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
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
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
Plasma-based CO_(2)conversion is promising for carbon capture and utilization.However,inconsistent reporting of the performance metrics makes it difficult to compare plasma processes systematically,complicates elucida...Plasma-based CO_(2)conversion is promising for carbon capture and utilization.However,inconsistent reporting of the performance metrics makes it difficult to compare plasma processes systematically,complicates elucidating the underlying mechanisms and compromises further development of this technology.Therefore,this critical review summarizes the correct definitions for gas conversion in plasma reactors and highlights common errors and inconsistencies observed throughout literature.This is done for pure CO_(2)splitting,dry reforming of methane and CO_(2)hydrogenation.We demonstrate that the change in volumetric flow rate is a critical aspect,inherent to these reactions,that is often not correctly taken into account.For dry reforming of methane and CO_(2)hydrogenation,we also demonstrate inconsistent reporting of energy efficiency,and through numerical examples,we show the significance of these deviations.Furthermore,we discuss how to measure changes in volumetric flow rate,supported by data from two experimental examples,showing that the sensitivity inherent to a standard component and a flow meter is essential to consider when deriving the performance metrics.Finally,some general recommendations and good practices are provided.This paper aims to be a comprehensive guideline for authors,to encourage more consistent calculations and stimulate the further development of this technology.展开更多
Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spect...Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.展开更多
The conversion of CO_(2) into fuels and valuable chemicals is one of the central topics to combat climate change and meet the growing demand for renewable energy.Herein,we show that the formate dehydrogenase from Clos...The conversion of CO_(2) into fuels and valuable chemicals is one of the central topics to combat climate change and meet the growing demand for renewable energy.Herein,we show that the formate dehydrogenase from Clostridium ljungdahlii(ClFDH)adsorbed on electrodes displays clear characteristic voltammetric signals that can be assigned to the reduction and oxidation potential of the[4Fe-4S]^(2+/+)cluster under nonturnover conditions.Upon adding substrates,the signals transform into a specific redox center that engages in catalytic electron transport.ClFDH catalyzes rapid and efficient reversible interconversion between CO_(2) and formate in the presence of substrates.The turnover frequency of electrochemical CO_(2) reduction is determined as 1210 s^(-1) at 25℃ and pH 7.0,which can be further enhanced up to 1786 s^(-1) at 50℃.The Faradaic efficiency at−0.6 V(vs.standard hydrogen electrode)is recorded as 99.3%in a 2-h reaction.Inhibition experiments and theoretical modeling disclose interesting pathways for CO_(2) entry,formate exit,and OCN−competition,suggesting an oxidation-state-dependent binding mechanism of catalysis.Our results provide a different perspective for understanding the catalytic mechanism of FDH and original insights into the design of synthetic catalysts.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financial support from the Fund for Scientific Research(FWO)Flanders(Grant ID 110221N)the European Research Council(ERC)under the European Union’s Horizon 2020 Research and Innovation Program(grant agreement No 810182-SCOPE ERC Synergy project)the Methusalem funding of the University of Antwerp。
文摘Plasma-based CO_(2)conversion is promising for carbon capture and utilization.However,inconsistent reporting of the performance metrics makes it difficult to compare plasma processes systematically,complicates elucidating the underlying mechanisms and compromises further development of this technology.Therefore,this critical review summarizes the correct definitions for gas conversion in plasma reactors and highlights common errors and inconsistencies observed throughout literature.This is done for pure CO_(2)splitting,dry reforming of methane and CO_(2)hydrogenation.We demonstrate that the change in volumetric flow rate is a critical aspect,inherent to these reactions,that is often not correctly taken into account.For dry reforming of methane and CO_(2)hydrogenation,we also demonstrate inconsistent reporting of energy efficiency,and through numerical examples,we show the significance of these deviations.Furthermore,we discuss how to measure changes in volumetric flow rate,supported by data from two experimental examples,showing that the sensitivity inherent to a standard component and a flow meter is essential to consider when deriving the performance metrics.Finally,some general recommendations and good practices are provided.This paper aims to be a comprehensive guideline for authors,to encourage more consistent calculations and stimulate the further development of this technology.
基金supported by Russian Science Foundation (No.#21-73-10235)
文摘Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.
基金support from the National Key Research and Development Program of China (No.2020YFA0907300)the National Natural Science Foundation of China (No.22077069)+1 种基金the Natural Science Foundation of Tianjin (19JCZDJC33400)the Fundamental Research Funds for the Central Universities,Nankai University (63201111).
文摘The conversion of CO_(2) into fuels and valuable chemicals is one of the central topics to combat climate change and meet the growing demand for renewable energy.Herein,we show that the formate dehydrogenase from Clostridium ljungdahlii(ClFDH)adsorbed on electrodes displays clear characteristic voltammetric signals that can be assigned to the reduction and oxidation potential of the[4Fe-4S]^(2+/+)cluster under nonturnover conditions.Upon adding substrates,the signals transform into a specific redox center that engages in catalytic electron transport.ClFDH catalyzes rapid and efficient reversible interconversion between CO_(2) and formate in the presence of substrates.The turnover frequency of electrochemical CO_(2) reduction is determined as 1210 s^(-1) at 25℃ and pH 7.0,which can be further enhanced up to 1786 s^(-1) at 50℃.The Faradaic efficiency at−0.6 V(vs.standard hydrogen electrode)is recorded as 99.3%in a 2-h reaction.Inhibition experiments and theoretical modeling disclose interesting pathways for CO_(2) entry,formate exit,and OCN−competition,suggesting an oxidation-state-dependent binding mechanism of catalysis.Our results provide a different perspective for understanding the catalytic mechanism of FDH and original insights into the design of synthetic catalysts.
