were detected,revealing the generality and universality of the catalyst.Furthermore,the system could be facilely reused for at least six runs,retaining the yield of 94%.A preliminary kinetic equation is calculated with the activation energy of 68 kJ·mol^(-1),and a plausible reaction mechanism was put forward.This study highlights that the[TMG][2-OPy]enables to activate CO_(2)carboxylation efficiently.展开更多
基金financial support from the King Abdullah University of Science and Technology(KAUST).
文摘The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.
基金support from the Tangshan Talent Funding Project(Grant No.A202202007)National Natural Science Foundation of China(Grant Nos.22102136 and 21703065)+2 种基金Natural Science Foundation of Hebei Province(Grant Nos.B2018209267 and E2022209039)Natural Science Foundation of Hubei Province(Grant No.2022CFB1001)Department of Education of Hubei Province(Grant No.Q20221701).
文摘Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.
基金supported by the National Key R&D program of China(2019YFA0706802)National Natural Science Foundation of China(52063029)+2 种基金Natural Science Basic Research Program of Shaanxi(2022JM-200,2021JQ-716)China Postdoctoral Science Foundation(2020M672269)Doctoral Research Program of Yan’an University(YDBK2019-02)
文摘Dendritic mesoporous silica nanoparticles own three-dimensional center-radial channels and hierarchical pores,which endows themselves with super-high specific surface area,extremely large pore volumes,especially accessible internal spaces,and so forth.Dissimilar guest species(such as organic groups or metal nanoparticles)could be readily decorated onto the interfaces of the channels and pores,realizing the functionalization of dendritic mesoporous silica nanoparticles for targeted applications.As adsorbents and catalysts,dendritic mesoporous silica nanoparticles-based materials have experienced nonignorable development in CO_(2)capture and catalytic conversion.This comprehensive review provides a critical survey on this pregnant subject,summarizing the designed construction of novel dendritic mesoporous silica nanoparticles-based materials,the involved chemical reactions(such as CO_(2)methanation,dry reforming of CH_(4)),the value-added chemicals from CO_(2)(such as cyclic carbonates,2-oxazolidinones,quinazoline-2,4(1H,3H)-diones),and so on.The adsorptive and catalytic performances have been compared with traditional silica mesoporous materials(such as SBA-15 or MCM-41),and the corresponding reaction mechanisms have been thoroughly revealed.It is sincerely expected that the in-depth discussion could give materials scientists certain inspiration to design brand-new dendritic mesoporous silica nanoparticles-based materials with superior capabilities towards CO_(2)capture,utilization,and storage.
基金supported by the Key Project of Guangzhou City,No.202206060002Science and Technology Project of Guangdong Province,No.2018B030332001Guangdong Provincial Pearl River Project,No.2021ZT09Y552 (all to GC)。
文摘Direct in vivo conversion of astrocytes into functional new neurons induced by neural transcription factors has been recognized as a potential new therapeutic intervention for neural injury and degenerative disorders. However, a few recent studies have claimed that neural transcription factors cannot convert astrocytes into neurons, attributing the converted neurons to pre-existing neurons mis-expressing transgenes. In this study, we overexpressed three distinct neural transcription factors––NeuroD1, Ascl1, and Dlx2––in reactive astrocytes in mouse cortices subjected to stab injury, resulting in a series of significant changes in astrocyte properties. Initially, the three neural transcription factors were exclusively expressed in the nuclei of astrocytes. Over time, however, these astrocytes gradually adopted neuronal morphology, and the neural transcription factors was gradually observed in the nuclei of neuron-like cells instead of astrocytes. Furthermore,we noted that transcription factor-infected astrocytes showed a progressive decrease in the expression of astrocytic markers AQP4(astrocyte endfeet signal), CX43(gap junction signal), and S100β. Importantly, none of these changes could be attributed to transgene leakage into preexisting neurons. Therefore, our findings suggest that neural transcription factors such as NeuroD1, Ascl1, and Dlx2 can effectively convert reactive astrocytes into neurons in the adult mammalian brain.
基金Natural Science Foundation of Hubei Province,Grant/Award Number:2021CFB242Research Project of Hubei Provincial Department of Education,Grant/Award Number:Q20202501+3 种基金China Postdoctoral Science Foundation,Grant/Award Number:2020M682878National Natural Science Foundation of China,Grant/Award Numbers:51971124,52104254,52171217State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Jiaotong University,Grant/Award Number:EIPE22208National Postdoctoral Program for Innovative Talents,Grant/Award Number:BX20200222。
文摘Unraveling atomic-level active sites of layered photocatalyst towards lowconcentration CO_(2) conversion is still challenging.Herein,the yield and selectivity of photocatalytic CO_(2) reduction of the Aurivillius-related oxide semiconductor Bi_(2)O_(2)SiO_(3) nanosheet(BOSO)were largely improved using a surface sulfidation strategy.The experiment and theoretical calculation confirmed that surface sulfidation of the Bi_(2)O_(2)SiO_(3) nanosheet(S-BOSO,6.28 nm)redistributed the charge-enriched Bi sites,extended the solar spectrum absorption to the whole visible range,and considerably enhanced the charge separation,in addition to creating new reaction active sites,as compared to pristine BOSO.Subsequently,surface sulfidation played a switchable role,wherein S-BOSO showed a very high CH_(3)OH generation rate(12.78μmol g^(-1) for 4 h,78.6%selectivity)from low-concentration CO_(2)(1000 ppm)under visible light irradiation,which outperforms most of the state-of-the-art photocatalysts under similar conditions.This study presents an atomic-level modification protocol for engineering reactive sites and charge behaviors to promote solar-to-energy conversion.
基金fundings from the National Natural Science Foundation of China (No. 51872173)Taishan Scholar Foundation of Shandong Province (No. tsqn201812068)+3 种基金Natural Science Foundation of Shandong Province (No. ZR2022JQ21)Higher School Youth Innovation Team of Shandong Province (No. 2019KJA013)Hong Kong Scholars Program (No. XJ2019042)Innovation and Technology Commission of the Hong Kong Special Administrative Region (No. ITC-CNERC14EG03)。
文摘Hydrophobic treatment of the catalyst surfaces can suppress the competitive hydrogen evolution reaction(HER) during the nitrogen reduction reaction(NRR).In this work,the surface of Ti_(3)C_(2)Ti_(x) MXene is modified by cetyltrimethylammonium bromide(CTAB) and trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-trideca fluorooctyl) silane(FOTS) to increase the hydrophobicity of MXenes.The ammonia(NH_(3)) production rate and faradaic efficiency(FE) are improved from 37.62 to 54.01 μg h^(-1)mg_(cat)^(-1).and 5.5% to 18.1% at-0.7 V vs.RHE,respectively after surface modification.^(15)N isotopic labeling experiment confirms that nitrogen in produced ammonia originates from N_(2) in the electrolyte.The excellent NRR activity of surface hydrophobic MXenes is mainly due to surfactant molecules,which inhibit the entry of water molecules and the competitive HER,which have been verified by in situ FT-IR,DFT and molecular dynamics calculations.This strategy provides an ingenious method to design more active NRR electrocatalysts.
基金supported by the National Natural Science Foundation of China(22278202)the Natural Science Foundation of Jiangsu Province(BM2018007.BK20210185).
文摘The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high efficiency catalytic system with environmentally benign characteristic are important determinants.In this work,protic ionic liquids[TMG][2-OPy]were prepared via one-step neutralization between 1,1,3,3-tetramethylguanidine and 2-hydroxypyridine,applying to the domain of synthesizing quinzoline-2,4(1 H,3H)-diones from CO_(2)and 2-aminobenzontiles without any solvent or metal,achieving the yield of 97%at 90℃for 8 h under atmospheric.A series of substrates with good to acceptable yield were detected,revealing the generality and universality of the catalyst.Furthermore,the system could be facilely reused for at least six runs,retaining the yield of 94%.A preliminary kinetic equation is calculated with the activation energy of 68 kJ·mol^(-1),and a plausible reaction mechanism was put forward.This study highlights that the[TMG][2-OPy]enables to activate CO_(2)carboxylation efficiently.
