The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportio...The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.展开更多
Combination of a bus system and cable car system can reduce the overall congestion of traffic in urban areas, where surrounding hills or mountains hold larger settlements or tourist and recreational infrastructure. Wi...Combination of a bus system and cable car system can reduce the overall congestion of traffic in urban areas, where surrounding hills or mountains hold larger settlements or tourist and recreational infrastructure. With this kind of integration number of individual car trips can be significantly reduced. In this paper, the authors present an analysis of the pilot project implementation, which was held in Maribor. The authors conducted a limited test trial of two means of transportation, combining them into a single operating transport offer for inhabitants and tourists. Combined transport option proved to be a good starting point for reduction of traffic and parking congestion during winter tourist season and beyond. Method used in the research, in order to gain actual potential of integrating two systems and improving public transport offer, was establishment and implementation of the pilot project in Maribor during January 2011. Data was gathered through interviews of two interest groups. The first covered the users who were brought to the foothills of Pohorje＇s ski center by bus. The second covered the cable car users that were traveling to the top of Pohorje. For a limited time period, a trial principle of a single ticket was established, which gave ski-pass holders free bus ride on bus line No. 6. With the aim of reducing CO2, test drives of hybrid bus and compressed natural gas bus were conducted alongside many promotional activities with which users were informed of importance of environmentally friendly mobility options.展开更多
Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by ...Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.展开更多
Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combi...Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combining these carbon-involved photocatalytic oxidation-reduction processes together,by which an artificial photocatalytic carbon cycling process can be established.The key challenge lies in the exploitation of efficient bifunctional photocatalysts,capable of triggering both aerobic oxidation and anaerobic reduction reactions.In this work,a bifunctional ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst is successfully constructed,which not only demonstrates superior aerobic photocatalytic oxidation performance in degrading an organic pollutant(using the dye,Rhodamine B as a model),but also exhibits impressive photocatalytic CO2 reduction performance under anaerobic conditions.Moreover,a direct conversion of Rhodamine B to solar fuels in a one-pot anaerobic reactor can be achieved with the as-prepared ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst.The excellent bifunctional photocatalytic performance of the g-C3N4/Bi/BiVO4 photocatalyst is associated with the formation of efficient S-scheme hybrid junctions,which contribute to promoting the appropriate charge dynamics,and sustaining favorable charge potentials.The formation of the S-scheme heterojunction is supported by scavenger studies and density functional theory calculations.Moreover,the in-situ formed plasmonic metallic Bi nanoparticles in the S-scheme hybrid g-C3N4/Bi/BiVO4 photocatalyst enhances vectorial interfacial electron transfer.This novel bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalyst system provides new insights for the further development of an integrated aerobic-anaerobic reaction system for photocatalytic carbon cycling.展开更多
The global steel production has been growing for the last 50 years, from 200 Mt in 1950s to 1 240 Mt in 2006. Iron and steel making industry is one of the most energy-intensive industries, with an annual energy consum...The global steel production has been growing for the last 50 years, from 200 Mt in 1950s to 1 240 Mt in 2006. Iron and steel making industry is one of the most energy-intensive industries, with an annual energy consumption of about 24 EJ, 5% of the world＇s total energy consumption. The steel industry accounts for 3%-4% of totat world greenhouse gas emissions. Enhancing energy efficiency and employing energy saving/recovering technologies such as coke dry quechning （CDQ） and top pressure recovery turbine （TRT） can be short-term approaches to the steel industry to reduce greenhouse gas emission. The long-term approaches to achieving a significant reduction in CO2 emissions from the steel industry would be through developing and applying CO2 breakthrough technologies for iron and steel making, and：through increasing use of renewable energy for iron and steel making. Thus, an overview of new CO2 breakthrough technologies for iron and steel making was made.展开更多
Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow micro...Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow microspheres(HS),were dedicatedly designed to boost overall photocatalytic efficiency.TiO_(2) nanoparticles were in-situ decorated on the inside and outside the shell of Cd S HS,ensuring close contact between TiO_(2) and CdS.The CdS/TiO2 HS with abundant mesopores inside of the shell boost the light absorption via multiscattering effect as well as accessible to reactions in all directions.The heterojunction was scrutinized and the charge transfer across it was revealed by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS).Ultimately,the charge transfer in this composite was determined to follow stepscheme mechanism,which not only facilitates the separation of charge carriers but also preserves strong redox ability.Benefited from the intimate linkage between Cd S and TiO_(2) and the favorable step-scheme heterojunction,enhanced photocatalytic CO_(2) reduction activity was accomplished.The CH4 yield rate of CdS/TiO_(2) reaches 27.85μmol g^(–1) h^(–1),which is 145.6 and 3.8 times higher than those of pristine CdS and TiO_(2),respectively.This work presents a novel insight into constructing step-scheme photocatalytic system with desirable performance.展开更多
The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is high...The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.展开更多
The Bi2S3,CdS and Bi2S3/CdS photocatalysts were prepared by direct reactions between their corresponding salt and thiourea in a hy- drothermal autoclave.The photocatalytic activities of these photocatalysts for reduci...The Bi2S3,CdS and Bi2S3/CdS photocatalysts were prepared by direct reactions between their corresponding salt and thiourea in a hy- drothermal autoclave.The photocatalytic activities of these photocatalysts for reducing CO2 to CH3OH under visible light irradiation have been investigated.The results show that the photocatalytic activity and visible light response of Bi2S3 are higher than those of CdS.The Bi2S3 modification can enhance the photocatalytic activity and visible light response of CdS.The photocatalytic activity of Bi2S3/CdS hetero-junction photocatalyst was the highest and the highest yields of methanol was 613μmol/g when the weight proportion of Bi2S3 to CdS was 15%,which was about three times as large as that of CdS or two times of that of Bi2S3.展开更多
Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially ...Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially improve the photocatalytic efficiency of semiconductors.Because the high cost and scarcity of noble metals markedly limit their large-scale applications,finding a noble-metal-alternative co-catalyst is crucial.MXene,a novel 2D transition metal material,has attracted considerable attention as a promising substitute for noble metal co-catalysts owing to its cost-efficiency,unique 2D layered structure,and excellent electrical,optical,and thermodynamic properties.This review focuses on the latest advancements in research on MXenes as co-catalysts in relatively popular photocatalytic applications(hydrogen production,CO2 reduction,nitrogen fixation,and organic pollutant oxidation).The synthesis methods and photocatalytic mechanisms of MXenes as co-catalysts are also summarized according to the type of MXene-based material.Finally,the crucial opportunities and challenges in the prospective development of MXene-based photocatalysts are outlined.We emphasize that modern techniques should be used to demonstrate the effects of MXenes on photocatalysis and that the photocatalytic activity of MXene-based photocatalysts can be further improved using defective engineering and recent phenomena such as the localized surface plasmon resonance effect and single-atom catalysis.展开更多
TiO2‐based Z‐scheme photocatalysts have attracted considerable attention because of the low recombination rate of their photogenerated electron–hole pairs and their high photocatalytic efficiency.In this review,the...TiO2‐based Z‐scheme photocatalysts have attracted considerable attention because of the low recombination rate of their photogenerated electron–hole pairs and their high photocatalytic efficiency.In this review,the reaction mechanism of Z‐scheme photocatalysts,recent research progress in the application of TiO2‐based Z‐scheme photocatalysts,and improved methods for photocatalytic performance enhancement are explored.Their applications,including water splitting,CO2reduction,decomposition of volatile organic compounds,and degradation of organic pollutants,are also described.The main factors affecting the photocatalytic performance of TiO2‐based Z‐scheme photocatalysts,such as pH,conductive medium,cocatalyst,architecture,and mass ratio,are discussed.Concluding remarks are presented,and some suggestions for the future development of TiO2‐based Z‐scheme photocatalysts are highlighted.展开更多
Herein,we prepa red novel three-dimensional(3D)gear-s haped Co3O4@C(Co3O4 modified by amorphous carbon)and sheet-like SnO2/CC(SnO2 grow on the carbon cloth)as anode and cathode to achieve efficient removal of 4-nitrop...Herein,we prepa red novel three-dimensional(3D)gear-s haped Co3O4@C(Co3O4 modified by amorphous carbon)and sheet-like SnO2/CC(SnO2 grow on the carbon cloth)as anode and cathode to achieve efficient removal of 4-nitrophenol(4-NP)in the presence of peroxymonosulfate(PMS)and simultaneous electrocatalytic reduction of CO2,respectively.In this process,4-NP was mineralized into CO2 by the Co3O4@C,and the generated CO2 was reduced into HCOOH by the sheet-like SnO2/CC cathode.Compared with the pure Co0.5(Co3O4 was prepared using 0.5 g urea)with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP(60 mL,10 mg/L)increased from 74.5%-85.1%in 60 min using the Co0.5 modified by amorphous carbon(Co0.5@C).Furthermore,when the voltage of 1.0 V was added in the anodic system of Co0.5@C with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP increased from 85.1%-99.1%when Pt was used as cathode.In the experiments of 4-NP degradation coupled with simultaneous electrocatalytic CO2 reduction,the degradation efficiency of 4-NP was 99.0%in the anodic system of Co0.5@C with addition of PMS(30 mg,0.5 g/L),while the Faraday efficiency(FE)of HCOOH was 24.1%at voltage of-1.3 V using the SnO2/CC as cathode.The results showed that the anode of Co3O4 modified by amorphous carbon can markedly improve the degradation efficiency of 4-NP,while the cathode of SnO2/CC can greatly improve the FE and selectivity of CO2 reduction to HCOOH and the stability of cathode.Finally,the promotion mechanism was proposed to explain the degradation of organic pollutants and reduction of CO2 into HCOOH in the process of electrocatalysis coupled with advanced oxidation processes(AOPs)and simultaneous CO2 reduction.展开更多
The chemical reduction of CO2 remains a challenge with respect to the reversal of the oxidative degradation of any organic materials. The conversion of CO2 into useful substances is essential in developing alternative...The chemical reduction of CO2 remains a challenge with respect to the reversal of the oxidative degradation of any organic materials. The conversion of CO2 into useful substances is essential in developing alternative fuels and various raw materials for different industries. This also aids in preventing the continuous rise in tropospheric temperature due to the green house effect of CO2. In this article an overview of the growth taken place so far in the field of CO2 chemical reduction is pre- sented. The discussion comprises of photochemical methods for the development of different products, viz. CO, CH3OH and CH4, through chemical reduction of CO2. This includes the use of photo catalysts, mainly TiO2, and the role of a hole scavenger （such as 2-propanol） for this purpose.展开更多
Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low...Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.展开更多
As the biggest iron and steel producer in the world and one of the highest CO2 emission sectors, China’s iron and steel industry is undergoing a low-carbon transition accompanied by remarkable technological progress ...As the biggest iron and steel producer in the world and one of the highest CO2 emission sectors, China’s iron and steel industry is undergoing a low-carbon transition accompanied by remarkable technological progress and investment adjustment, in response to the macroeconomic climate and policy intervention. Many drivers of the CO2 emissions of the iron and steel industry have been explored, but the relationships between CO2 abatement,investment and technological expenditure, and their connections with the economic growth and governmental policies in China, have not been conjointly and empirically examined. We proposed a concise conceptual model and an econometric model to investigate this crucial question. The results of regression, Granger causality test and impulse response analysis indicated that technological expenditure can significantly reduce CO2 emissions, and that investment expansion showed a negative impact on CO2 emission reduction. It was also argued with empirical evidence that a good economic situation favored CO2 abatement in China’s iron and steel industry, while achieving CO2 emission reduction in this industrial sector did not necessarily threaten economic growth.This shed light on the dispute over balancing emission cutting and economic growth.Regarding the policy aspects, the year 2000 was found to be an important turning point for policy evolution and the development of the iron and steel industry in China. The subsequent command and control policies had a significant, positive effect on CO2 abatement.展开更多
Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide(ZnO)-based photocatalysts.In this paper,we report the fabrication of graphitic-carbon-mediated ZnO nan...Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide(ZnO)-based photocatalysts.In this paper,we report the fabrication of graphitic-carbon-mediated ZnO nanorod arrays(NRAs)with enhanced photocatalytic activity and photostability for CO2 reduction under visible light irradiation.ZnO NRA/C-x(x=005,01,02,and 03)nanohybrids are prepared by calcining pre-synthesized ZnO NRAs with different amounts of glucose(0.05,0.1,0.2,and 0.3 g)as a carbon source via a hydrothermal method.X-ray photoelectron spectroscopy reveals that the obtained ZnO NRA/C-x nanohybrids are imparted with the effects of both carbon doping and carbon coating,as evidenced by the detected C-O-Zn bond and the C-C,C-O and C=O bonds,respectively.While the basic structure of ZnO remains unchanged,the UV-Vis absorption spectra show increased absorbance owing to the carbon doping effect in the ZnO NRA/C-x nanohybrids.The photoluminescence(PL)intensities of ZnO NRA/C-x nanohybrids are lower than that of bare ZnO NRA,indicating that the graphitic carbon layer coated on the surface of the ZnO NRA significantly enhances the charge carrier separation and transport,which in turn enhances the photoelectrochemical property and photocatalytic activity of the ZnO NRA/C-x nanohybrids for CO2 reduction.More importantly,a long-term reaction of photocatalytic CO2 reduction demonstrates that the photostability of ZnO NRA/C-x nanohybrids is significantly increased in comparison with the bare ZnO NRA.展开更多
Highly efficient photocatalytic reduction of CO2 is essential for solving the greenhouse effect and energy crisis.In this paper,the Sm-TiO2 nanocomposites were successfully prepared via sol-gel method.The CO2 photored...Highly efficient photocatalytic reduction of CO2 is essential for solving the greenhouse effect and energy crisis.In this paper,the Sm-TiO2 nanocomposites were successfully prepared via sol-gel method.The CO2 photoreduction activities of synthesized samples were tested under irradiation for 6 h and the results indicate that the 0.5% Sm-TiO2 catalyst has superior performance and stability.The CO and CH4 yields of0.5% Sm-TiO2 catalyst are 55.47 and 3.82 μmol/g·cat respectively,which are 5.02 and 2.67 times the yield of TiO2.The possible mechanism of Sm doped TiO2 was investigated through comprehensive characterization and photoetectrochemical analysis,After the Sm doping,the photo-generated electrons in TiO2 could migrate to Sm 4 f,and some of them can be captured by reducing Sm3+ o Sm2+,which can lower the recombination rate of electron and hole pairs.Therefore,the enhanced photocatalytic performance could be ascribed to large specific surface area,fast separation rate of electron-hole pairs and high visible light response.This report provides some meaningful attempts in researching the CO2 photocatalytic reduction.展开更多
Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a nov...Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.展开更多
The active site amount of photocatalysts,being the key factors in photocatalytic reactions,directly affects the photocatalytic performance of the photocatalyst.Pristine graphitic carbon nitride(g‐C_(3)N_(4))exhibits ...The active site amount of photocatalysts,being the key factors in photocatalytic reactions,directly affects the photocatalytic performance of the photocatalyst.Pristine graphitic carbon nitride(g‐C_(3)N_(4))exhibits moderate photocatalytic activity due to insufficient active sites.In this study,cyano‐modified porous g‐C_(3)N_(4)nanosheets(MCN‐0.5)were synthesized through molecular self‐assembly and alkali‐assisted strategies.The cyano group acted as the active site of the photocatalytic reaction,because the good electron‐withdrawing property of the cyano group promoted carrier separation.Benefiting from the effect of the active sites,MCN‐0.5 exhibited significantly enhanced photocatalytic activity for CO2 reduction under visible light irradiation.Notably,the photocatalytic activity of MCN‐0.5 was significantly reduced when the cyano groups were removed by hydrochloric acid(HCl)treatment,further verifying the role of cyano groups as active sites.The photoreduction of Pt nanoparticles provided an intuitive indication that the introduction of cyano groups provided more active sites for the photocatalytic reaction.Furthermore,the controlled experiments showed that g‐C_(3)N_(4)grafted with cyano groups using melamine as the precursor exhibited enhanced photocatalytic activity,which proved the versatility of the strategy for enhancing the activity of g‐C_(3)N_(4)via cyano group modification.In situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations were used to investigate the mechanism of enhanced photocatalytic activity for CO2 reduction by cyano‐modified g‐C_(3)N_(4).This work provides a promising route for promoting efficient solar energy conversion by designing active sites in photocatalysts.展开更多
The electrochemical reduction of CO2(CO2 RR) can substantially contribute to the production of useful chemicals and reduction of global CO2 emissions. Herein, we presented N and S dual-doped high-surface-area carbon m...The electrochemical reduction of CO2(CO2 RR) can substantially contribute to the production of useful chemicals and reduction of global CO2 emissions. Herein, we presented N and S dual-doped high-surface-area carbon materials(SZ-HCN) as CO2 RR catalysts. N and S were doped by one-step pyrolysis of a N-containing polymer and S powder. ZnCl2 was applied as a volatile porogen to prepare porous SZ-HCN. SZ-HCN with a high specific surface area(1510 m2 g–1) exhibited efficient electrocatalytic activity and selectivity for CO2 RR. Electrochemical measurements demonstrated that SZ-HCN showed excellent catalytic performance for CO2-to-CO reduction with a high CO Faradaic efficiency(~93%) at-0.6 V. Furthermore, SZ-HCN offered a stable current density and high CO selectivity over at least 20 h continuous operation, revealing remarkable electrocatalytic durability. The experimental results and density functional theory calculations indicated that N and S dual-doped carbon materials required lower Gibbs free energy to form the COOH* intermediate than that for single-N-doped carbon for CO2-to-CO reduction, thereby enhancing CO2 RR activity.展开更多
Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio...Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio from photocatalytic CO2 reduction reaction still poses a great challenge for the further application.Herein,we prepared a series of highly efficient heterostructure based on highly dispersed palladium supported on ultrathin Co Al-layered double hydroxide(LDH).In conjunction with a Ru-complex sensitizer,the molar ratios of CO/H2 can be tuned from 1:0.74 to 1:3 under visible-light irradiation(λ>400 nm).More interestingly,the syngas can be obtained under light irradiation atλ>600 nm.Structure characterization and density functional theory calculations revealed that the remarkable catalytic activity can be due to the supported palladium,which improved the charge transfer efficiency.Meanwhile,more H atoms were used to generate H2 on the supported palladium for further tunable CO/H2 ratio.This work demonstrates a new strategy for harnessing abundant solar-energy to produce syngas from a CO2 feedstock.展开更多
基金National Natural Science Foundation of China(grants 22072065,22178162,and 22222806)Distinguished Youth Foundation of Jiangsu Province(grant BK20220053)Six talent peaks project in Jiangsu Province(grant JNHB-035)。
文摘The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.
文摘Combination of a bus system and cable car system can reduce the overall congestion of traffic in urban areas, where surrounding hills or mountains hold larger settlements or tourist and recreational infrastructure. With this kind of integration number of individual car trips can be significantly reduced. In this paper, the authors present an analysis of the pilot project implementation, which was held in Maribor. The authors conducted a limited test trial of two means of transportation, combining them into a single operating transport offer for inhabitants and tourists. Combined transport option proved to be a good starting point for reduction of traffic and parking congestion during winter tourist season and beyond. Method used in the research, in order to gain actual potential of integrating two systems and improving public transport offer, was establishment and implementation of the pilot project in Maribor during January 2011. Data was gathered through interviews of two interest groups. The first covered the users who were brought to the foothills of Pohorje＇s ski center by bus. The second covered the cable car users that were traveling to the top of Pohorje. For a limited time period, a trial principle of a single ticket was established, which gave ski-pass holders free bus ride on bus line No. 6. With the aim of reducing CO2, test drives of hybrid bus and compressed natural gas bus were conducted alongside many promotional activities with which users were informed of importance of environmentally friendly mobility options.
基金supported by the National Basic Research Program of China(973 Program2013CB632402)+7 种基金the National Natural Science Foundation of China(513201050015137219051402025and 21433007)the Natural Science Foundation of Hubei Province(2015CFA001)the Fundamental Research Funds for the Central Universities(WUT:2014-VII-010)the Self-Determined and Innovative Research Funds of State Key Laboratory of Advanced Technology for Material Synthesis and ProcessingWuhan University of Technology(2013-ZD-1)~~
文摘Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.
基金financially supported by the National Natural Science Foundation of China(51872341,51572209)the Start-up Funds for High-Level Talents of Sun Yat-sen University(38000-31131105)+1 种基金the Fundamental Research Funds for the Central Universities(19lgzd29)the Science and Technology Program of Guangzhou(201707010095)~~
文摘Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combining these carbon-involved photocatalytic oxidation-reduction processes together,by which an artificial photocatalytic carbon cycling process can be established.The key challenge lies in the exploitation of efficient bifunctional photocatalysts,capable of triggering both aerobic oxidation and anaerobic reduction reactions.In this work,a bifunctional ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst is successfully constructed,which not only demonstrates superior aerobic photocatalytic oxidation performance in degrading an organic pollutant(using the dye,Rhodamine B as a model),but also exhibits impressive photocatalytic CO2 reduction performance under anaerobic conditions.Moreover,a direct conversion of Rhodamine B to solar fuels in a one-pot anaerobic reactor can be achieved with the as-prepared ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst.The excellent bifunctional photocatalytic performance of the g-C3N4/Bi/BiVO4 photocatalyst is associated with the formation of efficient S-scheme hybrid junctions,which contribute to promoting the appropriate charge dynamics,and sustaining favorable charge potentials.The formation of the S-scheme heterojunction is supported by scavenger studies and density functional theory calculations.Moreover,the in-situ formed plasmonic metallic Bi nanoparticles in the S-scheme hybrid g-C3N4/Bi/BiVO4 photocatalyst enhances vectorial interfacial electron transfer.This novel bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalyst system provides new insights for the further development of an integrated aerobic-anaerobic reaction system for photocatalytic carbon cycling.
基金Item Sponsored by Natural Science and Engineering Research Council of Canada (NSERC) (326868-06)
文摘The global steel production has been growing for the last 50 years, from 200 Mt in 1950s to 1 240 Mt in 2006. Iron and steel making industry is one of the most energy-intensive industries, with an annual energy consumption of about 24 EJ, 5% of the world＇s total energy consumption. The steel industry accounts for 3%-4% of totat world greenhouse gas emissions. Enhancing energy efficiency and employing energy saving/recovering technologies such as coke dry quechning （CDQ） and top pressure recovery turbine （TRT） can be short-term approaches to the steel industry to reduce greenhouse gas emission. The long-term approaches to achieving a significant reduction in CO2 emissions from the steel industry would be through developing and applying CO2 breakthrough technologies for iron and steel making, and：through increasing use of renewable energy for iron and steel making. Thus, an overview of new CO2 breakthrough technologies for iron and steel making was made.
基金financially supported by the National Natural Science Foundation of China(NSFC)(Nos.51872220,51932007,51961135303,21871217,U1905215 and U1705251)the National Key Research and Development Program of China(No.2018YFB1502001)the Fundamental Research Funds for the Central Universities(No.WUT:2019IVB050)。
文摘Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow microspheres(HS),were dedicatedly designed to boost overall photocatalytic efficiency.TiO_(2) nanoparticles were in-situ decorated on the inside and outside the shell of Cd S HS,ensuring close contact between TiO_(2) and CdS.The CdS/TiO2 HS with abundant mesopores inside of the shell boost the light absorption via multiscattering effect as well as accessible to reactions in all directions.The heterojunction was scrutinized and the charge transfer across it was revealed by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS).Ultimately,the charge transfer in this composite was determined to follow stepscheme mechanism,which not only facilitates the separation of charge carriers but also preserves strong redox ability.Benefited from the intimate linkage between Cd S and TiO_(2) and the favorable step-scheme heterojunction,enhanced photocatalytic CO_(2) reduction activity was accomplished.The CH4 yield rate of CdS/TiO_(2) reaches 27.85μmol g^(–1) h^(–1),which is 145.6 and 3.8 times higher than those of pristine CdS and TiO_(2),respectively.This work presents a novel insight into constructing step-scheme photocatalytic system with desirable performance.
文摘The solar-driven catalytic conversion of CO2 to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect.However,it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO2 in photoreduction processes.In this work,three-dimensional hierarchical Cd0.8Zn0.2S flowers(C8Z2S-F)with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director.The flower-like Cd0.8Zn0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO2,generating CO up to 41.4μmol g^−1 under visible-light illumination for 3 h;this was nearly three times greater than that of Cd0.8Zn0.2S nanoparticles(C8Z2S-NP)(14.7μmol g^−1).Particularly,a comparably high selectivity of 89.9%for the conversion of CO2 to CO,with a turnover number of 39.6,was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent.Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F.The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process.Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd0.8Zn0.2S solid solution possessed desirable CO2 adsorption properties and an enhanced charge-transfer capability,thus providing a highly effective photocatalytic reduction of CO2.
基金supported by the National Natural Science Foundation of China(No.20906034)the Key Academic Program of the 3rd Phase"211 Project" of South China Agricultural University(No.2009B010100001)China Postdoctoral Science Foundation(No.20080430820)
文摘The Bi2S3,CdS and Bi2S3/CdS photocatalysts were prepared by direct reactions between their corresponding salt and thiourea in a hy- drothermal autoclave.The photocatalytic activities of these photocatalysts for reducing CO2 to CH3OH under visible light irradiation have been investigated.The results show that the photocatalytic activity and visible light response of Bi2S3 are higher than those of CdS.The Bi2S3 modification can enhance the photocatalytic activity and visible light response of CdS.The photocatalytic activity of Bi2S3/CdS hetero-junction photocatalyst was the highest and the highest yields of methanol was 613μmol/g when the weight proportion of Bi2S3 to CdS was 15%,which was about three times as large as that of CdS or two times of that of Bi2S3.
文摘Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially improve the photocatalytic efficiency of semiconductors.Because the high cost and scarcity of noble metals markedly limit their large-scale applications,finding a noble-metal-alternative co-catalyst is crucial.MXene,a novel 2D transition metal material,has attracted considerable attention as a promising substitute for noble metal co-catalysts owing to its cost-efficiency,unique 2D layered structure,and excellent electrical,optical,and thermodynamic properties.This review focuses on the latest advancements in research on MXenes as co-catalysts in relatively popular photocatalytic applications(hydrogen production,CO2 reduction,nitrogen fixation,and organic pollutant oxidation).The synthesis methods and photocatalytic mechanisms of MXenes as co-catalysts are also summarized according to the type of MXene-based material.Finally,the crucial opportunities and challenges in the prospective development of MXene-based photocatalysts are outlined.We emphasize that modern techniques should be used to demonstrate the effects of MXenes on photocatalysis and that the photocatalytic activity of MXene-based photocatalysts can be further improved using defective engineering and recent phenomena such as the localized surface plasmon resonance effect and single-atom catalysis.
基金supported by the National Natural Science Foundation of China(51602207,21433007,51320105001,21573170)the Self-determined and Innovative Research Funds of SKLWUT(2017-ZD-4,2016-KF-17)the Natural Science Foundation of Hubei Province of China(2015CFA001)~~
文摘TiO2‐based Z‐scheme photocatalysts have attracted considerable attention because of the low recombination rate of their photogenerated electron–hole pairs and their high photocatalytic efficiency.In this review,the reaction mechanism of Z‐scheme photocatalysts,recent research progress in the application of TiO2‐based Z‐scheme photocatalysts,and improved methods for photocatalytic performance enhancement are explored.Their applications,including water splitting,CO2reduction,decomposition of volatile organic compounds,and degradation of organic pollutants,are also described.The main factors affecting the photocatalytic performance of TiO2‐based Z‐scheme photocatalysts,such as pH,conductive medium,cocatalyst,architecture,and mass ratio,are discussed.Concluding remarks are presented,and some suggestions for the future development of TiO2‐based Z‐scheme photocatalysts are highlighted.
基金the National Natural Science Foundation of China(Nos.51878325,51868050,51622806,51378246 and 51720105001)the Natural Science Foundation of Jiangxi Province(Nos.20162BCB22017,20165BCB18008,20171ACB20017,20133ACB21001 and 20171BAB206049)the Graduate Innovation Fund of Jiangxi Province(No.YC2018-S360)。
文摘Herein,we prepa red novel three-dimensional(3D)gear-s haped Co3O4@C(Co3O4 modified by amorphous carbon)and sheet-like SnO2/CC(SnO2 grow on the carbon cloth)as anode and cathode to achieve efficient removal of 4-nitrophenol(4-NP)in the presence of peroxymonosulfate(PMS)and simultaneous electrocatalytic reduction of CO2,respectively.In this process,4-NP was mineralized into CO2 by the Co3O4@C,and the generated CO2 was reduced into HCOOH by the sheet-like SnO2/CC cathode.Compared with the pure Co0.5(Co3O4 was prepared using 0.5 g urea)with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP(60 mL,10 mg/L)increased from 74.5%-85.1%in 60 min using the Co0.5 modified by amorphous carbon(Co0.5@C).Furthermore,when the voltage of 1.0 V was added in the anodic system of Co0.5@C with PMS(30 mg,0.5 g/L),the degradation efficiency of 4-NP increased from 85.1%-99.1%when Pt was used as cathode.In the experiments of 4-NP degradation coupled with simultaneous electrocatalytic CO2 reduction,the degradation efficiency of 4-NP was 99.0%in the anodic system of Co0.5@C with addition of PMS(30 mg,0.5 g/L),while the Faraday efficiency(FE)of HCOOH was 24.1%at voltage of-1.3 V using the SnO2/CC as cathode.The results showed that the anode of Co3O4 modified by amorphous carbon can markedly improve the degradation efficiency of 4-NP,while the cathode of SnO2/CC can greatly improve the FE and selectivity of CO2 reduction to HCOOH and the stability of cathode.Finally,the promotion mechanism was proposed to explain the degradation of organic pollutants and reduction of CO2 into HCOOH in the process of electrocatalysis coupled with advanced oxidation processes(AOPs)and simultaneous CO2 reduction.
文摘The chemical reduction of CO2 remains a challenge with respect to the reversal of the oxidative degradation of any organic materials. The conversion of CO2 into useful substances is essential in developing alternative fuels and various raw materials for different industries. This also aids in preventing the continuous rise in tropospheric temperature due to the green house effect of CO2. In this article an overview of the growth taken place so far in the field of CO2 chemical reduction is pre- sented. The discussion comprises of photochemical methods for the development of different products, viz. CO, CH3OH and CH4, through chemical reduction of CO2. This includes the use of photo catalysts, mainly TiO2, and the role of a hole scavenger （such as 2-propanol） for this purpose.
基金the National Natural Science Foundation of China(No.21875221,21571157,U1604123,and 21773016)the Youth Talent Support Program of High-Level Talents Special Support Plan in Henan Province(ZYQR201810148)+1 种基金Creative talents in the Education Department of Henan Province(19HASTIT039)the project supported by State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2019-KF-13).
文摘Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.
基金supported by the National Natural Science Foundation of China (No. 41071352)the National Social Science Foundation of China (No. 13BJY030)the National Science and Technology Support Program (No. 2012BAC03B01)
文摘As the biggest iron and steel producer in the world and one of the highest CO2 emission sectors, China’s iron and steel industry is undergoing a low-carbon transition accompanied by remarkable technological progress and investment adjustment, in response to the macroeconomic climate and policy intervention. Many drivers of the CO2 emissions of the iron and steel industry have been explored, but the relationships between CO2 abatement,investment and technological expenditure, and their connections with the economic growth and governmental policies in China, have not been conjointly and empirically examined. We proposed a concise conceptual model and an econometric model to investigate this crucial question. The results of regression, Granger causality test and impulse response analysis indicated that technological expenditure can significantly reduce CO2 emissions, and that investment expansion showed a negative impact on CO2 emission reduction. It was also argued with empirical evidence that a good economic situation favored CO2 abatement in China’s iron and steel industry, while achieving CO2 emission reduction in this industrial sector did not necessarily threaten economic growth.This shed light on the dispute over balancing emission cutting and economic growth.Regarding the policy aspects, the year 2000 was found to be an important turning point for policy evolution and the development of the iron and steel industry in China. The subsequent command and control policies had a significant, positive effect on CO2 abatement.
文摘Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide(ZnO)-based photocatalysts.In this paper,we report the fabrication of graphitic-carbon-mediated ZnO nanorod arrays(NRAs)with enhanced photocatalytic activity and photostability for CO2 reduction under visible light irradiation.ZnO NRA/C-x(x=005,01,02,and 03)nanohybrids are prepared by calcining pre-synthesized ZnO NRAs with different amounts of glucose(0.05,0.1,0.2,and 0.3 g)as a carbon source via a hydrothermal method.X-ray photoelectron spectroscopy reveals that the obtained ZnO NRA/C-x nanohybrids are imparted with the effects of both carbon doping and carbon coating,as evidenced by the detected C-O-Zn bond and the C-C,C-O and C=O bonds,respectively.While the basic structure of ZnO remains unchanged,the UV-Vis absorption spectra show increased absorbance owing to the carbon doping effect in the ZnO NRA/C-x nanohybrids.The photoluminescence(PL)intensities of ZnO NRA/C-x nanohybrids are lower than that of bare ZnO NRA,indicating that the graphitic carbon layer coated on the surface of the ZnO NRA significantly enhances the charge carrier separation and transport,which in turn enhances the photoelectrochemical property and photocatalytic activity of the ZnO NRA/C-x nanohybrids for CO2 reduction.More importantly,a long-term reaction of photocatalytic CO2 reduction demonstrates that the photostability of ZnO NRA/C-x nanohybrids is significantly increased in comparison with the bare ZnO NRA.
基金Project supported by the National Key R&D Program of China(2018YFB0605002)the National Natural Science Foundation of Shanghai(14ZR1417800)。
文摘Highly efficient photocatalytic reduction of CO2 is essential for solving the greenhouse effect and energy crisis.In this paper,the Sm-TiO2 nanocomposites were successfully prepared via sol-gel method.The CO2 photoreduction activities of synthesized samples were tested under irradiation for 6 h and the results indicate that the 0.5% Sm-TiO2 catalyst has superior performance and stability.The CO and CH4 yields of0.5% Sm-TiO2 catalyst are 55.47 and 3.82 μmol/g·cat respectively,which are 5.02 and 2.67 times the yield of TiO2.The possible mechanism of Sm doped TiO2 was investigated through comprehensive characterization and photoetectrochemical analysis,After the Sm doping,the photo-generated electrons in TiO2 could migrate to Sm 4 f,and some of them can be captured by reducing Sm3+ o Sm2+,which can lower the recombination rate of electron and hole pairs.Therefore,the enhanced photocatalytic performance could be ascribed to large specific surface area,fast separation rate of electron-hole pairs and high visible light response.This report provides some meaningful attempts in researching the CO2 photocatalytic reduction.
基金financially supported by the National Natural Science Foundation of China(21802089)Natural Science Foundation of Shandong Province(ZR2019BB015)+5 种基金The Science and Technology Plan of Shandong Province Colleges and Universities under Grant(No.J14LC16)the Natural Science Foundation of Shandong Province under Grant(No.ZR2017MB018)funding support from the Shandong Province Double Hundred Talents Program for Foreign Expertsthe Energy Education Trust of New Zealandthe Dodd Walls Centre for Photonic and Quantum Technologiesthe Mac Diarmid Institute for Advanced Materials and Nanotechnology
文摘Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.
文摘The active site amount of photocatalysts,being the key factors in photocatalytic reactions,directly affects the photocatalytic performance of the photocatalyst.Pristine graphitic carbon nitride(g‐C_(3)N_(4))exhibits moderate photocatalytic activity due to insufficient active sites.In this study,cyano‐modified porous g‐C_(3)N_(4)nanosheets(MCN‐0.5)were synthesized through molecular self‐assembly and alkali‐assisted strategies.The cyano group acted as the active site of the photocatalytic reaction,because the good electron‐withdrawing property of the cyano group promoted carrier separation.Benefiting from the effect of the active sites,MCN‐0.5 exhibited significantly enhanced photocatalytic activity for CO2 reduction under visible light irradiation.Notably,the photocatalytic activity of MCN‐0.5 was significantly reduced when the cyano groups were removed by hydrochloric acid(HCl)treatment,further verifying the role of cyano groups as active sites.The photoreduction of Pt nanoparticles provided an intuitive indication that the introduction of cyano groups provided more active sites for the photocatalytic reaction.Furthermore,the controlled experiments showed that g‐C_(3)N_(4)grafted with cyano groups using melamine as the precursor exhibited enhanced photocatalytic activity,which proved the versatility of the strategy for enhancing the activity of g‐C_(3)N_(4)via cyano group modification.In situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations were used to investigate the mechanism of enhanced photocatalytic activity for CO2 reduction by cyano‐modified g‐C_(3)N_(4).This work provides a promising route for promoting efficient solar energy conversion by designing active sites in photocatalysts.
文摘The electrochemical reduction of CO2(CO2 RR) can substantially contribute to the production of useful chemicals and reduction of global CO2 emissions. Herein, we presented N and S dual-doped high-surface-area carbon materials(SZ-HCN) as CO2 RR catalysts. N and S were doped by one-step pyrolysis of a N-containing polymer and S powder. ZnCl2 was applied as a volatile porogen to prepare porous SZ-HCN. SZ-HCN with a high specific surface area(1510 m2 g–1) exhibited efficient electrocatalytic activity and selectivity for CO2 RR. Electrochemical measurements demonstrated that SZ-HCN showed excellent catalytic performance for CO2-to-CO reduction with a high CO Faradaic efficiency(~93%) at-0.6 V. Furthermore, SZ-HCN offered a stable current density and high CO selectivity over at least 20 h continuous operation, revealing remarkable electrocatalytic durability. The experimental results and density functional theory calculations indicated that N and S dual-doped carbon materials required lower Gibbs free energy to form the COOH* intermediate than that for single-N-doped carbon for CO2-to-CO reduction, thereby enhancing CO2 RR activity.
基金supported by the Fundamental Research Funds for the Central Universities(XK1802-6,XK1902,XK1803-05,12060093063,2312018RC07)the National Natural Science Foundation of China(U1707603,21878008,21625101,20190816)。
文摘Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio from photocatalytic CO2 reduction reaction still poses a great challenge for the further application.Herein,we prepared a series of highly efficient heterostructure based on highly dispersed palladium supported on ultrathin Co Al-layered double hydroxide(LDH).In conjunction with a Ru-complex sensitizer,the molar ratios of CO/H2 can be tuned from 1:0.74 to 1:3 under visible-light irradiation(λ>400 nm).More interestingly,the syngas can be obtained under light irradiation atλ>600 nm.Structure characterization and density functional theory calculations revealed that the remarkable catalytic activity can be due to the supported palladium,which improved the charge transfer efficiency.Meanwhile,more H atoms were used to generate H2 on the supported palladium for further tunable CO/H2 ratio.This work demonstrates a new strategy for harnessing abundant solar-energy to produce syngas from a CO2 feedstock.
