Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illust...Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illustrated the morphological fates of waste leaf-derived graphitic carbon(WLGC)produced from waste ginkgo leaves via pyrolysis temperature regulation and used as bifunctional cathode catalyst for simultaneous H_(2)O_(2) electrochemical generation and organic pollutant degradation,discovering S/N-self-doping shown to facilitate a synergistic effect on reactive oxygen species(ROS)generation.Under the optimum temperature of 800℃,the WLGC exhibited a H_(2)O_(2) selectivity of 94.2%and tetracycline removal of 99.3%within 60 min.Density functional theory calculations and in-situ Fourier transformed infrared spectroscopy verified that graphitic N was the critical site for H_(2)O_(2) generation.While pyridinic N and thiophene S were the main active sites responsible for OH generation,N vacancies were the active sites to produce ^(1)O_(2) from O_(2).The performance of the novel cathode for tetracycline degradation remains well under a wide pH range(3–11),maintaining excellent stability in 10 cycles.It is also industrially applicable,achieving satisfactory performance treating in real water matrices.This system facilitates both radical and non-radical degradation,offering valuable advances in the preparation of cost-effective and sustainable electrocatalysts and hold strong potentials in metal-free EAOPs for organic pollutant degradation.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(...Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.展开更多
Plasma-based processes,particularly in carbon capture and utilization,hold great potential for addressing environmental challenges and advancing a circular carbon economy.While significant progress has been made in un...Plasma-based processes,particularly in carbon capture and utilization,hold great potential for addressing environmental challenges and advancing a circular carbon economy.While significant progress has been made in understanding plasma-induced reactions,plasma-catalyst interactions,and reactor development to enhance energy efficiency and conversion,there remains a notable gap in research concerning overall process development.This review emphasizes the critical need for considerations at the process level,including integration and intensification,to facilitate the industrialization of plasma technology for chemical production.Discussions centered on the development of plasma-based processes are made with a primary focus on CO_(2) conversion,offering insights to guide future work for the transition of the technology from laboratory scale to industrial applications.Identification of current research gaps,especially in upscaling and integrating plasma reactors with other process units,is the key to addressing critical issues.The review further delves into relevant research in process evaluation and assessment,providing methodological insights and highlighting key factors for comprehensive economic and sustainability analyses.Additionally,recent advancements in novel plasma systems are reviewed,presenting unique advantages and innovative concepts that could reshape the future of process development.This review provides essential information for navigating the path forward,ensuring a comprehensive understanding of challenges and opportunities in the development of plasma-based CCU process.展开更多
Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential.Unfortunately,safety concerns related to dendrite formation on...Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential.Unfortunately,safety concerns related to dendrite formation on the anode surface caused by the uneven distribution of Li-ions during the discharge process interfere with the use of Li-metal in industrial batteries.In this study,methyl vinyl sulfone(MVS),a sulfone-based functional electrolyte additive,is used in an additive engineering strategy to control Lielectrolyte interactions and address the aforementioned problems.Li dendrite growth may be restricted,and transition metal degradation on the surface of the cathode can be reduced by the MVS-derived functional electrolyte additive interfacial layer.The electrochemical performance of an ethylene carbonate/dimethyl carbonate(EC/DMC)+1 wt% MVS Li-metal anode of a Li||Li symmetric cell exhibits remarkable cycle stability,maintaining a low overvoltage for over 750 h at 1 mA cm^(-2),and capacity of 1 mA h cm^(-2).Additionally,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) full cells with the MVS additive exhibit enhanced electrochemical stability for 250 cycles at a current density of 100 mA g^(-1).This study provides an innovative approach for stabilizing the metal-electrolyte interfacial layer that may be used for practical applications in metal-based rechargeable batteries.展开更多
The high porosity and tunable chemical functionality of metal-organic frameworks(MOFs)make it a promising catalyst design platform.High-throughput screening of catalytic performance is feasible since the large MOF str...The high porosity and tunable chemical functionality of metal-organic frameworks(MOFs)make it a promising catalyst design platform.High-throughput screening of catalytic performance is feasible since the large MOF structure database is available.In this study,we report a machine learning model for high-throughput screening of MOF catalysts for the CO_(2) cycloaddition reaction.The descriptors for model training were judiciously chosen according to the reaction mechanism,which leads to high accuracy up to 97%for the 75%quantile of the training set as the classification criterion.The feature contribution was further evaluated with SHAP and PDP analysis to provide a certain physical understanding.12,415 hypothetical MOF structures and 100 reported MOFs were evaluated under 100℃ and 1 bar within one day using the model,and 239 potentially efficient catalysts were discovered.Among them,MOF-76(Y)achieved the top performance experimentally among reported MOFs,in good agreement with the prediction.展开更多
Lignocellulosic biomass is one of the viable solutions to alleviate the global warming. However, the limited utilization of biomass majorly focused on cellulose and hemicellulose restricts the economic and environment...Lignocellulosic biomass is one of the viable solutions to alleviate the global warming. However, the limited utilization of biomass majorly focused on cellulose and hemicellulose restricts the economic and environmental feasibilities. To cope with this issue, we proposed an integrated process of co-producing 1,6-hexanediol(1,6-HDO) with tetrahydrofuran and adipic acid from biomass, referred to as Strategy A. To compare the impacts of lignin upgrading and feedstock, Strategy B, which co-produces tetrahydrofuran alone, and Strategy C, which is the traditional route to produce 1,6-HDO from fossil fuels, were used. Heat networks are also designed to reduce operating costs and indirect carbon emissions due to energy consumption, saving 87% and 83% of the heat and cooling requirements, respectively, in Strategy A. The market competitiveness of Strategy A was evaluated by determining the minimum selling price through techno-economic analysis, and sustainability was thoroughly investigated by quantifying the environmental impacts through both midpoint and endpoint life-cycle assessments(LCAs).Strategy A was found to be the most favorable both economically(USRDSCHARDOLLAR3,402/ton) and environmentally(-26.9 kg CO_(2)eq.). This indicates that lignin valorization is not only economically but also environmentally preferred. Finally, changes in economic and environmental feasibilities depending on economic, process, and environmental parameters were investigated using sensitivity and uncertainty analyses. The results of these analyses provide valuable insight into bio-based chemical production.展开更多
A significant fraction of the conventional oil reserves globally is in carbonate formations which contain a substantial amount of residual oil. Since primary and secondary recovery methods fail to yield above 20%-40%o...A significant fraction of the conventional oil reserves globally is in carbonate formations which contain a substantial amount of residual oil. Since primary and secondary recovery methods fail to yield above 20%-40%of original oil in place from these reserves, the need for enhanced oil recovery（EOR） techniques for incremental oil recovery has become imperative. With the challenges presented by the highly heterogeneous carbonate rocks,evaluation of tertiary-stage recovery techniques including chemical EOR（c EOR） has been a high priority for researchers and oil producers. In this review, the latest developments in the surfactant-based c EOR techniques applied in carbonate formations are discussed, contemplating the future direction of existing methodologies. In connection with this, the characteristics of heterogeneous carbonate reservoirs are outlined. Detailed discussion on surfactant-led oil recovery mechanisms and related processes, such as wettability alteration, interfacial tension reduction, microemulsion phase behavior, surfactant adsorption and mitigation, and foams and their applications is presented. Laboratory experiments, as well as field study data obtained using several surfactants, are also included.This extensive discussion on the subject aims to help researchers and professionals in the field to understand the current situation and plan future enterprises accordingly.展开更多
Electrochemical biosensor holds great promise in the biomedical area due to its enhanced specificity, sensitivity, label-free nature and cost effectiveness for rapid point-of-care detection of diseases at bedside. In ...Electrochemical biosensor holds great promise in the biomedical area due to its enhanced specificity, sensitivity, label-free nature and cost effectiveness for rapid point-of-care detection of diseases at bedside. In this review, we are focusing on the working principle of electrochemical biosensor and how it can be employed in detecting biomarkers of fatal diseases like cancer, AIDS, hepatitis and cardiovascular diseases. Recent advances in the development of implantable biosensors and exploration of nanomaterials in fabrication of electrodes with increasing the sensitivity of biosensor for quick and easy detection of biomolecules have been elucidated in detail. Electrochemical-based detection of heavy metal ions which cause harmful effect on human health has been discussed. Key challenges associated with the electrochemical sensor and its future perspectives are also addressed.展开更多
Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a m...Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process： in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction （XRD） analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis （TGA） reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy （SEM） test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.展开更多
The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify ...The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify the catalytic active sites, surface intermediates, and reaction mechanisms to reveal the relationship between the active sites and catalytic performance. However, the structure of a heterogeneous catalyst usually dynamically changes during reaction, bringing a great challenge for the identification of catalytic active sites and reaction pathways. Therefore, in-situ/operando techniques have been employed to real-time monitor the dynamic evolution of the structure of active sites under actual reaction conditions to precisely build the structure–function relationship. Here, we review the recent progress in the application of various in-situ/operando techniques in identifying active sites for catalytic conversion of CO_(2) over heterogeneous catalysts. We systematically summarize the applications of various optical and X-ray spectroscopy techniques, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), in identifying active sites and determining reaction mechanisms of the CO_(2) thermochemical conversion with hydrogen and light alkanes over heterogeneous catalysts. Finally, we discuss challenges and opportunities for the development of in-situ characterization in the future to further enlarge the capability of these powerful techniques.展开更多
Eucommia ulmoides Oliver is a native plant and valuable tonic Chinese medicine in China with a long history,great economic value and comprehensive development potential.Traditionally,the comprehensive utilization rate...Eucommia ulmoides Oliver is a native plant and valuable tonic Chinese medicine in China with a long history,great economic value and comprehensive development potential.Traditionally,the comprehensive utilization rate of E.ulmoides Oliv.is still very low,only bark has been used as medicine and other parts of Eucommia ulmoides Oliv.cannot be fully utilized,even the leaves have been well utilized in food products in Japan in the past decades.In order to improve the comprehensive utilization efficiency of E.ulmoides Oliv.,in this review,we summarized the varieties and contents of main active compounds,biological functions and pharmacological effects in different parts of E.ulmoides Oliv.The findings suggest that other parts of E.ulmoides Oliv.could replace the bark of E.ulmoides Oliv.to some extent besides of their respective applications.The unique and extensive physiological functions between different parts of E.ulmoides Oliv.indicate that the comprehensive utilization of E.ulmoides Oliv.has a wide space to develop,which is also an effective way to protect E.ulmoides Oliv.resources and improve its the utilization rate.展开更多
Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for...Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for assisting in building conductive,hyperelastic,and ultralight Ti_(3)C_(2)T_(x)MXene hybrid aerogels with oriented tracheid-like texture.The biomimetic hybrid aerogels are constructed by a facile bidirectional freezing strategy with CNF,carbon nanotube(CNT),and MXene based on synergistic electrostatic interaction and hydrogen bonding.Entangled CNF and CNT“mortars”bonded with MXene“bricks”of the tracheid structure produce good interfacial binding,and superior mechanical strength(up to 80%compressibility and extraordinary fatigue resistance of 1000 cycles at 50%strain).Benefiting from the biomimetic texture,CNF/CNT/MXene aerogel shows ultralow density of 7.48 mg cm^(-3)and excellent electrical conductivity(~2400 S m^(-1)).Used as pressure sensors,such aerogels exhibit appealing sensitivity performance with the linear sensitivity up to 817.3 kPa^(-1),which affords their application in monitoring body surface information and detecting human motion.Furthermore,the aerogels can also act as electrode materials of compressive solid-state supercapacitors that reveal satisfactory electrochemical performance(849.2 mF cm^(-2)at 0.8 mA cm^(-2))and superior long cycle compression performance(88%after 10,000 cycles at a compressive strain of 30%).展开更多
In this topic, we first discussed the requirement and performance of supercapacitors using carbon nanotubes （CNTs） as the electrode, including specific surface area, purity and cost. Then we reviewed the preparation...In this topic, we first discussed the requirement and performance of supercapacitors using carbon nanotubes （CNTs） as the electrode, including specific surface area, purity and cost. Then we reviewed the preparation technique of single wailed CNTs （SWNTs） in relatively large scale by chemical vapor deposition method. Its catalysis on the decomposition of methane and other carbon source, the reactor type and the process control strategies were discussed. Special focus was concentrated on how to increase the yield, selectivity, and purity of SWNTs and how to inhibit the formation of impurities, including amorphous carbon, multiwalled CNTs and the carbon encapsulated metal particles, since these impurities seriously influenced the performance of SWNTs in supercapacitors. Wish it be helpful to further decrease its product cost and for the commercial use in supercapacitors.展开更多
A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.The...A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.展开更多
Solid-state batteries have received increasing attention in scientific and industrial communities,which benefits from the intrinsically safe solid electrolytes(SEs).Although much effort has been devoted to designing S...Solid-state batteries have received increasing attention in scientific and industrial communities,which benefits from the intrinsically safe solid electrolytes(SEs).Although much effort has been devoted to designing SEs with high ionic conductivities,it is extremely difficult to fully understand the ionic diffusion mechanisms in SEs through conventional experimental and theoretical methods.Herein,the temperature-dependent concerted diffusion mechanism of ions in SEs is explored through machinelearning molecular dynamics,taking Li_(10)GeP_(2)S_(12) as a prototype.Weaker diffusion anisotropy,more disordered Li distributions,and shorter residence time are observed at a higher temperature.Arrhenius-type temperature dependence is maintained within a wide temperature range,which is attributed to the linear temperature dependence of jump frequencies of various concerted diffusion modes.These results provide a theoretical framework to understand the ionic diffusion mechanisms in SEs and deepen the understanding of the chemical origin of temperature-dependent concerted diffusions in SEs.展开更多
Aqueous zinc-ion batteries(ZIBs) are attracting considerable attention because of their low cost,high safety and abundant anode material resources.However,the major challenge faced by aqueous ZIBs is the lack of stabl...Aqueous zinc-ion batteries(ZIBs) are attracting considerable attention because of their low cost,high safety and abundant anode material resources.However,the major challenge faced by aqueous ZIBs is the lack of stable and high capacity cathode materials due to their complicated reaction mechanism and slow Zn-ion transport kinetics.This study reports a unique 3 D ’flower-like’ zinc cobaltite(ZnCo_(2)O_(4-x)) with enriched oxygen vacancies as a new cathode material for aqueous ZIBs.Computational calculations reveal that the presence of oxygen vacancies significantly enhances the electronic conductivity and accelerates Zn^(2+) diffusion by providing enlarged channels.The as-fabricated batteries present an impressive specific capacity of 148.3 mAh g^(-1) at the current density of 0.05 A g^(-1),high energy(2.8 Wh kg^(-1)) and power densities(27.2 W kg^(-1)) based on the whole device,which outperform most of the reported aqueous ZIBs.Moreover,a flexible solid-state pouch cell was demonstrated,which delivers an extremely stable capacity under bending states.This work demonstrates that the performance of Zn-ion storage can be effectively enhanced by tailoring the atomic structure of cathode materials,guiding the development of low-cost and eco-friendly energy storage materials.展开更多
We have studied the redox potentials and electronic properties of C60 and C59N using density functional theory method. It is found that doping C60 with one nitrogen atom results in a slight increase in redox potential...We have studied the redox potentials and electronic properties of C60 and C59N using density functional theory method. It is found that doping C60 with one nitrogen atom results in a slight increase in redox potential. Next, we have also studied C59N functionalized with various redox-active oxygen containing functional groups and strongly electron withdrawing functional groups. It is found that the intrinsic electronic structure of the molecule is the major determinant of the redox potential. Our DFT calculations show that the electron affinity to redox potential of functionalized C59N is correlated with the LUMO of the systems very well. This is the first systematic study on the redox properties and electronic structures of N-doped C60 systems.展开更多
Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have pre...Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have prevented its practical applications.Both physical morphology confinement and chemical adsorption/diffusion regulation are two crucial approaches to designing lithiophilic materials to alleviate dendrite of Li metal anode.However,their roles in suppressing dendrite growth for long-life Li anode are not fully understood yet.Herein,three different Ni-based nanosheet arrays(NiO-NS,Ni_(3)N-NS,and Ni_(5)P_(4)-NS)on carbon cloth as proof-of-concept lithiophilic frame-works are proposed for Li metal anodes.The two-dimensional nanoarray is more promising to facilitate uniform Li^(+)flow and electric field.Compared with the NiO-NS and the Ni_(5)P_(4)-NS,the Ni_(3)N-NS on carbon cloth after reacting with molten Li(Li-Ni/Li_(3)N-NS@CC)can afford the strongest adsorption to Li+and the most rapid Li+diffusion path.Therefore,the Li-Ni/Li_(3)N-NS@CC electrode realizes the lowest overpotential and the most excellent electrochemical performance(60 mA cm^(−2)and 60 mAh cm^(−2)for 1000 h).Furthermore,a remarkable full battery(LiFePO_(4)||Li-Ni/Li_(3)N-NS@CC)reaches 300 cycles at 2C.This research provides valuable insight into designing dendrite-free alkali metal batteries.展开更多
Photocatalysts for harvesting solar energy to either electricity or chemical fuels have attracted much attention recently, but they have big obstacles such as wide bandgaps and rapid charge recombinations to overcome ...Photocatalysts for harvesting solar energy to either electricity or chemical fuels have attracted much attention recently, but they have big obstacles such as wide bandgaps and rapid charge recombinations to overcome for final applications. In this study, we investigates a useful method to utilize vanadium redox pairs, which are commonly applied for vanadium redox flow batteries, to diminish charge recombinations and thus to enhance photocurrent response in regenerative solar energy storage. The results reveal significant improvements in photocurrent density by forming cuprous and cupric oxides in TiO_(2)/Cu_(x)O electrodes under solar AM 1.5 illuminations using the vanadium photoelectrochemical storage cell at 0.025 mol L^(-1) of vanadium redox species in the acid electrolytes. In addition, the stabilized photocurrent density of the copper content optimized TiO_(2)/Cu_(x)O electrodes is almost tripled from the TiO_(2) only electrode because the charge recombinations can be mitigated with the content optimized TiO_(2)/Cu_(x)O electrodes. Therefore, the optimized TiO_(2)/Cu_(x)O electrode results in the highest charge storing performance in the catholyte chamber, and the roles of vanadium redox species are also clearly demonstrated.展开更多
Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utiliza...Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.展开更多
基金financially supported by National Key R&D Program International Cooperation Project(2023YFE0108100)Natural Science Foundation of China(No.52170085)+2 种基金Key Project of Natural Science Foundation of Tianjin(No.21JCZDJC00320)Tianjin Post-graduate Students Research and Innovation Project(2021YJSB013)Fundamental Research Funds for the Central Universities,Nankai University.
文摘Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illustrated the morphological fates of waste leaf-derived graphitic carbon(WLGC)produced from waste ginkgo leaves via pyrolysis temperature regulation and used as bifunctional cathode catalyst for simultaneous H_(2)O_(2) electrochemical generation and organic pollutant degradation,discovering S/N-self-doping shown to facilitate a synergistic effect on reactive oxygen species(ROS)generation.Under the optimum temperature of 800℃,the WLGC exhibited a H_(2)O_(2) selectivity of 94.2%and tetracycline removal of 99.3%within 60 min.Density functional theory calculations and in-situ Fourier transformed infrared spectroscopy verified that graphitic N was the critical site for H_(2)O_(2) generation.While pyridinic N and thiophene S were the main active sites responsible for OH generation,N vacancies were the active sites to produce ^(1)O_(2) from O_(2).The performance of the novel cathode for tetracycline degradation remains well under a wide pH range(3–11),maintaining excellent stability in 10 cycles.It is also industrially applicable,achieving satisfactory performance treating in real water matrices.This system facilitates both radical and non-radical degradation,offering valuable advances in the preparation of cost-effective and sustainable electrocatalysts and hold strong potentials in metal-free EAOPs for organic pollutant degradation.
基金supported by the National Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(No.22178197)。
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.
文摘Plasma-based processes,particularly in carbon capture and utilization,hold great potential for addressing environmental challenges and advancing a circular carbon economy.While significant progress has been made in understanding plasma-induced reactions,plasma-catalyst interactions,and reactor development to enhance energy efficiency and conversion,there remains a notable gap in research concerning overall process development.This review emphasizes the critical need for considerations at the process level,including integration and intensification,to facilitate the industrialization of plasma technology for chemical production.Discussions centered on the development of plasma-based processes are made with a primary focus on CO_(2) conversion,offering insights to guide future work for the transition of the technology from laboratory scale to industrial applications.Identification of current research gaps,especially in upscaling and integrating plasma reactors with other process units,is the key to addressing critical issues.The review further delves into relevant research in process evaluation and assessment,providing methodological insights and highlighting key factors for comprehensive economic and sustainability analyses.Additionally,recent advancements in novel plasma systems are reviewed,presenting unique advantages and innovative concepts that could reshape the future of process development.This review provides essential information for navigating the path forward,ensuring a comprehensive understanding of challenges and opportunities in the development of plasma-based CCU process.
基金supported by the Korea Institute for Advancement of Technology (KIAT) grant funded by the Korea Government (MOTIE) (P0017012, Human Resource Development Program for Industrial Innovation)the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (RS2024-00411892)。
文摘Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential.Unfortunately,safety concerns related to dendrite formation on the anode surface caused by the uneven distribution of Li-ions during the discharge process interfere with the use of Li-metal in industrial batteries.In this study,methyl vinyl sulfone(MVS),a sulfone-based functional electrolyte additive,is used in an additive engineering strategy to control Lielectrolyte interactions and address the aforementioned problems.Li dendrite growth may be restricted,and transition metal degradation on the surface of the cathode can be reduced by the MVS-derived functional electrolyte additive interfacial layer.The electrochemical performance of an ethylene carbonate/dimethyl carbonate(EC/DMC)+1 wt% MVS Li-metal anode of a Li||Li symmetric cell exhibits remarkable cycle stability,maintaining a low overvoltage for over 750 h at 1 mA cm^(-2),and capacity of 1 mA h cm^(-2).Additionally,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) full cells with the MVS additive exhibit enhanced electrochemical stability for 250 cycles at a current density of 100 mA g^(-1).This study provides an innovative approach for stabilizing the metal-electrolyte interfacial layer that may be used for practical applications in metal-based rechargeable batteries.
基金financial support from the National Key Research and Development Program of China(2021YFB 3501501)the National Natural Science Foundation of China(No.22225803,22038001,22108007 and 22278011)+1 种基金Beijing Natural Science Foundation(No.Z230023)Beijing Science and Technology Commission(No.Z211100004321001).
文摘The high porosity and tunable chemical functionality of metal-organic frameworks(MOFs)make it a promising catalyst design platform.High-throughput screening of catalytic performance is feasible since the large MOF structure database is available.In this study,we report a machine learning model for high-throughput screening of MOF catalysts for the CO_(2) cycloaddition reaction.The descriptors for model training were judiciously chosen according to the reaction mechanism,which leads to high accuracy up to 97%for the 75%quantile of the training set as the classification criterion.The feature contribution was further evaluated with SHAP and PDP analysis to provide a certain physical understanding.12,415 hypothetical MOF structures and 100 reported MOFs were evaluated under 100℃ and 1 bar within one day using the model,and 239 potentially efficient catalysts were discovered.Among them,MOF-76(Y)achieved the top performance experimentally among reported MOFs,in good agreement with the prediction.
基金Material Parts Technology Development Program (20017461, Development and Performance Improvement of Air Operated Valve for 105 MPa Hydrogen Charging Station) funded by the Ministry of Trade,Industry and Energy(MOTIE, Republic of Korea)Korea Evaluation Institute of Industrial Technology (KEIT, Republic of Korea)+1 种基金financial support from the Korea Institute of Energy Technology Evaluation and Planning (KETEP)Ministry of Trade,Industry&Energy (MOTIE) of the Republic of Korea(RS-2024-00419764)。
文摘Lignocellulosic biomass is one of the viable solutions to alleviate the global warming. However, the limited utilization of biomass majorly focused on cellulose and hemicellulose restricts the economic and environmental feasibilities. To cope with this issue, we proposed an integrated process of co-producing 1,6-hexanediol(1,6-HDO) with tetrahydrofuran and adipic acid from biomass, referred to as Strategy A. To compare the impacts of lignin upgrading and feedstock, Strategy B, which co-produces tetrahydrofuran alone, and Strategy C, which is the traditional route to produce 1,6-HDO from fossil fuels, were used. Heat networks are also designed to reduce operating costs and indirect carbon emissions due to energy consumption, saving 87% and 83% of the heat and cooling requirements, respectively, in Strategy A. The market competitiveness of Strategy A was evaluated by determining the minimum selling price through techno-economic analysis, and sustainability was thoroughly investigated by quantifying the environmental impacts through both midpoint and endpoint life-cycle assessments(LCAs).Strategy A was found to be the most favorable both economically(USRDSCHARDOLLAR3,402/ton) and environmentally(-26.9 kg CO_(2)eq.). This indicates that lignin valorization is not only economically but also environmentally preferred. Finally, changes in economic and environmental feasibilities depending on economic, process, and environmental parameters were investigated using sensitivity and uncertainty analyses. The results of these analyses provide valuable insight into bio-based chemical production.
文摘A significant fraction of the conventional oil reserves globally is in carbonate formations which contain a substantial amount of residual oil. Since primary and secondary recovery methods fail to yield above 20%-40%of original oil in place from these reserves, the need for enhanced oil recovery（EOR） techniques for incremental oil recovery has become imperative. With the challenges presented by the highly heterogeneous carbonate rocks,evaluation of tertiary-stage recovery techniques including chemical EOR（c EOR） has been a high priority for researchers and oil producers. In this review, the latest developments in the surfactant-based c EOR techniques applied in carbonate formations are discussed, contemplating the future direction of existing methodologies. In connection with this, the characteristics of heterogeneous carbonate reservoirs are outlined. Detailed discussion on surfactant-led oil recovery mechanisms and related processes, such as wettability alteration, interfacial tension reduction, microemulsion phase behavior, surfactant adsorption and mitigation, and foams and their applications is presented. Laboratory experiments, as well as field study data obtained using several surfactants, are also included.This extensive discussion on the subject aims to help researchers and professionals in the field to understand the current situation and plan future enterprises accordingly.
基金the Department of Science and Technology for providing INSPIRE Faculty Research Grant
文摘Electrochemical biosensor holds great promise in the biomedical area due to its enhanced specificity, sensitivity, label-free nature and cost effectiveness for rapid point-of-care detection of diseases at bedside. In this review, we are focusing on the working principle of electrochemical biosensor and how it can be employed in detecting biomarkers of fatal diseases like cancer, AIDS, hepatitis and cardiovascular diseases. Recent advances in the development of implantable biosensors and exploration of nanomaterials in fabrication of electrodes with increasing the sensitivity of biosensor for quick and easy detection of biomolecules have been elucidated in detail. Electrochemical-based detection of heavy metal ions which cause harmful effect on human health has been discussed. Key challenges associated with the electrochemical sensor and its future perspectives are also addressed.
基金Supported by the National Natural Science Foundation of China (No.50574046 and 50164002, )Natural Science Foun-dation of Yunnan Province (No. 2004E0012Q).
文摘Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process： in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction （XRD） analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis （TGA） reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy （SEM） test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.
基金Authors acknowledge the financial support from the National Natural Science Foundation of China(NSFC)under Grant No.21978148 and 21808120.
文摘The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify the catalytic active sites, surface intermediates, and reaction mechanisms to reveal the relationship between the active sites and catalytic performance. However, the structure of a heterogeneous catalyst usually dynamically changes during reaction, bringing a great challenge for the identification of catalytic active sites and reaction pathways. Therefore, in-situ/operando techniques have been employed to real-time monitor the dynamic evolution of the structure of active sites under actual reaction conditions to precisely build the structure–function relationship. Here, we review the recent progress in the application of various in-situ/operando techniques in identifying active sites for catalytic conversion of CO_(2) over heterogeneous catalysts. We systematically summarize the applications of various optical and X-ray spectroscopy techniques, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), in identifying active sites and determining reaction mechanisms of the CO_(2) thermochemical conversion with hydrogen and light alkanes over heterogeneous catalysts. Finally, we discuss challenges and opportunities for the development of in-situ characterization in the future to further enlarge the capability of these powerful techniques.
基金the National Key Research and Development Plan,China(2016YFD0400203-4).
文摘Eucommia ulmoides Oliver is a native plant and valuable tonic Chinese medicine in China with a long history,great economic value and comprehensive development potential.Traditionally,the comprehensive utilization rate of E.ulmoides Oliv.is still very low,only bark has been used as medicine and other parts of Eucommia ulmoides Oliv.cannot be fully utilized,even the leaves have been well utilized in food products in Japan in the past decades.In order to improve the comprehensive utilization efficiency of E.ulmoides Oliv.,in this review,we summarized the varieties and contents of main active compounds,biological functions and pharmacological effects in different parts of E.ulmoides Oliv.The findings suggest that other parts of E.ulmoides Oliv.could replace the bark of E.ulmoides Oliv.to some extent besides of their respective applications.The unique and extensive physiological functions between different parts of E.ulmoides Oliv.indicate that the comprehensive utilization of E.ulmoides Oliv.has a wide space to develop,which is also an effective way to protect E.ulmoides Oliv.resources and improve its the utilization rate.
基金supported by the Project of Jinan City(202228044)National Natural Science Foundation of China(32071720,32271814)+1 种基金the China Postdoctoral Science Foundation(2021M702456)China Scholarship Council for supporting their PhD program。
文摘Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for assisting in building conductive,hyperelastic,and ultralight Ti_(3)C_(2)T_(x)MXene hybrid aerogels with oriented tracheid-like texture.The biomimetic hybrid aerogels are constructed by a facile bidirectional freezing strategy with CNF,carbon nanotube(CNT),and MXene based on synergistic electrostatic interaction and hydrogen bonding.Entangled CNF and CNT“mortars”bonded with MXene“bricks”of the tracheid structure produce good interfacial binding,and superior mechanical strength(up to 80%compressibility and extraordinary fatigue resistance of 1000 cycles at 50%strain).Benefiting from the biomimetic texture,CNF/CNT/MXene aerogel shows ultralow density of 7.48 mg cm^(-3)and excellent electrical conductivity(~2400 S m^(-1)).Used as pressure sensors,such aerogels exhibit appealing sensitivity performance with the linear sensitivity up to 817.3 kPa^(-1),which affords their application in monitoring body surface information and detecting human motion.Furthermore,the aerogels can also act as electrode materials of compressive solid-state supercapacitors that reveal satisfactory electrochemical performance(849.2 mF cm^(-2)at 0.8 mA cm^(-2))and superior long cycle compression performance(88%after 10,000 cycles at a compressive strain of 30%).
基金financially supported by the National Basic Research Program of China (2011CB932602)the NSFC Key Program (20736007,20736004)the Foundation of Tsinghua University (2011THZ08,new energy)
文摘In this topic, we first discussed the requirement and performance of supercapacitors using carbon nanotubes （CNTs） as the electrode, including specific surface area, purity and cost. Then we reviewed the preparation technique of single wailed CNTs （SWNTs） in relatively large scale by chemical vapor deposition method. Its catalysis on the decomposition of methane and other carbon source, the reactor type and the process control strategies were discussed. Special focus was concentrated on how to increase the yield, selectivity, and purity of SWNTs and how to inhibit the formation of impurities, including amorphous carbon, multiwalled CNTs and the carbon encapsulated metal particles, since these impurities seriously influenced the performance of SWNTs in supercapacitors. Wish it be helpful to further decrease its product cost and for the commercial use in supercapacitors.
基金support from National Science Foundation of China(No.22075012).
文摘A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.
基金supported by the National Key Research and Development Program(2021YFB2500210)the Beijing Municipal Natural Science Foundation(Z20J00043)+4 种基金the National Natural Science Foundation of China(22109086 and 21825501)the China Postdoctoral Science Foundation(2021TQ0161 and 2021 M691709)the Guoqiang Institute at Tsinghua University(2020GQG1006)the support from the Shuimu Tsinghua Scholar Program of Tsinghua Universitythe support from the Tsinghua National Laboratory for Information Science and Technology for theoretical simulations。
文摘Solid-state batteries have received increasing attention in scientific and industrial communities,which benefits from the intrinsically safe solid electrolytes(SEs).Although much effort has been devoted to designing SEs with high ionic conductivities,it is extremely difficult to fully understand the ionic diffusion mechanisms in SEs through conventional experimental and theoretical methods.Herein,the temperature-dependent concerted diffusion mechanism of ions in SEs is explored through machinelearning molecular dynamics,taking Li_(10)GeP_(2)S_(12) as a prototype.Weaker diffusion anisotropy,more disordered Li distributions,and shorter residence time are observed at a higher temperature.Arrhenius-type temperature dependence is maintained within a wide temperature range,which is attributed to the linear temperature dependence of jump frequencies of various concerted diffusion modes.These results provide a theoretical framework to understand the ionic diffusion mechanisms in SEs and deepen the understanding of the chemical origin of temperature-dependent concerted diffusions in SEs.
基金supported by the National Natural Science Foundation of China(Nos.51873198,51503184 and 21703248)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB20000000)+1 种基金the Engineering and Physical Sciences Research Council(EPSRC,EP/R023581/1)the RSC Mobility Grant(M19-7656)and the STFC Batteries Network(ST/R006873/1)。
文摘Aqueous zinc-ion batteries(ZIBs) are attracting considerable attention because of their low cost,high safety and abundant anode material resources.However,the major challenge faced by aqueous ZIBs is the lack of stable and high capacity cathode materials due to their complicated reaction mechanism and slow Zn-ion transport kinetics.This study reports a unique 3 D ’flower-like’ zinc cobaltite(ZnCo_(2)O_(4-x)) with enriched oxygen vacancies as a new cathode material for aqueous ZIBs.Computational calculations reveal that the presence of oxygen vacancies significantly enhances the electronic conductivity and accelerates Zn^(2+) diffusion by providing enlarged channels.The as-fabricated batteries present an impressive specific capacity of 148.3 mAh g^(-1) at the current density of 0.05 A g^(-1),high energy(2.8 Wh kg^(-1)) and power densities(27.2 W kg^(-1)) based on the whole device,which outperform most of the reported aqueous ZIBs.Moreover,a flexible solid-state pouch cell was demonstrated,which delivers an extremely stable capacity under bending states.This work demonstrates that the performance of Zn-ion storage can be effectively enhanced by tailoring the atomic structure of cathode materials,guiding the development of low-cost and eco-friendly energy storage materials.
文摘We have studied the redox potentials and electronic properties of C60 and C59N using density functional theory method. It is found that doping C60 with one nitrogen atom results in a slight increase in redox potential. Next, we have also studied C59N functionalized with various redox-active oxygen containing functional groups and strongly electron withdrawing functional groups. It is found that the intrinsic electronic structure of the molecule is the major determinant of the redox potential. Our DFT calculations show that the electron affinity to redox potential of functionalized C59N is correlated with the LUMO of the systems very well. This is the first systematic study on the redox properties and electronic structures of N-doped C60 systems.
基金supported by the National Key R&D Research Program of China the National Key Research Program(No.2018YFB0905400)the National Natural Science Foundation of China(Nos.51925207,U1910210,51872277,52002083,52102322 and 22109011)+5 种基金National Synchrotron Radiation Laboratory(KY2060000173)the“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDA21000000)the Fundamental Research Funds for the Central Universities(Wk2060140026,Wk2400000004,Wk20720220010)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(Grant.YLU-DNL Fund 2021002)the National Postdoctoral Program for Innovative Talents(BX20200047)the China Postdoctoral Science Foundation(2021M690380).
文摘Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have prevented its practical applications.Both physical morphology confinement and chemical adsorption/diffusion regulation are two crucial approaches to designing lithiophilic materials to alleviate dendrite of Li metal anode.However,their roles in suppressing dendrite growth for long-life Li anode are not fully understood yet.Herein,three different Ni-based nanosheet arrays(NiO-NS,Ni_(3)N-NS,and Ni_(5)P_(4)-NS)on carbon cloth as proof-of-concept lithiophilic frame-works are proposed for Li metal anodes.The two-dimensional nanoarray is more promising to facilitate uniform Li^(+)flow and electric field.Compared with the NiO-NS and the Ni_(5)P_(4)-NS,the Ni_(3)N-NS on carbon cloth after reacting with molten Li(Li-Ni/Li_(3)N-NS@CC)can afford the strongest adsorption to Li+and the most rapid Li+diffusion path.Therefore,the Li-Ni/Li_(3)N-NS@CC electrode realizes the lowest overpotential and the most excellent electrochemical performance(60 mA cm^(−2)and 60 mAh cm^(−2)for 1000 h).Furthermore,a remarkable full battery(LiFePO_(4)||Li-Ni/Li_(3)N-NS@CC)reaches 300 cycles at 2C.This research provides valuable insight into designing dendrite-free alkali metal batteries.
基金supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Science and ICT (NRF-2018R1D1A1A09082239)。
文摘Photocatalysts for harvesting solar energy to either electricity or chemical fuels have attracted much attention recently, but they have big obstacles such as wide bandgaps and rapid charge recombinations to overcome for final applications. In this study, we investigates a useful method to utilize vanadium redox pairs, which are commonly applied for vanadium redox flow batteries, to diminish charge recombinations and thus to enhance photocurrent response in regenerative solar energy storage. The results reveal significant improvements in photocurrent density by forming cuprous and cupric oxides in TiO_(2)/Cu_(x)O electrodes under solar AM 1.5 illuminations using the vanadium photoelectrochemical storage cell at 0.025 mol L^(-1) of vanadium redox species in the acid electrolytes. In addition, the stabilized photocurrent density of the copper content optimized TiO_(2)/Cu_(x)O electrodes is almost tripled from the TiO_(2) only electrode because the charge recombinations can be mitigated with the content optimized TiO_(2)/Cu_(x)O electrodes. Therefore, the optimized TiO_(2)/Cu_(x)O electrode results in the highest charge storing performance in the catholyte chamber, and the roles of vanadium redox species are also clearly demonstrated.
基金financially supported by the National Key Research and Development Program of China (2018YFA0702002)the Beijing Natural Science Foundation (Z210016)the National Natural Science Foundation of China (21935001)。
文摘Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.
