Considering the serious electromagnetic wave(EMW)pollution problems and complex application condition,there is a pressing need to amalgamate multiple functionalities within a single substance.However,the effective int...Considering the serious electromagnetic wave(EMW)pollution problems and complex application condition,there is a pressing need to amalgamate multiple functionalities within a single substance.However,the effective integration of diverse functions into designed EMW absorption materials still faces the huge challenges.Herein,reduced graphene oxide/carbon foams(RGO/CFs)with two-dimensional/three-dimensional(2D/3D)van der Waals(vdWs)heterostructures were meticulously engineered and synthesized utilizing an efficient methodology involving freeze-drying,immersing absorption,secondary freeze-drying,followed by carbonization treatment.Thanks to their excellent linkage effect of amplified dielectric loss and optimized impedance matching,the designed 2D/3D RGO/CFs vdWs heterostructures demonstrated commendable EMW absorption performances,achieving a broad absorption bandwidth of 6.2 GHz and a reflection loss of-50.58 dB with the low matching thicknesses.Furthermore,the obtained 2D/3D RGO/CFs vdWs heterostructures also displayed the significant radar stealth properties,good corrosion resistance performances as well as outstanding thermal insulation capabilities,displaying the great potential in complex and variable environments.Accordingly,this work not only demonstrated a straightforward method for fabricating 2D/3D vdWs heterostructures,but also outlined a powerful mixeddimensional assembly strategy for engineering multifunctional foams for electromagnetic protection,aerospace and other complex conditions.展开更多
Nanostructured gold catalyst supported on metal oxide is highly active for the CO oxidation reac‐tion. In this work, a new type of oxide support, zinc tin oxide, has been used to deposit 0.7 wt%Au via a deposition‐p...Nanostructured gold catalyst supported on metal oxide is highly active for the CO oxidation reac‐tion. In this work, a new type of oxide support, zinc tin oxide, has been used to deposit 0.7 wt%Au via a deposition‐precipitation method. The textural properties of Zn2SnO4 support have been tuned by varying the molar ratio between base (N2H4·H2O) and metal ion (Zn2+) to be 4/1, 8/1 and 16/1. The catalytic tests for CO oxidation reaction revealed that the reactivity on Au‐Zn2SnO4 with N2H4·H2O/Zn2+ = 8/1 was the highest, while the reactivity on Au‐Zn2SnO4 with N2H4·H2O/Zn2+ =16/1 was almost identical to that of the pure support. Both fresh and used catalysts have been characterized by multiple techniques including nitrogen adsorption‐desorption, X‐ray diffraction, transmission electron microscopy, high‐angle annular dark‐field scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, X‐ray adsorption fine structure, and tempera‐ture‐programmed reduction by hydrogen. These demonstrated that the textural properties, espe‐cially pore volume and pore size distribution, of Zn2SnO4 play crucial roles in the averaged size of gold nanoparticles, and thus determine the catalytic activity of Au‐Zn2SnO4 for CO oxidation.展开更多
The high-energy lithium/sulfur(Li/S) battery has become a very popular topic of research in recent years due to its high theoretical capacity of 1672 m Ah/g. However, the polysulfide shuttle effect remains of great co...The high-energy lithium/sulfur(Li/S) battery has become a very popular topic of research in recent years due to its high theoretical capacity of 1672 m Ah/g. However, the polysulfide shuttle effect remains of great concern with a great number of publications dedicated to its mitigation. In this contribution, a three-dimensional(3D) reduced graphene oxide/activated carbon(RGO/AC) film, synthesized by a simple hydrothermal method and convenient mechanical pressing, is sandwiched between the separator and the sulfur-based cathode, acting as a functional interlayer to capture and trap polysulfide species. Consequently, the Li/S cell with this interlayer shows an impressive initial discharge capacity of 1078 m Ah/g and a reversible capacity of 655 m Ah/g even after 100 cycles. The RGO/AC interlayer impedes the movement of polysulfide while providing unimpeded channels for lithium ion mass transfer. Therefore, the RGO/AC interlayer with a well-designed structure represents strong potential for high-performance Li/S batteries.展开更多
The effect of a wide variety of metal oxide (MOx) supports has been discussed for CO oxidation on nanoparticulate gold catalysts. By using typical co‐precipitation and deposition–precipitation methods and under id...The effect of a wide variety of metal oxide (MOx) supports has been discussed for CO oxidation on nanoparticulate gold catalysts. By using typical co‐precipitation and deposition–precipitation methods and under identical calcination conditions, supported gold catalysts were prepared on a wide variety of MOx supports, and the temperature for 50%conversion was measured to qualita‐tively evaluate the catalytic activities of these simple MOx and supported Au catalysts. Furthermore, the difference in these temperatures for the simple MOx compared to the supported Au catalysts is plotted against the metal–oxygen binding energies of the support MOx. A clear volcano‐like correla‐tion between the temperature difference and the metal–oxygen binding energies is observed. This correlation suggests that the use of MOx with appropriate metal–oxygen binding energies (300–500 kJ/atom O) greatly improves the catalytic activity of MOx by the deposition of Au NPs.展开更多
This study was carried out in paddy fields to explore how organic manure applications would affect greenhouse emissions in South China. The results showed that the seasonal emission of CH4 under the chemical fertiliz...This study was carried out in paddy fields to explore how organic manure applications would affect greenhouse emissions in South China. The results showed that the seasonal emission of CH4 under the chemical fertilizer (CF) treatment was 271.47 kg/hm^2. In comparison, the seasonal emissions of CH4 under the treatment of pig manure (PM), chicken manure (CM) and rice straw (RS) increased by 50.61,260.22 and 602.82 kg/hm^2, respectively. N2O emission under the CF treatment was 1.22 kg/hm^2, while the N20 seasonal emissions under tile PM, CM and RS treatment decreased by 23.6% (P〈0.05), 31.7% (P〈0.05) and 30.9% (P〈0.05), respectively. Meanwhile, the readily oxidized organic carbon (which was oxidized by 167 mmol/L potassium permanganate, ROC167) of manure, paddy soil Eh value and temperature could also affect the CH4 emissions. The average yield of the organic fertilizer treatments increased by 6.8% compared with that of the CF treatment. Among all the organic fertilizer treatments, the PM treatment offered the lowest global warming potential and greenhouse gas intensity, in which the PM was of no significant difference from NF (no fertilizing) and CF. Therefore, the pig manure is capable of coordinating the relationship between environment and yield, and it also has a low ROC167 content, so the PM is considered worthy of recommendation.展开更多
Direct carbon solid oxide fuel cells(DC-SOFCs)are promising,green,and efficient power-generating devices that are fueled by solid carbons and comprise all-solid-state structures.Developing suitable anode materials for...Direct carbon solid oxide fuel cells(DC-SOFCs)are promising,green,and efficient power-generating devices that are fueled by solid carbons and comprise all-solid-state structures.Developing suitable anode materials for DC-SOFCs is a substantial scientific challenge.Herein we investigated the use of La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3)-δ−Ce_(0.8)Gd_(0.2)O_(1.9)(LSCM−GDC)composite electrodes as anodes for La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3)-δelectrolyte-based DC-SOFCs,with Camellia oleifera shell char as the carbon fuel.The LSCM−GDC-anode DC-SOFC delivered a maximum power density of 221 mW/cm^(2) at 800℃ and it significantly improved to 425 mW/cm^(2) after Ni nanoparticles were introduced into the LSCM−GDC anode through wet impregnation.The microstructures of the prepared anodes were characterized,and the stability of the anode in a DC-SOFC and the influence of catalytic activity on open circuit voltage were studied.The above results indicate that LSCM–GDC anode is promising to be applied in DC-SOFCs.展开更多
The invasions of the alien species such as Spartina alterniflora along the northern Jiangsu coastlines have posed a threat to biodiversity and the ecosystem function.Yet,limited attention has been given to their poten...The invasions of the alien species such as Spartina alterniflora along the northern Jiangsu coastlines have posed a threat to biodiversity and the ecosystem function.Yet,limited attention has been given to their potential influence on greenhouse gas(GHG) emissions,including the diurnal variations of GHG fluxes that are fundamental in estimating the carbon and nitrogen budget.In this study,we examined the diurnal variation in fluxes of carbon dioxide(CO_2),methane(CH_4),and nitrous oxide(N2O) from a S.alterniflora intertidal flat in June,October,and December of 2013 and April of 2014 representing the summer,autumn,winter,and spring seasons,respectively.We found that the average CH_4 fluxes on the diurnal scale were positive during the growing season while negative otherwise.The tidal flat of S.alterniflora acted as a source of CH_4 in summer(June) and a combination of source and sink in other seasons.We observed higher diurnal variations in the CO_2 and N_2O fluxes during the growing season(1 536.5 mg CO_2 m^(–2) h^(–1) and 25.6 μg N_2O m^(–2) h^(–1)) compared with those measured in the non-growing season(379.1 mg CO_2 m^(–2) h^(–1) and 16.5 μg N_2O m^(–2) h^(–1)).The mean fluxes of CH_4 were higher at night than that in the daytime during all the seasons but October.The diurnal variation in the fluxes of CO_2 in June and N_2O in December fluctuated more than that in October and April.However,two peak curves in October and April were observed for the diurnal changes in CO_2 and N_2O fluxes(prominent peaks were found in the morning of October and in the afternoon of April,respectively).The highest diurnal variation in the N_2O fluxes took place at 15:00(86.4 μg N_2O m^(–2) h^(–1)) in June with an unimodal distribution.Water logging in October increased the emission of CO_2(especially at nighttime),yet decreased N_2O and CH_4 emissions to a different degree on the daily scale because of the restrained diffusion rates of the gases.The seasonal and diurnal variations of CH_4 and CO_2 fluxes did not correlate to the air and soil temperatures,whereas the seasonal and diurnal variation of the fluxes of N_2O in June exhibited a significant correlation with air temperature.When N_2O and CH_4 fluxes were converted to CO_2-e equivalents,the emissions of N_2O had a remarkable potential to impact the global warming.The mean daily flux(MF) and total daily flux(TDF) were higher in the growing season,nevertheless,the MF and TDF of CO_2 were higher in October and those of CH_4 and N_2O were higher in June.In spite of the difference in the optimal sampling times throughout the observation period,our results obtained have implications for sampling and scaling strategies in estimating the GHG fluxes in coastal saline wetlands.展开更多
Poly(amide-6-b-ethylene oxide)(Pebax1657)/1-butyl-3-methylimidazo-lium bis[trifluoromethyl)sulfonyl]-imide([Bmim][Tf2N]) blend membranes with different [Bmim][Tf2N] contents were prepared via solution casting a...Poly(amide-6-b-ethylene oxide)(Pebax1657)/1-butyl-3-methylimidazo-lium bis[trifluoromethyl)sulfonyl]-imide([Bmim][Tf2N]) blend membranes with different [Bmim][Tf2N] contents were prepared via solution casting and solvent evaporation method. The permeation properties of the blend membranes for CO2, N2,CH4 and H2 were studied, and the physical properties were characterized by differential scanning calorimeter(DSC) and X-ray diffraction(XRD). Results showed that [Bmim][Tf2N] was dispersed as amorphous phase in the blend membranes, which caused the decrease of Tg(PE) and crystallinity(PA). With the addition of [Bmim][Tf2N], the CO2 permeability increased and reached up to approximately 286 Barrer at 40 wt%[Bmim][Tf2N], which was nearly double that of pristine Pebax1657 membrane. The increase of CO2 permeability may be attributed to high intrinsic permeability of [Bmim][Tf2N], the increase of fractional free of volume(FFV) and plasticization effect. However, the CO2 permeability reduced firstly when the [Bmim][Tf2N]content was below 10 wt%, which may be due to that the small ions of [Bmim][Tf2N] in the gap of polymer chain inhibited the flexibility of polymer chain; the interaction between Pebax1657 and [Bmim][Tf2N]decreased the content of EO units available for CO2 transport and led to a more compact structure. For Pebax1657/[Bmim][Tf2N] blend membranes, the permeabilities of N2, H2 and CH4decreased with the increase of feed pressure due to the hydrostatic pressure effect, while CO2 permeability increased with the increase of feed pressure for that the CO2-induced plasticization effect was stronger than hydrostatic pressure effect.展开更多
Based on the basis of analysis and interpretation of the products distribution of catalytic cracking of high acidic crude, the mechanism for decarboxylation of petroleum acids during FCC process was discussed. The pro...Based on the basis of analysis and interpretation of the products distribution of catalytic cracking of high acidic crude, the mechanism for decarboxylation of petroleum acids during FCC process was discussed. The protons originated from the Bronsted acid sites can combine with oxygen of the carbonyl groups with more negative charges to form reaction intermediates that can be subjected to cleavage at the weak bonds, leading to breaking of carboxylic groups from the carboxylic acids followed by its decomposition to form alkyl three-coordinated carbenium ions, CO and H2O. The Lewis acid as an electrophilic reagent can abstract carboxylic groups from carboxylic acids to subsequently release CO2.展开更多
The rare earth elements(REE)geochemistry and the isotope(δ^(13)C,δ^(18)O)composition of manganese ores of the Chiatura(Georgia)deposit were studied.One of the major features of all types of manganese ores is negativ...The rare earth elements(REE)geochemistry and the isotope(δ^(13)C,δ^(18)O)composition of manganese ores of the Chiatura(Georgia)deposit were studied.One of the major features of all types of manganese ores is negative cerium(Ce/Ce*_(PAAS))anomaly and the absence of europium(Eu/Eu*_(PAAS))anomaly.Oxide oolitic manganese ores were formed in oxic shallow marine environments.The content and distribution of REEs(in particular Ce and Eu)in these ores are connected mainly with ferrous oxides.The performed C-and O-isotope research in Mn-carbonates(oolitic and massive)has indicated that carbonate ores were formed by the participation of isotopic ally light CO_(2)which is a result of the oxidation of organic matter in the sediment strata by reducing environments of early diagenesis(and,partially,catagenesis)zone.Obtained negative cerium anomalies in the studied carbonate ores reflect the specific REE patterns in pore waters of sediments of earlier isdiagenesis zone of the Oligocene Chiatura's basin.The deficiency of cerium in this zone remains debatable and requires further study.Formation of manganese carbonates took place multistage by the input of incisional solutions of different chemistry into sea bottom waters and sediments.The absence of europium anomaly indicates about lack of hydrothermal solution input.展开更多
CO oxidation is probably the most studied reaction in heterogeneous catalysis.This reaction has become a hot topic with the discovery of nanogold catalysts,which are active at low temperatures(at or below room temper...CO oxidation is probably the most studied reaction in heterogeneous catalysis.This reaction has become a hot topic with the discovery of nanogold catalysts,which are active at low temperatures(at or below room temperature).Au catalysts are the benchmark for judging the activities of other metals in CO oxidation.Pt-group metals(PGMs) that give comparable performances are of particular interest.In this mini-review,we summarize the advances in various PGM(Pt,Pd,Ir,Rh,Ru)catalysts that have high catalytic activities in low-temperature CO oxidation arising from reducible supports or the presence of OH species.The effects of the size of the metal species and the importance of the interface between the metal and the reducible support are covered and discussed in terms of their promotional role in CO oxidation at low temperatures.展开更多
TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties ...TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties of the catalysts were studied by N2 adsorption-desorption,X-ray diffraction,transmission electron microscopy,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy,H2 temperature-programmed reduction and Fourier transform infrared spectroscopy.TiO2/γ-Al2O3 supported In/Ag is a good catalyst for the reduction of NO to N2.It displayed high dispersion,large amounts of surface active components and high NO adsorption capacity,which gave good catalytic performance and stability for the reduction of NO with CO under lean burn conditions.The silver species stabilized and improved the dispersion of the indium species.The introduction of TiO2 into the γ-Al2O3 support promoted NO adsorption and improved the dispersion of the indium species and silver species.展开更多
A molten salt method was developed to prepare porous La1‐xSrxMn0.8Fe0.2O3 (0≤ x ≤ 0.6) micro‐spheres using hierarchical porous δ‐MnO2 microspheres as a template in eutectic NaNO3‐KNO3. X‐ray diffraction patt...A molten salt method was developed to prepare porous La1‐xSrxMn0.8Fe0.2O3 (0≤ x ≤ 0.6) micro‐spheres using hierarchical porous δ‐MnO2 microspheres as a template in eutectic NaNO3‐KNO3. X‐ray diffraction patterns showed that single phase LaMn0.8Fe0.2O3 with good crystallinity was syn‐thesized at 450℃ after 4 h. Transmission electron microscope images exhibited that the LaMn0.8Fe0.2O3 sample obtained at 450?? after 4 h possessed a porous spherical morphology com‐posed of aggregated nanocrystallites. Field emission scanning electron microscope images indicated that the growth of the porous LaMn0.8Fe0.2O3 microspheres has two stages. SEM pictures showed that a higher calcination temperature than 450?? had an adverse effect on the formation of a po‐rous spherical structure. The LaMn0.8Fe0.2O3 sample obtained at 450?? after 4 h displayed a high BET surface area of 55.73 m2/g with a pore size of 9.38 nm. Fourier transform infrared spectra suggested that Sr2+ions entered the A sites and induced a decrease of the binding energy between Mn and O. The CO conversion with the La1‐xSrxMn0.8Fe0.2O3 (0≤x≤0.6) samples indicated that the La0.4Sr0.6Mn0.8Fe0.2O3 sample had the best catalytic activity and stability. Further analysis by X‐ray photoelectron spectroscopy demonstrated that Sr2+doping altered the content of Mn4+ions, oxygen vacancies and adsorbed oxygen species on the surface, which affected the catalytic performance for CO oxidation.展开更多
We have designed and prepared β-cyclodextrin (β-CD)-functionalized multi-walled nanotubes (MWCNTs-g-CD) for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effec...We have designed and prepared β-cyclodextrin (β-CD)-functionalized multi-walled nanotubes (MWCNTs-g-CD) for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effect of combining MWCNTs with β-CD led to a remarkable increase in the performance of the MWCNTs-g-CD for the catalytic oxidation of cinnamaldehyde, which exhibited 95% cinnamaldehyde conversion and 85% selectivity to natural benzaldehyde with a short reaction time of 10 rain. The MWCNTs-g-CD also exhibited outstanding recyclability with good stability, showing no discernible decrease in their catalytic activity over five reaction cycles.展开更多
It is crucial to understand the mechanism of low temperature CO oxidation reaction catalyzed by gold nanoparticles so as to find out the origin of the high catalytic reactivity and extend the indus‐trialization appli...It is crucial to understand the mechanism of low temperature CO oxidation reaction catalyzed by gold nanoparticles so as to find out the origin of the high catalytic reactivity and extend the indus‐trialization applications of nano gold catalysts. In this work, some theoretical works on CO adsorp‐tion, O2 adsorption, atomic oxygen adsorption, formation of surface gold oxide films, reaction mechanisms of CO oxidation involving O2 reaction with CO and O2 dissociation before reacting with CO on gold surfaces and Au/metal oxide were summarized, and the influences of coordination number, charge transfer and relativity of gold on CO oxidation reaction were briefly reviewed. It was found that CO reaction mechanism depended on the systems with or without oxide and the strong relativistic effects might play an important role in CO oxidation reaction on gold catalysts. In particular, the relativistic effects are related to the unique behaviors of CO adsorption, O adsorption, O2 activation on gold surfaces, effects of coordination number and the wide gap between the chem‐ical inertness of bulk gold and high catalytic activity of nano gold. The present work helps us to understand the CO oxidation reaction mechanism on gold catalysts and the influence of relativistic effects on gold catalysis.展开更多
Developing efficient supported Pd catalysts and understanding their catalytic mechanism in CO oxidation are challenging research topics in recent years.This paper describes the synthesis of Pd nanoparticles supported ...Developing efficient supported Pd catalysts and understanding their catalytic mechanism in CO oxidation are challenging research topics in recent years.This paper describes the synthesis of Pd nanoparticles supported on CeO2 nanotubes via an alcohol reduction method.The effect of the support morphology on the catalytic reaction was explored.Subsequently,the performance of the prepared catalysts was investigated toward CO oxidation reaction and characterized by Nitrogen sorption,X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,and CO-temperature-programmed desorption techniques.The results indicated that the catalyst of Pd on CeO2 nanotubes exhibits excellent activity in CO oxidation at low temperatures,due to its large surface area,the high dispersion of Pd species,the mesoporous and tubular structure of the CeO2-nanotube support,the abundant Ce3+,formation of Pd–O–Ce bonding,and enhanced metal–support interaction on the catalyst surface.展开更多
This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hy...This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies(i.e.,nanorods,nanosheets,and nanocubes) were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures(≤ 140℃).Nanorods can be synthesized in CoCl2 solution,while Co(NO3)2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature(higher than 140 ℃) results in the formation of nanocubes in either Co(NO3)2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^(3+) on the surface,much higher reducibility,and better oxygen desorption capacity.展开更多
The physicochemical properties of nanosized Au catalysts supported on doped CeO2 and their cata‐lytic performance for the CO oxidation reaction were investigated. The Au/Zr‐doped CeO2 catalyst is much more active th...The physicochemical properties of nanosized Au catalysts supported on doped CeO2 and their cata‐lytic performance for the CO oxidation reaction were investigated. The Au/Zr‐doped CeO2 catalyst is much more active than undoped Au/CeO2, while Au/ZrLa‐doped CeO2 shows the highest activity. Characterization of the catalysts by X‐ray diffraction, transmission electron microscopy (TEM), high‐resolution TEM, and the X‐ray absorption fine structure technique shows high homogeneity of the oxide supports and well‐dispersed nanosized Au nanoparticles. Raman spectroscopy, X‐ray photoelectron spectroscopy, and H2‐tempeature‐programmed reduction show that the surface oxygen species are the main factor for the catalytic activity in the CO oxidation reaction, while the supported Au species can improve the redox properties and create oxygen vacancy sites on the support. The oxidation state of Au is not the main factor governing the activity of Au/doped‐CeO2 catalysts. Additionally, the synergistic effect of Zr and La is discussed.展开更多
A photocatalyst composed of TiO 2 nanotube arrays(TNTs) and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was ...A photocatalyst composed of TiO 2 nanotube arrays(TNTs) and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time(5 min) resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time(45 min) gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.展开更多
基金provided by Guizhou Provincial Science and Technology Projects for Platform and Talent Team Plan(GCC[2023]007)Fok Ying Tung Education Foundation(171095)National Natural Science Foundation of China(11964006).
文摘Considering the serious electromagnetic wave(EMW)pollution problems and complex application condition,there is a pressing need to amalgamate multiple functionalities within a single substance.However,the effective integration of diverse functions into designed EMW absorption materials still faces the huge challenges.Herein,reduced graphene oxide/carbon foams(RGO/CFs)with two-dimensional/three-dimensional(2D/3D)van der Waals(vdWs)heterostructures were meticulously engineered and synthesized utilizing an efficient methodology involving freeze-drying,immersing absorption,secondary freeze-drying,followed by carbonization treatment.Thanks to their excellent linkage effect of amplified dielectric loss and optimized impedance matching,the designed 2D/3D RGO/CFs vdWs heterostructures demonstrated commendable EMW absorption performances,achieving a broad absorption bandwidth of 6.2 GHz and a reflection loss of-50.58 dB with the low matching thicknesses.Furthermore,the obtained 2D/3D RGO/CFs vdWs heterostructures also displayed the significant radar stealth properties,good corrosion resistance performances as well as outstanding thermal insulation capabilities,displaying the great potential in complex and variable environments.Accordingly,this work not only demonstrated a straightforward method for fabricating 2D/3D vdWs heterostructures,but also outlined a powerful mixeddimensional assembly strategy for engineering multifunctional foams for electromagnetic protection,aerospace and other complex conditions.
基金supported by the National Natural Science Foundation of China (21373259, 21301107)the Hundred Talents Project of the Chinese Academy of Sciences, the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA09030102)+2 种基金the Open Funding from Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciencesthe Fundamental Research Fund-ing of Shandong University (2014JC005)the Taishan Scholar Project of Shandong Province (China)~~
文摘Nanostructured gold catalyst supported on metal oxide is highly active for the CO oxidation reac‐tion. In this work, a new type of oxide support, zinc tin oxide, has been used to deposit 0.7 wt%Au via a deposition‐precipitation method. The textural properties of Zn2SnO4 support have been tuned by varying the molar ratio between base (N2H4·H2O) and metal ion (Zn2+) to be 4/1, 8/1 and 16/1. The catalytic tests for CO oxidation reaction revealed that the reactivity on Au‐Zn2SnO4 with N2H4·H2O/Zn2+ = 8/1 was the highest, while the reactivity on Au‐Zn2SnO4 with N2H4·H2O/Zn2+ =16/1 was almost identical to that of the pure support. Both fresh and used catalysts have been characterized by multiple techniques including nitrogen adsorption‐desorption, X‐ray diffraction, transmission electron microscopy, high‐angle annular dark‐field scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, X‐ray adsorption fine structure, and tempera‐ture‐programmed reduction by hydrogen. These demonstrated that the textural properties, espe‐cially pore volume and pore size distribution, of Zn2SnO4 play crucial roles in the averaged size of gold nanoparticles, and thus determine the catalytic activity of Au‐Zn2SnO4 for CO oxidation.
基金financial support from the National Natural Science Foundation of China(grant no.21406052the Program for the Outstanding Young Talents of Hebei Province(grant no.BJ2014010)the Scientific Research Foundation for Selected Overseas Chinese Scholars,Ministry of Human Resources and Social Security of China(grant no.CG2015003002)
文摘The high-energy lithium/sulfur(Li/S) battery has become a very popular topic of research in recent years due to its high theoretical capacity of 1672 m Ah/g. However, the polysulfide shuttle effect remains of great concern with a great number of publications dedicated to its mitigation. In this contribution, a three-dimensional(3D) reduced graphene oxide/activated carbon(RGO/AC) film, synthesized by a simple hydrothermal method and convenient mechanical pressing, is sandwiched between the separator and the sulfur-based cathode, acting as a functional interlayer to capture and trap polysulfide species. Consequently, the Li/S cell with this interlayer shows an impressive initial discharge capacity of 1078 m Ah/g and a reversible capacity of 655 m Ah/g even after 100 cycles. The RGO/AC interlayer impedes the movement of polysulfide while providing unimpeded channels for lithium ion mass transfer. Therefore, the RGO/AC interlayer with a well-designed structure represents strong potential for high-performance Li/S batteries.
文摘The effect of a wide variety of metal oxide (MOx) supports has been discussed for CO oxidation on nanoparticulate gold catalysts. By using typical co‐precipitation and deposition–precipitation methods and under identical calcination conditions, supported gold catalysts were prepared on a wide variety of MOx supports, and the temperature for 50%conversion was measured to qualita‐tively evaluate the catalytic activities of these simple MOx and supported Au catalysts. Furthermore, the difference in these temperatures for the simple MOx compared to the supported Au catalysts is plotted against the metal–oxygen binding energies of the support MOx. A clear volcano‐like correla‐tion between the temperature difference and the metal–oxygen binding energies is observed. This correlation suggests that the use of MOx with appropriate metal–oxygen binding energies (300–500 kJ/atom O) greatly improves the catalytic activity of MOx by the deposition of Au NPs.
文摘This study was carried out in paddy fields to explore how organic manure applications would affect greenhouse emissions in South China. The results showed that the seasonal emission of CH4 under the chemical fertilizer (CF) treatment was 271.47 kg/hm^2. In comparison, the seasonal emissions of CH4 under the treatment of pig manure (PM), chicken manure (CM) and rice straw (RS) increased by 50.61,260.22 and 602.82 kg/hm^2, respectively. N2O emission under the CF treatment was 1.22 kg/hm^2, while the N20 seasonal emissions under tile PM, CM and RS treatment decreased by 23.6% (P〈0.05), 31.7% (P〈0.05) and 30.9% (P〈0.05), respectively. Meanwhile, the readily oxidized organic carbon (which was oxidized by 167 mmol/L potassium permanganate, ROC167) of manure, paddy soil Eh value and temperature could also affect the CH4 emissions. The average yield of the organic fertilizer treatments increased by 6.8% compared with that of the CF treatment. Among all the organic fertilizer treatments, the PM treatment offered the lowest global warming potential and greenhouse gas intensity, in which the PM was of no significant difference from NF (no fertilizing) and CF. Therefore, the pig manure is capable of coordinating the relationship between environment and yield, and it also has a low ROC167 content, so the PM is considered worthy of recommendation.
基金Project(2019YFC1907405)supported by the National Key R&D Program of ChinaProject(GJJ200809)supported by the Education Department Project Fund of Jiangxi Province,ChinaProject(2020BAB214021)supported by the Natural Science Foundation of Jiangxi Province,China。
文摘Direct carbon solid oxide fuel cells(DC-SOFCs)are promising,green,and efficient power-generating devices that are fueled by solid carbons and comprise all-solid-state structures.Developing suitable anode materials for DC-SOFCs is a substantial scientific challenge.Herein we investigated the use of La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3)-δ−Ce_(0.8)Gd_(0.2)O_(1.9)(LSCM−GDC)composite electrodes as anodes for La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3)-δelectrolyte-based DC-SOFCs,with Camellia oleifera shell char as the carbon fuel.The LSCM−GDC-anode DC-SOFC delivered a maximum power density of 221 mW/cm^(2) at 800℃ and it significantly improved to 425 mW/cm^(2) after Ni nanoparticles were introduced into the LSCM−GDC anode through wet impregnation.The microstructures of the prepared anodes were characterized,and the stability of the anode in a DC-SOFC and the influence of catalytic activity on open circuit voltage were studied.The above results indicate that LSCM–GDC anode is promising to be applied in DC-SOFCs.
基金The National Basic Research Program of China under contract No.2013CB956503the State Oceanic Administration People’s Republic of China under contract No.201005006the National Natural Science Foundation of China under contract No.41471413
文摘The invasions of the alien species such as Spartina alterniflora along the northern Jiangsu coastlines have posed a threat to biodiversity and the ecosystem function.Yet,limited attention has been given to their potential influence on greenhouse gas(GHG) emissions,including the diurnal variations of GHG fluxes that are fundamental in estimating the carbon and nitrogen budget.In this study,we examined the diurnal variation in fluxes of carbon dioxide(CO_2),methane(CH_4),and nitrous oxide(N2O) from a S.alterniflora intertidal flat in June,October,and December of 2013 and April of 2014 representing the summer,autumn,winter,and spring seasons,respectively.We found that the average CH_4 fluxes on the diurnal scale were positive during the growing season while negative otherwise.The tidal flat of S.alterniflora acted as a source of CH_4 in summer(June) and a combination of source and sink in other seasons.We observed higher diurnal variations in the CO_2 and N_2O fluxes during the growing season(1 536.5 mg CO_2 m^(–2) h^(–1) and 25.6 μg N_2O m^(–2) h^(–1)) compared with those measured in the non-growing season(379.1 mg CO_2 m^(–2) h^(–1) and 16.5 μg N_2O m^(–2) h^(–1)).The mean fluxes of CH_4 were higher at night than that in the daytime during all the seasons but October.The diurnal variation in the fluxes of CO_2 in June and N_2O in December fluctuated more than that in October and April.However,two peak curves in October and April were observed for the diurnal changes in CO_2 and N_2O fluxes(prominent peaks were found in the morning of October and in the afternoon of April,respectively).The highest diurnal variation in the N_2O fluxes took place at 15:00(86.4 μg N_2O m^(–2) h^(–1)) in June with an unimodal distribution.Water logging in October increased the emission of CO_2(especially at nighttime),yet decreased N_2O and CH_4 emissions to a different degree on the daily scale because of the restrained diffusion rates of the gases.The seasonal and diurnal variations of CH_4 and CO_2 fluxes did not correlate to the air and soil temperatures,whereas the seasonal and diurnal variation of the fluxes of N_2O in June exhibited a significant correlation with air temperature.When N_2O and CH_4 fluxes were converted to CO_2-e equivalents,the emissions of N_2O had a remarkable potential to impact the global warming.The mean daily flux(MF) and total daily flux(TDF) were higher in the growing season,nevertheless,the MF and TDF of CO_2 were higher in October and those of CH_4 and N_2O were higher in June.In spite of the difference in the optimal sampling times throughout the observation period,our results obtained have implications for sampling and scaling strategies in estimating the GHG fluxes in coastal saline wetlands.
基金supported by the National High Technology Research and Development Program of China(863 Program)(No.2012AA03A611)
文摘Poly(amide-6-b-ethylene oxide)(Pebax1657)/1-butyl-3-methylimidazo-lium bis[trifluoromethyl)sulfonyl]-imide([Bmim][Tf2N]) blend membranes with different [Bmim][Tf2N] contents were prepared via solution casting and solvent evaporation method. The permeation properties of the blend membranes for CO2, N2,CH4 and H2 were studied, and the physical properties were characterized by differential scanning calorimeter(DSC) and X-ray diffraction(XRD). Results showed that [Bmim][Tf2N] was dispersed as amorphous phase in the blend membranes, which caused the decrease of Tg(PE) and crystallinity(PA). With the addition of [Bmim][Tf2N], the CO2 permeability increased and reached up to approximately 286 Barrer at 40 wt%[Bmim][Tf2N], which was nearly double that of pristine Pebax1657 membrane. The increase of CO2 permeability may be attributed to high intrinsic permeability of [Bmim][Tf2N], the increase of fractional free of volume(FFV) and plasticization effect. However, the CO2 permeability reduced firstly when the [Bmim][Tf2N]content was below 10 wt%, which may be due to that the small ions of [Bmim][Tf2N] in the gap of polymer chain inhibited the flexibility of polymer chain; the interaction between Pebax1657 and [Bmim][Tf2N]decreased the content of EO units available for CO2 transport and led to a more compact structure. For Pebax1657/[Bmim][Tf2N] blend membranes, the permeabilities of N2, H2 and CH4decreased with the increase of feed pressure due to the hydrostatic pressure effect, while CO2 permeability increased with the increase of feed pressure for that the CO2-induced plasticization effect was stronger than hydrostatic pressure effect.
文摘Based on the basis of analysis and interpretation of the products distribution of catalytic cracking of high acidic crude, the mechanism for decarboxylation of petroleum acids during FCC process was discussed. The protons originated from the Bronsted acid sites can combine with oxygen of the carbonyl groups with more negative charges to form reaction intermediates that can be subjected to cleavage at the weak bonds, leading to breaking of carboxylic groups from the carboxylic acids followed by its decomposition to form alkyl three-coordinated carbenium ions, CO and H2O. The Lewis acid as an electrophilic reagent can abstract carboxylic groups from carboxylic acids to subsequently release CO2.
基金accomplished in accordance with the Research Program of the Geological Institute of the Russian Academy of Sciences。
文摘The rare earth elements(REE)geochemistry and the isotope(δ^(13)C,δ^(18)O)composition of manganese ores of the Chiatura(Georgia)deposit were studied.One of the major features of all types of manganese ores is negative cerium(Ce/Ce*_(PAAS))anomaly and the absence of europium(Eu/Eu*_(PAAS))anomaly.Oxide oolitic manganese ores were formed in oxic shallow marine environments.The content and distribution of REEs(in particular Ce and Eu)in these ores are connected mainly with ferrous oxides.The performed C-and O-isotope research in Mn-carbonates(oolitic and massive)has indicated that carbonate ores were formed by the participation of isotopic ally light CO_(2)which is a result of the oxidation of organic matter in the sediment strata by reducing environments of early diagenesis(and,partially,catagenesis)zone.Obtained negative cerium anomalies in the studied carbonate ores reflect the specific REE patterns in pore waters of sediments of earlier isdiagenesis zone of the Oligocene Chiatura's basin.The deficiency of cerium in this zone remains debatable and requires further study.Formation of manganese carbonates took place multistage by the input of incisional solutions of different chemistry into sea bottom waters and sediments.The absence of europium anomaly indicates about lack of hydrothermal solution input.
基金supported by the National Natural Science Foundation of China(21076211,21203181,21576251,21676269)the "Strategic Priority Research Program" of the Chinese Academy of Sciences(XDB17020100)+1 种基金the National Key projects for Fundamental Research and Development of China(2016YFA0202801)Department of Science and Technology of Liaoning Province under contract of 2015020086-101~~
文摘CO oxidation is probably the most studied reaction in heterogeneous catalysis.This reaction has become a hot topic with the discovery of nanogold catalysts,which are active at low temperatures(at or below room temperature).Au catalysts are the benchmark for judging the activities of other metals in CO oxidation.Pt-group metals(PGMs) that give comparable performances are of particular interest.In this mini-review,we summarize the advances in various PGM(Pt,Pd,Ir,Rh,Ru)catalysts that have high catalytic activities in low-temperature CO oxidation arising from reducible supports or the presence of OH species.The effects of the size of the metal species and the importance of the interface between the metal and the reducible support are covered and discussed in terms of their promotional role in CO oxidation at low temperatures.
基金supported by the National Science & Technology Pillar Program(2012BAF03B02)National Natural Science Foundation of China(21101085,U1162203)+3 种基金Natural Science Foundation of Liaoning Province(2015020196)Doctoral Fund of Shandong Province(BS2015HZ003)Fushun Science & Technology Program(FSKJHT 201423)Liaoning Excellent Talents Program in University(LJQ2012031)~~
文摘TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties of the catalysts were studied by N2 adsorption-desorption,X-ray diffraction,transmission electron microscopy,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy,H2 temperature-programmed reduction and Fourier transform infrared spectroscopy.TiO2/γ-Al2O3 supported In/Ag is a good catalyst for the reduction of NO to N2.It displayed high dispersion,large amounts of surface active components and high NO adsorption capacity,which gave good catalytic performance and stability for the reduction of NO with CO under lean burn conditions.The silver species stabilized and improved the dispersion of the indium species.The introduction of TiO2 into the γ-Al2O3 support promoted NO adsorption and improved the dispersion of the indium species and silver species.
基金supported by the National Science Foundation for Young Scientists of China (51202171)~~
文摘A molten salt method was developed to prepare porous La1‐xSrxMn0.8Fe0.2O3 (0≤ x ≤ 0.6) micro‐spheres using hierarchical porous δ‐MnO2 microspheres as a template in eutectic NaNO3‐KNO3. X‐ray diffraction patterns showed that single phase LaMn0.8Fe0.2O3 with good crystallinity was syn‐thesized at 450℃ after 4 h. Transmission electron microscope images exhibited that the LaMn0.8Fe0.2O3 sample obtained at 450?? after 4 h possessed a porous spherical morphology com‐posed of aggregated nanocrystallites. Field emission scanning electron microscope images indicated that the growth of the porous LaMn0.8Fe0.2O3 microspheres has two stages. SEM pictures showed that a higher calcination temperature than 450?? had an adverse effect on the formation of a po‐rous spherical structure. The LaMn0.8Fe0.2O3 sample obtained at 450?? after 4 h displayed a high BET surface area of 55.73 m2/g with a pore size of 9.38 nm. Fourier transform infrared spectra suggested that Sr2+ions entered the A sites and induced a decrease of the binding energy between Mn and O. The CO conversion with the La1‐xSrxMn0.8Fe0.2O3 (0≤x≤0.6) samples indicated that the La0.4Sr0.6Mn0.8Fe0.2O3 sample had the best catalytic activity and stability. Further analysis by X‐ray photoelectron spectroscopy demonstrated that Sr2+doping altered the content of Mn4+ions, oxygen vacancies and adsorbed oxygen species on the surface, which affected the catalytic performance for CO oxidation.
基金supported by the National Natural Science Foundation of China (21376279, 21276102, 21425627)Guangdong Technology Research Center for Synthesis and Separation of Thermosensitive Chemicals (2015B090903061)+1 种基金the Fundamental Research Funds for the Central Universities (14lgpy28)Guangzhou Science and Technology Plan Projects (2014J4100125)~~
文摘We have designed and prepared β-cyclodextrin (β-CD)-functionalized multi-walled nanotubes (MWCNTs-g-CD) for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effect of combining MWCNTs with β-CD led to a remarkable increase in the performance of the MWCNTs-g-CD for the catalytic oxidation of cinnamaldehyde, which exhibited 95% cinnamaldehyde conversion and 85% selectivity to natural benzaldehyde with a short reaction time of 10 rain. The MWCNTs-g-CD also exhibited outstanding recyclability with good stability, showing no discernible decrease in their catalytic activity over five reaction cycles.
基金supported by the National Natural Science Foundation of China (21103165)
文摘It is crucial to understand the mechanism of low temperature CO oxidation reaction catalyzed by gold nanoparticles so as to find out the origin of the high catalytic reactivity and extend the indus‐trialization applications of nano gold catalysts. In this work, some theoretical works on CO adsorp‐tion, O2 adsorption, atomic oxygen adsorption, formation of surface gold oxide films, reaction mechanisms of CO oxidation involving O2 reaction with CO and O2 dissociation before reacting with CO on gold surfaces and Au/metal oxide were summarized, and the influences of coordination number, charge transfer and relativity of gold on CO oxidation reaction were briefly reviewed. It was found that CO reaction mechanism depended on the systems with or without oxide and the strong relativistic effects might play an important role in CO oxidation reaction on gold catalysts. In particular, the relativistic effects are related to the unique behaviors of CO adsorption, O adsorption, O2 activation on gold surfaces, effects of coordination number and the wide gap between the chem‐ical inertness of bulk gold and high catalytic activity of nano gold. The present work helps us to understand the CO oxidation reaction mechanism on gold catalysts and the influence of relativistic effects on gold catalysis.
基金supported by the National Natural Science Foundation of China(21376209,21376169)Zhejiang Provincial Natural Science Foundation(LZ13B060004)+1 种基金Program for Zhejiang Leading Team of S&T Innovation(2013TD07)Program of Introducing Talents of Discipline to Universities(B06006)~~
文摘Developing efficient supported Pd catalysts and understanding their catalytic mechanism in CO oxidation are challenging research topics in recent years.This paper describes the synthesis of Pd nanoparticles supported on CeO2 nanotubes via an alcohol reduction method.The effect of the support morphology on the catalytic reaction was explored.Subsequently,the performance of the prepared catalysts was investigated toward CO oxidation reaction and characterized by Nitrogen sorption,X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,and CO-temperature-programmed desorption techniques.The results indicated that the catalyst of Pd on CeO2 nanotubes exhibits excellent activity in CO oxidation at low temperatures,due to its large surface area,the high dispersion of Pd species,the mesoporous and tubular structure of the CeO2-nanotube support,the abundant Ce3+,formation of Pd–O–Ce bonding,and enhanced metal–support interaction on the catalyst surface.
基金supported by the National Natural Science Foundation of China (51374004,51204083)the Candidate Talents Training Fund of Yun-nan Province (2012HB009,2014HB006)+2 种基金the Applied Basic Research Program of Yunnan Province (2014FB123)a School-Enterprise Cooperation Project from Jinchuan Corporation (Jinchuan 201115)the Talents Training Program of Kunming University of Science and Technology (KKZ3201352038)~~
文摘This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies(i.e.,nanorods,nanosheets,and nanocubes) were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures(≤ 140℃).Nanorods can be synthesized in CoCl2 solution,while Co(NO3)2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature(higher than 140 ℃) results in the formation of nanocubes in either Co(NO3)2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^(3+) on the surface,much higher reducibility,and better oxygen desorption capacity.
基金supported by the National Natural Science Foundation of China (21301107,21373259)~~
文摘The physicochemical properties of nanosized Au catalysts supported on doped CeO2 and their cata‐lytic performance for the CO oxidation reaction were investigated. The Au/Zr‐doped CeO2 catalyst is much more active than undoped Au/CeO2, while Au/ZrLa‐doped CeO2 shows the highest activity. Characterization of the catalysts by X‐ray diffraction, transmission electron microscopy (TEM), high‐resolution TEM, and the X‐ray absorption fine structure technique shows high homogeneity of the oxide supports and well‐dispersed nanosized Au nanoparticles. Raman spectroscopy, X‐ray photoelectron spectroscopy, and H2‐tempeature‐programmed reduction show that the surface oxygen species are the main factor for the catalytic activity in the CO oxidation reaction, while the supported Au species can improve the redox properties and create oxygen vacancy sites on the support. The oxidation state of Au is not the main factor governing the activity of Au/doped‐CeO2 catalysts. Additionally, the synergistic effect of Zr and La is discussed.
基金supported by the National Natural Science Foundation of China(2137704421573085)+5 种基金the Key Project of Natural Science Foundation of Hubei Province(2015CFA037)Wuhan Planning Project of Science and Technology(2014010101010023)Self-determined Research Funds of CCNU from the Colleges’Basic Research and Operation of MOE(CCNU15ZD007CCNU15KFY005)China Postdoctoral Science Foundation(2015M572187)Hubei Provincial Department of Education(D20152702)~~
文摘A photocatalyst composed of TiO 2 nanotube arrays(TNTs) and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time(5 min) resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time(45 min) gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.