Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars wi...Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars with concurrent production of H_(2),which remains challenging.Here,the photo-catalytic activity for glucose decomposition to HCOOH,CO(C_(1) chemicals),and H_(2) on Cu/TiO_(2)was enhanced by nitrogen doping.Owing to nitrogen doping,atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO_(2).The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2p orbit,distinct from undoped Cu/TiO_(2).Therefore,the lifetime of charge carriers is prolonged,resulting in the pro-duction of C_(1) chemicals and H_(2) with productivities 1.7 and 2.1 folds that of Cu/TiO_(2).This work pro-vides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.展开更多
Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic ...Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic CO_(2) conversion.Herein,a modified TiO_(2)/In_(2)O_(3)(R-P2 5/In_(2)O_(3-x)) type Ⅱ heterojunction composite with oxygen vacancies is designed for photocatalytic CO_(2) reduction,which exhibits excellent CO_(2) reduction activity,with a C_(2) selectivity of 56.66%(in terms of R_(electron)).In situ Fourier-transform infrared spectroscopy(DRIFTS) and time-resolved photoluminescence(TR-PL) spectroscopy are used to reveal the intermediate formation of the photocatalytic mechanism and photogenerated electron lifetime,respectively.The experimental characterizations reveal that the R-P25/In_(2)O_(3-x) composite shows a remarkable behavior for coupling C-C bonds.Besides,efficient charge separation contributes to the improved CO_(2) conversion performance of photocatalysts.This work introduces a type Ⅱ heterojunction composite photocatalyst,which promotes understanding the CO_(2) reduction mechanisms on heterojunction composites and is valuable for the development of photocatalysts.展开更多
Molecular copper catalysts serve as exemplary models for correlating the structure-reaction-mechanism relationship in the electrochemical CO_(2) reduction(eCO_(2)R),owing to their adaptable environments surrounding th...Molecular copper catalysts serve as exemplary models for correlating the structure-reaction-mechanism relationship in the electrochemical CO_(2) reduction(eCO_(2)R),owing to their adaptable environments surrounding the copper metal centres.This investigation,employing density functional theory calculations,focuses on a novel family of binuclear Cu molecular catalysts.The modulation of their coordination configuration through the introduction of organic groups aims to assess their efficacy in converting CO_(2) to C_(2)products.Our findings highlight the crucial role of chemical valence state in shaping the characteristics of binuclear Cu catalysts,consequently influencing the eCO_(2)R behaviour,Notably,the Cu(Ⅱ)Cu(Ⅱ)macrocycle catalyst exhibits enhanced suppression of the hydrogen evolution reaction(HER),facilitating proton trans fer and the eCO_(2)R process.Fu rthermore,we explo re the impact of diverse electro n-withdrawing and electron-donating groups coordinated to the macrocycle(R=-F,-H,and-OCH_3)on the electron distribution in the molecular catalysts.Strategic placement of-OCH_3 groups in the macrocycles leads to a favourable oxidation state of the Cu centres and subsequent C-C coupling to form C_(2) products.This research provides fundamental insights into the design and optimization of binuclear Cu molecular catalysts for the electrochemical conversion of CO_(2) to value-added C_(2) products.展开更多
Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has gar...Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.展开更多
Our previous study has revealed that procyanidin A_(1)(A_(1))and its simulated digestive product(D-A,)can alleviate acrylamide(ACR)-induced intestine cell damage.However,the underlying mechanism remains unknown.In thi...Our previous study has revealed that procyanidin A_(1)(A_(1))and its simulated digestive product(D-A,)can alleviate acrylamide(ACR)-induced intestine cell damage.However,the underlying mechanism remains unknown.In this study,we elucidated the molecular mechanism for and D-A_(1) to alleviate ACR-stimulated IPEC-J2 cell damage.ACR slightly activated nuclear factor erythroid 2-related factor 2(Nrf2)signaling and its target genes,but this activation could not reduce intestine cell damage.A_(1) and D-A_(1) could alleviate ACR-induced cell damage,but the effect was abrogated in cells transiently transfected with Nrf2 small interfering RNA(siRNA).Further investigation confirmed that A_(1) and D-A_(1) interacted with Ketch-like ECH-associated protein 1(Keapl),which boosted the stabilization of Nrf2,subsequently promoted the translocation of Nrf2 into the nucleus,and further increased the expression of antioxidant proteins,thereby inhibiting glutathione(GSH)consumption,maintaining redox balance and eventually alleviating ACR-induced cell damage.Importantly,there was no difference between A_(1) and D-A_(1) treated groups,indicating that A_(1) can tolerate gastrointestinal digestion and may be a potential compound to limit the toxicity of ACR.展开更多
Cu-based electrocatalysts have become the focus in the field of electrochemical CO_(2) reduction reaction(ECO_(2) RR)due to their ability to produce multicarbon products.However,the research on generating single carbo...Cu-based electrocatalysts have become the focus in the field of electrochemical CO_(2) reduction reaction(ECO_(2) RR)due to their ability to produce multicarbon products.However,the research on generating single carbon products with higher economic feasibility via ECO_(2) RR based on Cu-based electrocatalysts is rather rare,and the roles of the surface architecture and oxides of the electrocatalysts have not been explained exactly.In this work,a two-step method including thermal oxidation and electroreduction is proposed to introduce Cuþinto pure Cu foil to form Cu_(2)O/Cu electrocatalyst.By regulating the surface composition and morphology of the electrocatalyst in this way,the activity of ECO 2 RR to C_(1) products has been greatly improved.The Faradaic efficiency of carbon products of the Cu_(2)O/Cu electrode reaches 84%at?0.7 V vs.RHE with good selectivity for HCOOH and CO.The current density of Cu_(2)O/Cu electrode reaches-12.21 mA cm^(2) at-0.8 V vs.RHE,which is much higher than that of the Cu foil electrode(?0.09 mA cm?2).In-situ Raman characterization shows that Cuþin Cu_(2)O/Cu electrode could inhibit hydrogen generation and promote ECO_(2) RR by stabilizing the adsorption of CO_(2).展开更多
Solar-driven water splitting for photocatalytic hydrogen evolution is considered a highly promising and costeffective solution to achieve a stable renewable energy supply.However,the sluggish kinetics of electron-hole...Solar-driven water splitting for photocatalytic hydrogen evolution is considered a highly promising and costeffective solution to achieve a stable renewable energy supply.However,the sluggish kinetics of electron-hole pairs’separation poses challenges in attaining satisfactory hydrogen production efficiency.Herein,we synthesized the exceptional performance of highly crystalline C_(3)N_(5)(HC–C_(3)N_(5))nanosheet as a photocatalyst,demonstrating a remarkable hydrogen evolution rate of 3.01 mmol h^(-1)g^(-1),which surpasses that of bulk C_(3)N_(5)(B–C_(3)N_(5))by a factor of 3.27.Experimental and theoretical analyses reveal that HC-C_(3)N_(5)nanosheets exhibit intriguing macroscopic photoinduced color changes,effectively broadening the absorption spectrum and significantly enhancing the generation of excitons.Besides,the cyano groups in HC-C_(3)N_(5)efficiently captures and converts photoexcited electrons into bound states,thereby prolonging their lifetimes and effectively separating electrons and holes into catalytically active regions.This research provides valuable insights into the establishment of bound electronic states for developing efficient photocatalysts.展开更多
[Objective] This study discussed the SNPs of SLC27A1 gene and its relationship with milk production traits in Chinese Holstein Cattle in order to find the SNP site which had significant effect on milk production trait...[Objective] This study discussed the SNPs of SLC27A1 gene and its relationship with milk production traits in Chinese Holstein Cattle in order to find the SNP site which had significant effect on milk production traits in Chinese Holstein Cattle.[Method] DNA was extracted from the bleed of 48 Chinese Holstein Cattle selected according to phenotypic character and mixed into DNA pool for SNPs detection by polymerase chain reaction-single strand conformation polymorphism（PCR-SSCP）and cloning sequencing.Then different genotypes were detected in other 231 Chinese Holstein Cattle by PCR-RFLP.The association between genotype and production traits was assessed by GLM procedure,SAS version 8.02.[Result] There were T112C in exon3 and G64A loci in 3＇UTR,among them the T112C in exon3 was synonymous mutation.There were 3 genotypes TT,TC and CC in T112C locus and 3 genotypes GG,GA and AA in G64A locus.The population was at Hardy-Weinberg equilibration.Cows with genotype CC had significantly highest milk yield than those with genotype TC（P0.01）,and there were no significant differences among the 3 genotypes on milk protein percent and milk fat percent（P0.05）,but the tendency of CC TC TT on milk protein percent and the tendency of TT TC CC on milk fat percent were showed.There was no significant difference among the 3 genotypes of G64A loci on milk yield,milk protein percent and milk fat percent（P0.05）,but the tendency of GA GG AA on milk yield and the tendency of AA GG GA both on milk protein percent and milk fat percent were showed.[Conclusion] There was certain relation between the T112C locus and milk yield traits;It may improve milk yield to raise the frequency of genotype CC;SLC27A1 gene could be a useful candidate gene in selection program on milk yield traits in Chinese Holstein Cattle,which provided a theoretical basis for the marker-assisted breeding and further study of SLC27A1 gene.展开更多
文摘Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars with concurrent production of H_(2),which remains challenging.Here,the photo-catalytic activity for glucose decomposition to HCOOH,CO(C_(1) chemicals),and H_(2) on Cu/TiO_(2)was enhanced by nitrogen doping.Owing to nitrogen doping,atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO_(2).The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2p orbit,distinct from undoped Cu/TiO_(2).Therefore,the lifetime of charge carriers is prolonged,resulting in the pro-duction of C_(1) chemicals and H_(2) with productivities 1.7 and 2.1 folds that of Cu/TiO_(2).This work pro-vides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.
基金National Research Foundation (NRF) of Korea grant funded by the Korea Government (MSIT) (NRF-2022R1A2C2093415)partially funding from the Circle Foundation (Republic of Korea) (Grant Number: 2023 TCF Innovative Science Project-03))partially Korea Basic Science Institute (National Research Facilities and Equipment Center) grant funded by the Ministry of Education (2022R1A6C101A751)。
文摘Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic CO_(2) conversion.Herein,a modified TiO_(2)/In_(2)O_(3)(R-P2 5/In_(2)O_(3-x)) type Ⅱ heterojunction composite with oxygen vacancies is designed for photocatalytic CO_(2) reduction,which exhibits excellent CO_(2) reduction activity,with a C_(2) selectivity of 56.66%(in terms of R_(electron)).In situ Fourier-transform infrared spectroscopy(DRIFTS) and time-resolved photoluminescence(TR-PL) spectroscopy are used to reveal the intermediate formation of the photocatalytic mechanism and photogenerated electron lifetime,respectively.The experimental characterizations reveal that the R-P25/In_(2)O_(3-x) composite shows a remarkable behavior for coupling C-C bonds.Besides,efficient charge separation contributes to the improved CO_(2) conversion performance of photocatalysts.This work introduces a type Ⅱ heterojunction composite photocatalyst,which promotes understanding the CO_(2) reduction mechanisms on heterojunction composites and is valuable for the development of photocatalysts.
基金the HUST-QMUL Strategic Partnership Research Funding(No.2022-HUST-QMUL-SPRF-03),which funded the project“Design of Binuclear Copper Electrocatalysts for CO_(2) Conversion from First Principles”the China Scholarship Council for financial support。
文摘Molecular copper catalysts serve as exemplary models for correlating the structure-reaction-mechanism relationship in the electrochemical CO_(2) reduction(eCO_(2)R),owing to their adaptable environments surrounding the copper metal centres.This investigation,employing density functional theory calculations,focuses on a novel family of binuclear Cu molecular catalysts.The modulation of their coordination configuration through the introduction of organic groups aims to assess their efficacy in converting CO_(2) to C_(2)products.Our findings highlight the crucial role of chemical valence state in shaping the characteristics of binuclear Cu catalysts,consequently influencing the eCO_(2)R behaviour,Notably,the Cu(Ⅱ)Cu(Ⅱ)macrocycle catalyst exhibits enhanced suppression of the hydrogen evolution reaction(HER),facilitating proton trans fer and the eCO_(2)R process.Fu rthermore,we explo re the impact of diverse electro n-withdrawing and electron-donating groups coordinated to the macrocycle(R=-F,-H,and-OCH_3)on the electron distribution in the molecular catalysts.Strategic placement of-OCH_3 groups in the macrocycles leads to a favourable oxidation state of the Cu centres and subsequent C-C coupling to form C_(2) products.This research provides fundamental insights into the design and optimization of binuclear Cu molecular catalysts for the electrochemical conversion of CO_(2) to value-added C_(2) products.
基金supported by the National Key R&D Program of China(No.2021YFB2800700)National Natural Science Foundation of China(Nos.12274210,62227820,and 12174183)+1 种基金Partial support is from NSF of Jiangsu Province(No.BK20220006)the Fundamental Research Funds for the Central Universities and Jiangsu Key Laboratory of Advanced Techniques for Manipulating Electromagnetic Waves。
文摘Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.
基金supported by the project from National Natural Science Foundation of China (31671962)Fundamental Research Funds for the Central Universities (2662019PY034)。
文摘Our previous study has revealed that procyanidin A_(1)(A_(1))and its simulated digestive product(D-A,)can alleviate acrylamide(ACR)-induced intestine cell damage.However,the underlying mechanism remains unknown.In this study,we elucidated the molecular mechanism for and D-A_(1) to alleviate ACR-stimulated IPEC-J2 cell damage.ACR slightly activated nuclear factor erythroid 2-related factor 2(Nrf2)signaling and its target genes,but this activation could not reduce intestine cell damage.A_(1) and D-A_(1) could alleviate ACR-induced cell damage,but the effect was abrogated in cells transiently transfected with Nrf2 small interfering RNA(siRNA).Further investigation confirmed that A_(1) and D-A_(1) interacted with Ketch-like ECH-associated protein 1(Keapl),which boosted the stabilization of Nrf2,subsequently promoted the translocation of Nrf2 into the nucleus,and further increased the expression of antioxidant proteins,thereby inhibiting glutathione(GSH)consumption,maintaining redox balance and eventually alleviating ACR-induced cell damage.Importantly,there was no difference between A_(1) and D-A_(1) treated groups,indicating that A_(1) can tolerate gastrointestinal digestion and may be a potential compound to limit the toxicity of ACR.
基金supported by National Natural Science Foundation of China(No.52071183).
文摘Cu-based electrocatalysts have become the focus in the field of electrochemical CO_(2) reduction reaction(ECO_(2) RR)due to their ability to produce multicarbon products.However,the research on generating single carbon products with higher economic feasibility via ECO_(2) RR based on Cu-based electrocatalysts is rather rare,and the roles of the surface architecture and oxides of the electrocatalysts have not been explained exactly.In this work,a two-step method including thermal oxidation and electroreduction is proposed to introduce Cuþinto pure Cu foil to form Cu_(2)O/Cu electrocatalyst.By regulating the surface composition and morphology of the electrocatalyst in this way,the activity of ECO 2 RR to C_(1) products has been greatly improved.The Faradaic efficiency of carbon products of the Cu_(2)O/Cu electrode reaches 84%at?0.7 V vs.RHE with good selectivity for HCOOH and CO.The current density of Cu_(2)O/Cu electrode reaches-12.21 mA cm^(2) at-0.8 V vs.RHE,which is much higher than that of the Cu foil electrode(?0.09 mA cm?2).In-situ Raman characterization shows that Cuþin Cu_(2)O/Cu electrode could inhibit hydrogen generation and promote ECO_(2) RR by stabilizing the adsorption of CO_(2).
基金supported by the National Natural Science Foundation of China(No.22006057,21906072 and 21908115)Postgraduate Research&Practice Innovation Program of Jiangsu Province(China)(SJCX23_2197)Natural Science Foundation of Zhejiang Province of China(LY20E080014).
文摘Solar-driven water splitting for photocatalytic hydrogen evolution is considered a highly promising and costeffective solution to achieve a stable renewable energy supply.However,the sluggish kinetics of electron-hole pairs’separation poses challenges in attaining satisfactory hydrogen production efficiency.Herein,we synthesized the exceptional performance of highly crystalline C_(3)N_(5)(HC–C_(3)N_(5))nanosheet as a photocatalyst,demonstrating a remarkable hydrogen evolution rate of 3.01 mmol h^(-1)g^(-1),which surpasses that of bulk C_(3)N_(5)(B–C_(3)N_(5))by a factor of 3.27.Experimental and theoretical analyses reveal that HC-C_(3)N_(5)nanosheets exhibit intriguing macroscopic photoinduced color changes,effectively broadening the absorption spectrum and significantly enhancing the generation of excitons.Besides,the cyano groups in HC-C_(3)N_(5)efficiently captures and converts photoexcited electrons into bound states,thereby prolonging their lifetimes and effectively separating electrons and holes into catalytically active regions.This research provides valuable insights into the establishment of bound electronic states for developing efficient photocatalysts.
基金Supported by National Science and Technology R&D Program(2006BAD04A01)National Natural Science Foundation of China(30571329)~~
文摘[Objective] This study discussed the SNPs of SLC27A1 gene and its relationship with milk production traits in Chinese Holstein Cattle in order to find the SNP site which had significant effect on milk production traits in Chinese Holstein Cattle.[Method] DNA was extracted from the bleed of 48 Chinese Holstein Cattle selected according to phenotypic character and mixed into DNA pool for SNPs detection by polymerase chain reaction-single strand conformation polymorphism（PCR-SSCP）and cloning sequencing.Then different genotypes were detected in other 231 Chinese Holstein Cattle by PCR-RFLP.The association between genotype and production traits was assessed by GLM procedure,SAS version 8.02.[Result] There were T112C in exon3 and G64A loci in 3＇UTR,among them the T112C in exon3 was synonymous mutation.There were 3 genotypes TT,TC and CC in T112C locus and 3 genotypes GG,GA and AA in G64A locus.The population was at Hardy-Weinberg equilibration.Cows with genotype CC had significantly highest milk yield than those with genotype TC（P0.01）,and there were no significant differences among the 3 genotypes on milk protein percent and milk fat percent（P0.05）,but the tendency of CC TC TT on milk protein percent and the tendency of TT TC CC on milk fat percent were showed.There was no significant difference among the 3 genotypes of G64A loci on milk yield,milk protein percent and milk fat percent（P0.05）,but the tendency of GA GG AA on milk yield and the tendency of AA GG GA both on milk protein percent and milk fat percent were showed.[Conclusion] There was certain relation between the T112C locus and milk yield traits;It may improve milk yield to raise the frequency of genotype CC;SLC27A1 gene could be a useful candidate gene in selection program on milk yield traits in Chinese Holstein Cattle,which provided a theoretical basis for the marker-assisted breeding and further study of SLC27A1 gene.
