A dye-sensitized photocatalyst combining Pt-loaded TiO_(2) and Ru(Ⅱ)tris-diimine sensitizer(RuP)was constructed and its activity for photochemical hydrogen evolution was compared with that of Pt-intercalated HCa_(2)N...A dye-sensitized photocatalyst combining Pt-loaded TiO_(2) and Ru(Ⅱ)tris-diimine sensitizer(RuP)was constructed and its activity for photochemical hydrogen evolution was compared with that of Pt-intercalated HCa_(2)Nb_(3)O_(10) nanosheets.When the sacrificial donor ethylenediaminetetraacetic acid(EDTA)disodium salt dihydrate was used,RuP/Pt/TiO_(2) showed higher activity than RuP/Pt/HCa_(2)Nb_(3)O_(10).In contrast,when NaI(a reversible electron donor)was used,RuP/Pt/TiO_(2) showed little activity due to back electron transfer to the electron acceptor(I_(3)-),which was gener-ated as the oxidation product of I-.By modification with anionic polymers(sodium poly(styrenesulfonate)or sodium polymethacrylate)that could inhibit the scavenging of conduction band electrons by I_(3)-,the H_(2) production activity from aqueous NaI was improved,but it did not exceed that of RuP/Pt/HCa_(2)Nb_(3)O_(10).Transient absorption measurements showed that the rate of semiconductor-to-dye back electron transfer was slower in the case of TiO_(2) than HCa_(2)Nb_(3)O_(10),but the electron transfer reaction to I3-was much faster.These results indicate that Pt/TiO_(2) is useful for reactions with sacrificial reductants(e.g.,EDTA),where the back electron transfer reaction to the more reducible product can be neglected.However,more careful design of the catalyst will be nec-essary when a reversible electron donor is employed.展开更多
Microbial fuel cells have already been used as biosensors to monitor assimilable organic carbon(AOC).However,their signal production from AOC is known to be completely suppressed by dissoved oxygen(DO).In this study,t...Microbial fuel cells have already been used as biosensors to monitor assimilable organic carbon(AOC).However,their signal production from AOC is known to be completely suppressed by dissoved oxygen(DO).In this study,two identical microbial electrolysis cell(MEC)based biosensors were inoculated with marine sediment and operated at two different anodic potentials,namely-300 mV and+250 mV relative to Ag/AgCl.The MEC biosensor operated under positive anodic potential conditions had electrochemically active microbial communities on the anode,including members of the Shewanellaceae,Pseudoalteromonadaceae,and Clostridiaceae families.However,the strictly anaerobic members of the Desulfuromonadaceae,Desulfobulbaceae and Desulfobacteraceae families were found only in the negative anodic potential MEC biosensor.The positive anodic potential MEC biosensor showed several other advantages as well,such as faster start-up,significantly higher maximum current production,fivefold improvement in the AOC detection limit,and tolerance of low dissolved oxygen,compared to those obtained from the negative anodic potential MEC biosensor.The developed positive anodic potential MEC biosensor can thus be used as a real-time and inexpensive detector of AOC concentrations in high saline and low DO seawater.展开更多
The experimental study of natural convection in allglass evacuated tube solar collectors is performed through the experimental platform of the solar-assisted fuel cell system.The experimental facility includes solar c...The experimental study of natural convection in allglass evacuated tube solar collectors is performed through the experimental platform of the solar-assisted fuel cell system.The experimental facility includes solar collectors with different length and diameter tubes, different coating materials, and with / without guide plates, respectively. Threedimensional mathematical models on natural and forced convections in the solar collectors are established and the experimental data is validated by field synergy and entransy principles. The results of natural convection show that the water temperature increases and thermal efficiency decreases gradually with the evacuated tube length. The thermal efficiency increases when absorption rates increase from 0. 95 to 1. 0 and emission rates decrease from 0. 16 to 0. 06. The thermal efficiency of solar collectors is increased after being equipped with the guide plate, which is attributed to the disappearance of the mixed flowand the enhancement of the heat transfer at the bottom of the evacuated tube. The results of forced convertion indicate that the Reynolds, Nusselt and entransy increments of the horizontal double collectors are higher than those of the vertical single collector while the entransy dissipation is lower than that of the vertical single collector. It is concluded that the solar collectors with guide plates are suitable for natural convection while the double horizontal collectors are suitable for forced convection in the thermal field of solar-assisted fuel cell systems with lowand medium temperatures.展开更多
Photocatalysis is believed to be one of the best methods to realize sustainable H2 production. However, achieving this through heterogeneous photocatalysis still remains a great challenge owing to the absence of activ...Photocatalysis is believed to be one of the best methods to realize sustainable H2 production. However, achieving this through heterogeneous photocatalysis still remains a great challenge owing to the absence of active sites, sluggish surface reaction kinetics, insufficient charge separation, and a high thermodynamic barrier. Therefore, cocatalysts are necessary and of great significance in boosting photocatalytic H2 generation. This review will focus on the promising and appealing low-cost Ni-based H2-generation cocatalysts as the alternatives for the high-cost and low-abundance noble metal cocatalysts. Special emphasis has been placed on the design principle, modification strategies for further enhancing the activity and stability of Ni-based cocatalysts, and identification of the exact active sites and surface reaction mechanisms. Particularly, four types of modification strategies based on increased light harvesting, enhanced charge separation, strengthened interface interaction, and improved electrocatalytic activity have been thoroughly discussed and compared in detail. This review may open a new avenue for designing highly active and durable Ni-based cocatalysts for photocatalytic H2 generation.展开更多
Photocatalytic solar fuel generation is currently a hot topic because of its potential for solving the energy crisis owing to its low cost and zero-carbon emissions.However,the rapid bulk recombination of photoexcited...Photocatalytic solar fuel generation is currently a hot topic because of its potential for solving the energy crisis owing to its low cost and zero-carbon emissions.However,the rapid bulk recombination of photoexcited carrier pairs is a fundamental disadvantage.To resolve this problem,we synthesized a dual cocatalysts system of cobalt phosphide(Co P)and molybdenum carbide(Mo_(2)C)embedded on strontium titanate(Sr TiO_(3))nanofibers.Compared with those of pristine SrTiO_(3) and binary samples,the dual cocatalysts system(denoted SCM)showed a significant improvement in the hydrogen evolution and CO_(2) reduction performance.Further,the structure of SCM effectively promoted spatial charge separation and enhanced the photocatalytic performance.In addition,the Schottky junction formed between the SrTiO_(3) and cocatalysts enabled the rapid transfer of photoexcited electrons from SrTiO_(3) to the cocatalysts,resulting in effective separation and prolonged photoexcited electron lifetimes.The electron migration route between SrTiO_(3) and the cocatalysts was determined by in situ irradiation X-ray spectroscopy,and band structures of Sr TiO_(3) and the cocatalysts are proposed based on results obtained from UV-vis diffraction reflection spectroscopy and ultraviolet photoelectron spectroscopy measurements.On the basis of our results,the dual cocatalysts unambiguously boosts charge separation and enhances photocatalytic performance.In summary,we have investigated the flux of photoexcited electrons in a dual cocatalysts system and provided a theoretical basis and ideas for subsequent research.展开更多
Pt‐loaded graphitic carbon nitride(g‐C_(3)N_(4))is known to be a good photocatalyst for H_(2) evolution under visible light.In most cases,however,sacrificial electron donors such as triethanolamine are required for ...Pt‐loaded graphitic carbon nitride(g‐C_(3)N_(4))is known to be a good photocatalyst for H_(2) evolution under visible light.In most cases,however,sacrificial electron donors such as triethanolamine are required for the water‐splitting operation,and nonsacrificial H_(2) evolution by g‐C_(3)N_(4) remains a challenge.In this work,we investigated the photocatalytic activities of carbon nitride nanosheet(NS‐C_(3)N_(4)),which was prepared by thermal treatment of urea,for nonsacrificial H_(2) evolution using reversible electron donors under visible light(λ>400 nm).Whereas Pt‐loaded NS‐C_(3)N_(4) did not produce H_(2) from aqueous solutions containing I−,Fe^(2+),or[Fe(CN)_(6)]^(4−),modification of the Pt/NS‐C_(3)N_(4) photocatalyst with CrO_(x) led to observable H_(2) evolution.Transmission electron microscopy observations and energy‐dispersive X‐ray spectroscopic analysis suggested that a Pt‐core/CrO_(x)‐shell structure was formed on the NS‐C_(3)N_(4).The CrO_(x)/Pt/NS‐C_(3)N_(4) served as a H_(2)‐evolution photocatalyst for visible‐light‐driven Z‐scheme overall water splitting,in combination with a modified WO_(3) photocatalyst,in the presence of a[Fe(CN)_(6)]^(3−/4−)redox mediator.展开更多
Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites...Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites,few‐layer carbon nitride(FLCN)materials present great potential for production of solar fuels and chemicals and set off a new wave of research in the last few years.Herein,the recent progress in synthesis and regulation of FLCN‐based photocatalysts,and their applications in the conversion of sunlight into fuels and chemicals,is summarized.More importantly,the regulation strategies from chemical modification to microstructure control toward the production of solar fuels and chemicals has been deeply analyzed,aiming to inspire critical thinking about the effective approaches for photocatalyst modification rather than developing new materials.At the end,the key scientific challenges and some future trend of FLCN‐based materials as advanced photocatalysts are also discussed.展开更多
As a kind of valuable chemicals,hydrogen peroxide(H2O2)has aroused growing attention in many fields.However,H2O2 production via traditional anthraquinone process suffers from challenges of large energy consumption and...As a kind of valuable chemicals,hydrogen peroxide(H2O2)has aroused growing attention in many fields.However,H2O2 production via traditional anthraquinone process suffers from challenges of large energy consumption and heavy carbon footprint.Alternatively,photoelectrocatalytic(PEC)production of H2O2 has shown great promises to make H2O2 a renewable fuel to store solar energy.Transition‐metal‐oxide(TMO)semiconductor based photoelectrocatalysts are among the most promising candidates for PEC H2O2 production.In this work,the fundamentals of H2O2 synthesis through PEC process are briefly introduced,followed by the state‐of‐the‐art of TMO semiconductor based photoelectrocatalysts for PEC production H2O2.Then,the progress on H2O2 fuel cells from on‐site PEC production is presented.Furthermore,the challenges and future perspectives of PEC H2O2 production are discussed.This review aims to provide inspiration for the PEC production of H2O2 as a renewable solar fuel.展开更多
Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energ...Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energy crisis and environmental challenges.It enables not only the realization of clean,renewable,and high-heating-value solar fuels,but also the reduction of CO_(2) emissions.Layered double hydroxides(LDHs)are a type of two-dimensional anionic clay with a brucite-like structure,and are characterized by a unique,delaminable,multidimensional,layered structure;tunable intralayer metal cations;and exchangeable interlayer guest anions.Therefore,it has been widely investigated in the fields of CO_(2) reduction,photoelectrocatalytic water oxidation,and water photolysis to produce H2.However,the low carrier mobility and poor quantum efficiency of pure LDH limit its application.An increasing number of scholars are exploring methods to obtain LDH-based photocatalysts with high energy conversion efficiency,such as assembling photoactive components into LDH laminates,designing multidimensional structures,or coupling different types of semiconductors to construct heterojunctions.This review first summarizes the main characteristics of LDH,i.e.,metal-cation tunability,intercalated guest-anion substitutability,thermal decomposability,memory effect,multidimensionality,and delaminability.Second,LDHs,LDH-based composites(metal sulfide-LDH composites,metal oxide-LDH composites,graphite phase carbon nitride-LDH composites),ternary LDH-based composites,and mixed-metal oxides for splitting water to produce H_(2) are reviewed.Third,graphite phase carbon nitride-LDH composites,MgAl-LDH composites,CuZn-LDH composites,and other semiconductor-LDH composites for CO_(2) reduction are introduced.Although the field of LDH-based photocatalysts has advanced considerably,the photocatalytic mechanism of LDHs has not been thoroughly elucidated;moreover,the photocatalytic active sites,the synergy between different components,and the interfacial reaction mechanism of LDH-based photocatalysts require further investigation.Therefore,LDH composite materials for photocatalysis could be developed through structural regulation and function-oriented design to investigate the effects of different components and interface reactions,the influence of photogenerated carriers,and the impact of material composition on the physical and chemical properties of the LDH-based photocatalyst.展开更多
After short introducing the crucial role of e‐fuels to meet net‐zero emissions targets,this perspective paper discusses the differences between reactive catalysis(electro‐,photo‐and plasma‐catalysis,with focus on...After short introducing the crucial role of e‐fuels to meet net‐zero emissions targets,this perspective paper discusses the differences between reactive catalysis(electro‐,photo‐and plasma‐catalysis,with focus on the first for conciseness)and thermal catalysis used at most.The main point is to evidence that to progress in producing e‐fuels,the gap is not in terms of scaling‐up and pilot testing,but rather in the fundamental needs to turn the current approach and methodologies to develop reactive catalysis,including from a mechanistic perspective,to go beyond the current methods largely derived from thermal catalysis.Developing thus new fundamental bases to understand reactive catalysis is the challenge to accelerate the progress in this area to enable the potential role towards a sustainable net‐zero emissions future.Some novel aspects are highlighted,but the general aim is rather to stimulate discussion in rethinking catalysis from an alternative perspective.展开更多
Solar‐driven thermochemical water splitting represents one efficient route to the generation of H2as a clean and renewable fuel.Due to their outstanding catalytic abilities and promising solar fuel production capacit...Solar‐driven thermochemical water splitting represents one efficient route to the generation of H2as a clean and renewable fuel.Due to their outstanding catalytic abilities and promising solar fuel production capacities,perovskite‐type redox catalysts have attracted significant attention in this regard.In the present study,the perovskite series La1‐xCaxMn1‐yAlyO3(x,y=0.2,0.4,0.6,or0.8)was fabricated using a modified Pechini method and comprehensively investigated to determine the applicability of these materials to solar H2production via two‐step thermochemical water splitting.The thermochemical redox behaviors of these perovskites were optimized by doping at either the A(Ca)or B(Al)sites over a broad range of substitution values,from0.2to0.8.Through this doping,a highly efficient perovskite(La0.6Ca0.4Mn0.6Al0.4O3)was developed,which yielded a remarkable H2production rate of429μmol/g during two‐step thermochemical H2O splitting,going between1400and1000°C.Moreover,the performance of the optimized perovskite was found to be eight times higher than that of the benchmark catalyst CeO2under the same experimental conditions.Furthermore,these perovskites also showed impressive catalytic stability during two‐step thermochemical cycling tests.These newly developed La1‐xCaxMn1‐yAlyO3redox catalysts appear to have great potential for future practical applications in thermochemical solar fuel production.展开更多
Band engineering based on the construction of solid solutions is an effective approach to enhance the efficiency of semiconductor photocatalysts, via which the balance between light absorption and driving force can be...Band engineering based on the construction of solid solutions is an effective approach to enhance the efficiency of semiconductor photocatalysts, via which the balance between light absorption and driving force can be well achieved by continuously tuning the band structure. Here the ZnS1–xSex nanobelt solid solutions have been prepared via thermal treatment of ZnS1–xSex(en)0.5 precursors. The compositions are adjusted by changing the mole ratio of Se to S powder in the starting materials, resulting in continuously modulating the alignment of energy levels of the obtained solid solutions. The band structure is also studied via theoretical calculation. Accordingly, the light harvesting can be tuned too, as confirmed by the UV-vis absorption spectra. XPS valence spectra are used to determine the valence band maximum. Transient photoluminescence spectra are employed to study the separation of photogenerated charge carriers. BET specific surface area and CO2 adsorption isotherms of different catalysts are measured. The obtained ZnS1–xSex nanobelts exhibit different photocatalytic activity for solar-fuel production, dependent on many factors like the light harvesting and alignment of energy levels. The related mechanism is studied in detail.展开更多
Solar-driven CO_(2) reduction is an efficient way to convert sustainable solar energy and massive CO_(2) to renewable solar fuels,such as CH_(4),HCOOH,HCHO,and CH_(3)OH,etc.Up to now,significant research efforts have ...Solar-driven CO_(2) reduction is an efficient way to convert sustainable solar energy and massive CO_(2) to renewable solar fuels,such as CH_(4),HCOOH,HCHO,and CH_(3)OH,etc.Up to now,significant research efforts have been devoted to exploring the reaction path and developing the photocatalysts.In heterogeneous photocatalysis,among the semiconductor-based photocatalysts,titania(TiO_(2)),as an inexpensive and practically sustainable metal oxides,remains the most extensively studied photocatalyst over the past decades.In this review,we summarize the most recent advances in the solar-driven CO_(2) reduction using TiO_(2)-based photocatalysts,which include the fabrication of heterojunction,surface functional modification,band structure engineering,and morphology design,aiming to improve the CO_(2) conversion efficiency and selectivity to the desired product.Additionally,photoelectrochemical and photothermal approaches are introduced and the fundamental principles to activate and enhance the performance of TiO_(2) for the specific reaction are discussed.The exploration of the solar-driven approaches and discussion on the underlying mechanism allow the comprehensive understanding of CO_(2) photoreduction,that can lead to a rational design and synthesis of TiO_(2)-based photocatalysts.展开更多
In this study,conductive polymer polyaniline(PANI)is employed to modify the anodes of benthic microbial fuel cells(BMFC).Four electrochemical methods are used to synthesize the polyaniline anodes;the results show that...In this study,conductive polymer polyaniline(PANI)is employed to modify the anodes of benthic microbial fuel cells(BMFC).Four electrochemical methods are used to synthesize the polyaniline anodes;the results show that the PANI modification,especially the pulse potential method for PANI synthesis could obviously improve the cell energy output and reduce the anode internal resistance.The anode is modified by PANI doped with Fe or Mn to further improve the BMFC performance.A maximum power density of 17.51 mW/m2 is obtained by PANI-Fe anode BMFC,which is 8.1 times higher than that of control.The PANI-Mn anode BMFC also gives a favorable maximum power density(16.78 mW/m2).Fe or Mn modification has better effect in improving the conductivity of polyaniline,thus improving the energy output of BMFCs.This work applying PANI composite anode into BMFC brings new development prospect and could promote the practical application of BMFC.展开更多
Control design is important for proton exchange membrane fuel cell (PEMFC) generator. This work researched the anode system of a 60-kW PEMFC generator. Both anode pressure and humidity must be maintained at ideal leve...Control design is important for proton exchange membrane fuel cell (PEMFC) generator. This work researched the anode system of a 60-kW PEMFC generator. Both anode pressure and humidity must be maintained at ideal levels during steady operation. In view of characteristics and requirements of the system, a hybrid intelligent PID controller is designed specifically based on dynamic simulation. A single neuron PI controller is used for anode humidity by adjusting the water injection to the hydrogen cell. Another incremental PID controller, based on the diagonal recurrent neural network (DRNN) dynamic identification, is used to control anode pressure to be more stable and exact by adjusting the hydrogen flow rate. This control strategy can avoid the coupling problem of the PEMFC and achieve a more adaptive ability. Simulation results showed that the control strategy can maintain both anode humidity and pressure at ideal levels regardless of variable load, nonlinear dynamic and coupling characteristics of the system. This work will give some guides for further control design and applications of the total PEMFC generator.展开更多
Post-combustion amine absorption and stripping can remove 90% of the CO2 from power plant flue gas, but systems can reduce electrical output by approximately 30% due to energy requirements for stripping CO2 from solve...Post-combustion amine absorption and stripping can remove 90% of the CO2 from power plant flue gas, but systems can reduce electrical output by approximately 30% due to energy requirements for stripping CO2 from solvent and CO2 compression. The CO2 capture energy penalty can be reduced while developing renewable energy technologies by meeting CO2 capture energy requirements with a solar thermal energy system, particularly when electricity demand and prices are the highest. This study presents an initial review of solar thermal technologies for supplying CO2 capture energy, with a focus on high temperature systems. Parabolic troughs and central receivers are technically able to provide energy for CO2 capture. However, the solar system's capital costs would be roughly half that of the base coal-fired plant with CO2 capture, and high electricity prices are required to offset the costs of operating the solar thermal system. For high temperature solar thermal systems, direct electricity generation is likely a more efficient way to use solar energy to replace output lost to CO2 capture energy. However, low temperature solar thermal systems might integrate better with solvent stripping equipment, and more rigorous analysis is required to definitively assess the feasibility of using solar energy for CO2 capture.展开更多
文摘A dye-sensitized photocatalyst combining Pt-loaded TiO_(2) and Ru(Ⅱ)tris-diimine sensitizer(RuP)was constructed and its activity for photochemical hydrogen evolution was compared with that of Pt-intercalated HCa_(2)Nb_(3)O_(10) nanosheets.When the sacrificial donor ethylenediaminetetraacetic acid(EDTA)disodium salt dihydrate was used,RuP/Pt/TiO_(2) showed higher activity than RuP/Pt/HCa_(2)Nb_(3)O_(10).In contrast,when NaI(a reversible electron donor)was used,RuP/Pt/TiO_(2) showed little activity due to back electron transfer to the electron acceptor(I_(3)-),which was gener-ated as the oxidation product of I-.By modification with anionic polymers(sodium poly(styrenesulfonate)or sodium polymethacrylate)that could inhibit the scavenging of conduction band electrons by I_(3)-,the H_(2) production activity from aqueous NaI was improved,but it did not exceed that of RuP/Pt/HCa_(2)Nb_(3)O_(10).Transient absorption measurements showed that the rate of semiconductor-to-dye back electron transfer was slower in the case of TiO_(2) than HCa_(2)Nb_(3)O_(10),but the electron transfer reaction to I3-was much faster.These results indicate that Pt/TiO_(2) is useful for reactions with sacrificial reductants(e.g.,EDTA),where the back electron transfer reaction to the more reducible product can be neglected.However,more careful design of the catalyst will be nec-essary when a reversible electron donor is employed.
基金Zhenjiang City Key R&D Plan Modern Agriculture Project(No.SH2021017)Zhenjiang“Jinshan Talents”Project 2021Jiangsu Province“Six Talent Peak”Program(No.XCL-111)。
文摘Microbial fuel cells have already been used as biosensors to monitor assimilable organic carbon(AOC).However,their signal production from AOC is known to be completely suppressed by dissoved oxygen(DO).In this study,two identical microbial electrolysis cell(MEC)based biosensors were inoculated with marine sediment and operated at two different anodic potentials,namely-300 mV and+250 mV relative to Ag/AgCl.The MEC biosensor operated under positive anodic potential conditions had electrochemically active microbial communities on the anode,including members of the Shewanellaceae,Pseudoalteromonadaceae,and Clostridiaceae families.However,the strictly anaerobic members of the Desulfuromonadaceae,Desulfobulbaceae and Desulfobacteraceae families were found only in the negative anodic potential MEC biosensor.The positive anodic potential MEC biosensor showed several other advantages as well,such as faster start-up,significantly higher maximum current production,fivefold improvement in the AOC detection limit,and tolerance of low dissolved oxygen,compared to those obtained from the negative anodic potential MEC biosensor.The developed positive anodic potential MEC biosensor can thus be used as a real-time and inexpensive detector of AOC concentrations in high saline and low DO seawater.
基金The National Natural Science Foundation of China(No.51376110,51541604)the Major International(Regional) Joint Research Project of the National Natural Science Foundation of China(No.61320106011)
文摘The experimental study of natural convection in allglass evacuated tube solar collectors is performed through the experimental platform of the solar-assisted fuel cell system.The experimental facility includes solar collectors with different length and diameter tubes, different coating materials, and with / without guide plates, respectively. Threedimensional mathematical models on natural and forced convections in the solar collectors are established and the experimental data is validated by field synergy and entransy principles. The results of natural convection show that the water temperature increases and thermal efficiency decreases gradually with the evacuated tube length. The thermal efficiency increases when absorption rates increase from 0. 95 to 1. 0 and emission rates decrease from 0. 16 to 0. 06. The thermal efficiency of solar collectors is increased after being equipped with the guide plate, which is attributed to the disappearance of the mixed flowand the enhancement of the heat transfer at the bottom of the evacuated tube. The results of forced convertion indicate that the Reynolds, Nusselt and entransy increments of the horizontal double collectors are higher than those of the vertical single collector while the entransy dissipation is lower than that of the vertical single collector. It is concluded that the solar collectors with guide plates are suitable for natural convection while the double horizontal collectors are suitable for forced convection in the thermal field of solar-assisted fuel cell systems with lowand medium temperatures.
基金supprted by the National Natural Science Foundation of China(51672089,51672099)Specical Funding on Applied Science and Technology in Guangdong(2017B020238005)the State Key Laboratory of Advanced Technology for Material Synthesis and Processing(Wuhan University of Technology)(2015-KF-7)~~
文摘Photocatalysis is believed to be one of the best methods to realize sustainable H2 production. However, achieving this through heterogeneous photocatalysis still remains a great challenge owing to the absence of active sites, sluggish surface reaction kinetics, insufficient charge separation, and a high thermodynamic barrier. Therefore, cocatalysts are necessary and of great significance in boosting photocatalytic H2 generation. This review will focus on the promising and appealing low-cost Ni-based H2-generation cocatalysts as the alternatives for the high-cost and low-abundance noble metal cocatalysts. Special emphasis has been placed on the design principle, modification strategies for further enhancing the activity and stability of Ni-based cocatalysts, and identification of the exact active sites and surface reaction mechanisms. Particularly, four types of modification strategies based on increased light harvesting, enhanced charge separation, strengthened interface interaction, and improved electrocatalytic activity have been thoroughly discussed and compared in detail. This review may open a new avenue for designing highly active and durable Ni-based cocatalysts for photocatalytic H2 generation.
文摘Photocatalytic solar fuel generation is currently a hot topic because of its potential for solving the energy crisis owing to its low cost and zero-carbon emissions.However,the rapid bulk recombination of photoexcited carrier pairs is a fundamental disadvantage.To resolve this problem,we synthesized a dual cocatalysts system of cobalt phosphide(Co P)and molybdenum carbide(Mo_(2)C)embedded on strontium titanate(Sr TiO_(3))nanofibers.Compared with those of pristine SrTiO_(3) and binary samples,the dual cocatalysts system(denoted SCM)showed a significant improvement in the hydrogen evolution and CO_(2) reduction performance.Further,the structure of SCM effectively promoted spatial charge separation and enhanced the photocatalytic performance.In addition,the Schottky junction formed between the SrTiO_(3) and cocatalysts enabled the rapid transfer of photoexcited electrons from SrTiO_(3) to the cocatalysts,resulting in effective separation and prolonged photoexcited electron lifetimes.The electron migration route between SrTiO_(3) and the cocatalysts was determined by in situ irradiation X-ray spectroscopy,and band structures of Sr TiO_(3) and the cocatalysts are proposed based on results obtained from UV-vis diffraction reflection spectroscopy and ultraviolet photoelectron spectroscopy measurements.On the basis of our results,the dual cocatalysts unambiguously boosts charge separation and enhances photocatalytic performance.In summary,we have investigated the flux of photoexcited electrons in a dual cocatalysts system and provided a theoretical basis and ideas for subsequent research.
基金supported by the Grants-in-Aid for Scientific Research on the Innovative Area “Mixed Anion” (Project JP16H06441) by the Japan Society for the Promotion of Science (JSPS), and the Japan Association for Chemical Innovation
文摘Pt‐loaded graphitic carbon nitride(g‐C_(3)N_(4))is known to be a good photocatalyst for H_(2) evolution under visible light.In most cases,however,sacrificial electron donors such as triethanolamine are required for the water‐splitting operation,and nonsacrificial H_(2) evolution by g‐C_(3)N_(4) remains a challenge.In this work,we investigated the photocatalytic activities of carbon nitride nanosheet(NS‐C_(3)N_(4)),which was prepared by thermal treatment of urea,for nonsacrificial H_(2) evolution using reversible electron donors under visible light(λ>400 nm).Whereas Pt‐loaded NS‐C_(3)N_(4) did not produce H_(2) from aqueous solutions containing I−,Fe^(2+),or[Fe(CN)_(6)]^(4−),modification of the Pt/NS‐C_(3)N_(4) photocatalyst with CrO_(x) led to observable H_(2) evolution.Transmission electron microscopy observations and energy‐dispersive X‐ray spectroscopic analysis suggested that a Pt‐core/CrO_(x)‐shell structure was formed on the NS‐C_(3)N_(4).The CrO_(x)/Pt/NS‐C_(3)N_(4) served as a H_(2)‐evolution photocatalyst for visible‐light‐driven Z‐scheme overall water splitting,in combination with a modified WO_(3) photocatalyst,in the presence of a[Fe(CN)_(6)]^(3−/4−)redox mediator.
文摘Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites,few‐layer carbon nitride(FLCN)materials present great potential for production of solar fuels and chemicals and set off a new wave of research in the last few years.Herein,the recent progress in synthesis and regulation of FLCN‐based photocatalysts,and their applications in the conversion of sunlight into fuels and chemicals,is summarized.More importantly,the regulation strategies from chemical modification to microstructure control toward the production of solar fuels and chemicals has been deeply analyzed,aiming to inspire critical thinking about the effective approaches for photocatalyst modification rather than developing new materials.At the end,the key scientific challenges and some future trend of FLCN‐based materials as advanced photocatalysts are also discussed.
基金support from the Australian Research Council through its DECRA(DE210100930)Discovery Project (DP200101900)+2 种基金Lau-reate Fellowship (FL190100139) schemesfinancial support from Research Donation Generic(2020003431) from the Faculty of EngineeringArchitecture and Information Technology,The University of Queensland
文摘As a kind of valuable chemicals,hydrogen peroxide(H2O2)has aroused growing attention in many fields.However,H2O2 production via traditional anthraquinone process suffers from challenges of large energy consumption and heavy carbon footprint.Alternatively,photoelectrocatalytic(PEC)production of H2O2 has shown great promises to make H2O2 a renewable fuel to store solar energy.Transition‐metal‐oxide(TMO)semiconductor based photoelectrocatalysts are among the most promising candidates for PEC H2O2 production.In this work,the fundamentals of H2O2 synthesis through PEC process are briefly introduced,followed by the state‐of‐the‐art of TMO semiconductor based photoelectrocatalysts for PEC production H2O2.Then,the progress on H2O2 fuel cells from on‐site PEC production is presented.Furthermore,the challenges and future perspectives of PEC H2O2 production are discussed.This review aims to provide inspiration for the PEC production of H2O2 as a renewable solar fuel.
文摘Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energy crisis and environmental challenges.It enables not only the realization of clean,renewable,and high-heating-value solar fuels,but also the reduction of CO_(2) emissions.Layered double hydroxides(LDHs)are a type of two-dimensional anionic clay with a brucite-like structure,and are characterized by a unique,delaminable,multidimensional,layered structure;tunable intralayer metal cations;and exchangeable interlayer guest anions.Therefore,it has been widely investigated in the fields of CO_(2) reduction,photoelectrocatalytic water oxidation,and water photolysis to produce H2.However,the low carrier mobility and poor quantum efficiency of pure LDH limit its application.An increasing number of scholars are exploring methods to obtain LDH-based photocatalysts with high energy conversion efficiency,such as assembling photoactive components into LDH laminates,designing multidimensional structures,or coupling different types of semiconductors to construct heterojunctions.This review first summarizes the main characteristics of LDH,i.e.,metal-cation tunability,intercalated guest-anion substitutability,thermal decomposability,memory effect,multidimensionality,and delaminability.Second,LDHs,LDH-based composites(metal sulfide-LDH composites,metal oxide-LDH composites,graphite phase carbon nitride-LDH composites),ternary LDH-based composites,and mixed-metal oxides for splitting water to produce H_(2) are reviewed.Third,graphite phase carbon nitride-LDH composites,MgAl-LDH composites,CuZn-LDH composites,and other semiconductor-LDH composites for CO_(2) reduction are introduced.Although the field of LDH-based photocatalysts has advanced considerably,the photocatalytic mechanism of LDHs has not been thoroughly elucidated;moreover,the photocatalytic active sites,the synergy between different components,and the interfacial reaction mechanism of LDH-based photocatalysts require further investigation.Therefore,LDH composite materials for photocatalysis could be developed through structural regulation and function-oriented design to investigate the effects of different components and interface reactions,the influence of photogenerated carriers,and the impact of material composition on the physical and chemical properties of the LDH-based photocatalyst.
基金supported by EU with ERC Synergy SCOPE(Surface-Confined Fast-modulated Plasma for Process and Energy Intensification in Small Molecules Conversion,810182)ProjectItalian MUR by PRIN 2017 Projects MULTI-e (Multielectron Transfer for the Conversion of Small Moleculesan Enabling Technology for the Chemical Use of Renewable Energy,20179337R7)CO_(2) ONLY (CO_(2) as Only Source of Carbons for Monomers and PolymersA Step Forwards Circular economy) Project,017WR2LRS
文摘After short introducing the crucial role of e‐fuels to meet net‐zero emissions targets,this perspective paper discusses the differences between reactive catalysis(electro‐,photo‐and plasma‐catalysis,with focus on the first for conciseness)and thermal catalysis used at most.The main point is to evidence that to progress in producing e‐fuels,the gap is not in terms of scaling‐up and pilot testing,but rather in the fundamental needs to turn the current approach and methodologies to develop reactive catalysis,including from a mechanistic perspective,to go beyond the current methods largely derived from thermal catalysis.Developing thus new fundamental bases to understand reactive catalysis is the challenge to accelerate the progress in this area to enable the potential role towards a sustainable net‐zero emissions future.Some novel aspects are highlighted,but the general aim is rather to stimulate discussion in rethinking catalysis from an alternative perspective.
基金supported by the Australian Research Council(FT120100913)the National Natural Science Foundation of China(51372248,51432009)~~
文摘Solar‐driven thermochemical water splitting represents one efficient route to the generation of H2as a clean and renewable fuel.Due to their outstanding catalytic abilities and promising solar fuel production capacities,perovskite‐type redox catalysts have attracted significant attention in this regard.In the present study,the perovskite series La1‐xCaxMn1‐yAlyO3(x,y=0.2,0.4,0.6,or0.8)was fabricated using a modified Pechini method and comprehensively investigated to determine the applicability of these materials to solar H2production via two‐step thermochemical water splitting.The thermochemical redox behaviors of these perovskites were optimized by doping at either the A(Ca)or B(Al)sites over a broad range of substitution values,from0.2to0.8.Through this doping,a highly efficient perovskite(La0.6Ca0.4Mn0.6Al0.4O3)was developed,which yielded a remarkable H2production rate of429μmol/g during two‐step thermochemical H2O splitting,going between1400and1000°C.Moreover,the performance of the optimized perovskite was found to be eight times higher than that of the benchmark catalyst CeO2under the same experimental conditions.Furthermore,these perovskites also showed impressive catalytic stability during two‐step thermochemical cycling tests.These newly developed La1‐xCaxMn1‐yAlyO3redox catalysts appear to have great potential for future practical applications in thermochemical solar fuel production.
文摘Band engineering based on the construction of solid solutions is an effective approach to enhance the efficiency of semiconductor photocatalysts, via which the balance between light absorption and driving force can be well achieved by continuously tuning the band structure. Here the ZnS1–xSex nanobelt solid solutions have been prepared via thermal treatment of ZnS1–xSex(en)0.5 precursors. The compositions are adjusted by changing the mole ratio of Se to S powder in the starting materials, resulting in continuously modulating the alignment of energy levels of the obtained solid solutions. The band structure is also studied via theoretical calculation. Accordingly, the light harvesting can be tuned too, as confirmed by the UV-vis absorption spectra. XPS valence spectra are used to determine the valence band maximum. Transient photoluminescence spectra are employed to study the separation of photogenerated charge carriers. BET specific surface area and CO2 adsorption isotherms of different catalysts are measured. The obtained ZnS1–xSex nanobelts exhibit different photocatalytic activity for solar-fuel production, dependent on many factors like the light harvesting and alignment of energy levels. The related mechanism is studied in detail.
文摘Solar-driven CO_(2) reduction is an efficient way to convert sustainable solar energy and massive CO_(2) to renewable solar fuels,such as CH_(4),HCOOH,HCHO,and CH_(3)OH,etc.Up to now,significant research efforts have been devoted to exploring the reaction path and developing the photocatalysts.In heterogeneous photocatalysis,among the semiconductor-based photocatalysts,titania(TiO_(2)),as an inexpensive and practically sustainable metal oxides,remains the most extensively studied photocatalyst over the past decades.In this review,we summarize the most recent advances in the solar-driven CO_(2) reduction using TiO_(2)-based photocatalysts,which include the fabrication of heterojunction,surface functional modification,band structure engineering,and morphology design,aiming to improve the CO_(2) conversion efficiency and selectivity to the desired product.Additionally,photoelectrochemical and photothermal approaches are introduced and the fundamental principles to activate and enhance the performance of TiO_(2) for the specific reaction are discussed.The exploration of the solar-driven approaches and discussion on the underlying mechanism allow the comprehensive understanding of CO_(2) photoreduction,that can lead to a rational design and synthesis of TiO_(2)-based photocatalysts.
基金Project(HIT.NSRIF.2014128)supported by the Fundamental Research Funds for the Central Universities,ChinaProject(2014M551257)supported by the China Postdoctoral Science FoundationProject(WH20150208)supported by the Subject Development Foundation of Harbin Institute of Technology at Weihai,China
文摘In this study,conductive polymer polyaniline(PANI)is employed to modify the anodes of benthic microbial fuel cells(BMFC).Four electrochemical methods are used to synthesize the polyaniline anodes;the results show that the PANI modification,especially the pulse potential method for PANI synthesis could obviously improve the cell energy output and reduce the anode internal resistance.The anode is modified by PANI doped with Fe or Mn to further improve the BMFC performance.A maximum power density of 17.51 mW/m2 is obtained by PANI-Fe anode BMFC,which is 8.1 times higher than that of control.The PANI-Mn anode BMFC also gives a favorable maximum power density(16.78 mW/m2).Fe or Mn modification has better effect in improving the conductivity of polyaniline,thus improving the energy output of BMFCs.This work applying PANI composite anode into BMFC brings new development prospect and could promote the practical application of BMFC.
基金Project (No. 2002AA517020) supported by the Hi-Tech Research and Development Program (863) of China
文摘Control design is important for proton exchange membrane fuel cell (PEMFC) generator. This work researched the anode system of a 60-kW PEMFC generator. Both anode pressure and humidity must be maintained at ideal levels during steady operation. In view of characteristics and requirements of the system, a hybrid intelligent PID controller is designed specifically based on dynamic simulation. A single neuron PI controller is used for anode humidity by adjusting the water injection to the hydrogen cell. Another incremental PID controller, based on the diagonal recurrent neural network (DRNN) dynamic identification, is used to control anode pressure to be more stable and exact by adjusting the hydrogen flow rate. This control strategy can avoid the coupling problem of the PEMFC and achieve a more adaptive ability. Simulation results showed that the control strategy can maintain both anode humidity and pressure at ideal levels regardless of variable load, nonlinear dynamic and coupling characteristics of the system. This work will give some guides for further control design and applications of the total PEMFC generator.
文摘Post-combustion amine absorption and stripping can remove 90% of the CO2 from power plant flue gas, but systems can reduce electrical output by approximately 30% due to energy requirements for stripping CO2 from solvent and CO2 compression. The CO2 capture energy penalty can be reduced while developing renewable energy technologies by meeting CO2 capture energy requirements with a solar thermal energy system, particularly when electricity demand and prices are the highest. This study presents an initial review of solar thermal technologies for supplying CO2 capture energy, with a focus on high temperature systems. Parabolic troughs and central receivers are technically able to provide energy for CO2 capture. However, the solar system's capital costs would be roughly half that of the base coal-fired plant with CO2 capture, and high electricity prices are required to offset the costs of operating the solar thermal system. For high temperature solar thermal systems, direct electricity generation is likely a more efficient way to use solar energy to replace output lost to CO2 capture energy. However, low temperature solar thermal systems might integrate better with solvent stripping equipment, and more rigorous analysis is required to definitively assess the feasibility of using solar energy for CO2 capture.