Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenati...Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.展开更多
Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capp...Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capped triphasic heterostructure Cu_(3)P/Co_(2)P/CoP@NC stands for nitrogen doped carbon nanorods were designed and synthesized through a combination of phosphide and carbonization.Kinetic analyses(cyclic voltammetry,electrochemical impedance spectroscopy,and galvanostatic intermittent titration technique)and density functional theory calculations show that the three-phase heterostructure and carbon layer effectively improve Na adsorption and migration as well as the electrochemical reactivity of the electrode.Based on this,Cu_(3)P/Co_(2)P/CoP@NC demonstrated excellent rate performance(305.9 mAh g^(-1)at 0.3 A g^(-1)and 202.8 mAh g^(-1)even at 10 A g^(-1))and cycling stability(the capacity decay rate is only 0.12%from the 5th to 300th cycle)when it is used for sodium-ion battery anodes.The in situ X-ray diffraction,ex situ X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy tests showed that Cu_(3)P/Co_(2)P/CoP@NC is based on a conversion reaction mechanism for sodium-ion storage.In addition,the NVP@reduced graphene oxide(rGO)//Cu_(3)P/Co_(2)P/CoP@NC full-cell delivers a high capacity of 210.2 mAh g^(-1)after 50 cycles at 0.3 A g^(-1).This work can provide a reference for the design of high-performance sodium electrode anode materials.展开更多
Herein,a modified screen printed carbon electrode(SPCE)based on a composite material,graphene oxide-gold nanoparticles(GO-AuNPs),and poly(3-aminobenzoic acid)(P3ABA)for the detection of paraquat(PQ)is introduced.The m...Herein,a modified screen printed carbon electrode(SPCE)based on a composite material,graphene oxide-gold nanoparticles(GO-AuNPs),and poly(3-aminobenzoic acid)(P3ABA)for the detection of paraquat(PQ)is introduced.The modified electrode was fabricated by drop casting of the GO-AuNPs,followed by electropolymerization of 3-aminobenzoic acid to achieve SPCE/GO-AuNPs/P3ABA.The morphology and microstructural characteristics of the modified electrodes were revealed by scanning electron microscopy(SEM)for each step of modification.The composite GO-AuNPs can provide high surface area and enhance electroconductivity of the electrode.In addition,the presence of negatively charged P3ABA notably improved PQ adsorption and electron transfer rate,which stimulate redox reaction on the modified electrode,thus improving the sensitivity of PQ analysis.The SPCE/GOAuNPs/P3ABA offered a wide linear range of PQ determination(10^(−9)-10^(−4) mol/L)and low limit of detection(LOD)of 0.45×10^(−9) mol/L or 0.116μg/L,which is far below international safety regulations.The modified electrode showed minimum interference effect with percent recovery ranging from 96.5%to 116.1%after addition of other herbicides,pesticides,metal ions,and additives.The stability of the SPCE/GO-AuNPs/P3ABA was evaluated,and the results indicated negligible changes in the detection signal over 9 weeks.Moreover,this modified electrode was successfully implemented for PQ analysis in both natural and tapped water with high accuracy.展开更多
文摘Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.
基金supported by the National Natural Science Foundation of China (No. 22305210, 52371238 to C. D.)the Shandong Provincial Natural Science Foundation (No. ZR2020QB108)+1 种基金the Graduate Innovation Foundation of Yantai University (GIFYTU)the Shandong Laboratory of Advanced Materials and Green Manufacturing (Yantai, AMGM2024A01)
文摘Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capped triphasic heterostructure Cu_(3)P/Co_(2)P/CoP@NC stands for nitrogen doped carbon nanorods were designed and synthesized through a combination of phosphide and carbonization.Kinetic analyses(cyclic voltammetry,electrochemical impedance spectroscopy,and galvanostatic intermittent titration technique)and density functional theory calculations show that the three-phase heterostructure and carbon layer effectively improve Na adsorption and migration as well as the electrochemical reactivity of the electrode.Based on this,Cu_(3)P/Co_(2)P/CoP@NC demonstrated excellent rate performance(305.9 mAh g^(-1)at 0.3 A g^(-1)and 202.8 mAh g^(-1)even at 10 A g^(-1))and cycling stability(the capacity decay rate is only 0.12%from the 5th to 300th cycle)when it is used for sodium-ion battery anodes.The in situ X-ray diffraction,ex situ X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy tests showed that Cu_(3)P/Co_(2)P/CoP@NC is based on a conversion reaction mechanism for sodium-ion storage.In addition,the NVP@reduced graphene oxide(rGO)//Cu_(3)P/Co_(2)P/CoP@NC full-cell delivers a high capacity of 210.2 mAh g^(-1)after 50 cycles at 0.3 A g^(-1).This work can provide a reference for the design of high-performance sodium electrode anode materials.
基金supported by the ProgramManagement Unit on Area Based Development (PMUA),Thailand (No.4594393)the National Science and Technology Development Agency (NSTDA),Thailand (No.P2250367).
文摘Herein,a modified screen printed carbon electrode(SPCE)based on a composite material,graphene oxide-gold nanoparticles(GO-AuNPs),and poly(3-aminobenzoic acid)(P3ABA)for the detection of paraquat(PQ)is introduced.The modified electrode was fabricated by drop casting of the GO-AuNPs,followed by electropolymerization of 3-aminobenzoic acid to achieve SPCE/GO-AuNPs/P3ABA.The morphology and microstructural characteristics of the modified electrodes were revealed by scanning electron microscopy(SEM)for each step of modification.The composite GO-AuNPs can provide high surface area and enhance electroconductivity of the electrode.In addition,the presence of negatively charged P3ABA notably improved PQ adsorption and electron transfer rate,which stimulate redox reaction on the modified electrode,thus improving the sensitivity of PQ analysis.The SPCE/GOAuNPs/P3ABA offered a wide linear range of PQ determination(10^(−9)-10^(−4) mol/L)and low limit of detection(LOD)of 0.45×10^(−9) mol/L or 0.116μg/L,which is far below international safety regulations.The modified electrode showed minimum interference effect with percent recovery ranging from 96.5%to 116.1%after addition of other herbicides,pesticides,metal ions,and additives.The stability of the SPCE/GO-AuNPs/P3ABA was evaluated,and the results indicated negligible changes in the detection signal over 9 weeks.Moreover,this modified electrode was successfully implemented for PQ analysis in both natural and tapped water with high accuracy.
