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1.
Photocatalytic reduction of CO2 using solar energy to decrease CO2 emission is a promising clean renewable fuel production technology. Recently, Bi-based semiconductors with excellent photocatalytic activity and carbon-based carriers with large specific surface areas and strong CO2 adsorption capacity have attracted extensive attention. In this study, activated carbon spheres (ACSs) were obtained via carbonization and steam activation of phenolic resin-based carbon spheres at 850 °C synthesized by suspension polymerization. Then, the BiOBr/ACSs sample was successfully prepared via a simple impregnation method. The as-prepared samples were characterized by XRD, SEM, EDX, DRS, PL, EIS, XPS, BET, CO2 adsorption isotherm and CO2-TPD. The BiOBr and BiOBr/ACSs samples exhibited high CO selectivity for photocatalytic CO2 reduction, and BiOBr/ACSs achieved a rather higher photocatalytic activity (23.74 μmol g−1 h−1) than BiOBr (2.39 μmol g−1 h−1) under simulated sunlight irradiation. Moreover, the analysis of the obtained results indicates that in this photocatalyst system, due to their higher micropore surface area and larger micropore volume, ACSs provide enough physical adsorption sites for CO2 adsorption, and the intrinsic structure of ACSs can offer effective electron transfer ability for a fast and efficient separation of photo-induced electron–hole pairs. Finally, a possible enhanced photocatalytic mechanism of BiOBr/ACSs was investigated and proposed. Our findings should provide new and important research ideas for the construction of highly efficient photocatalyst systems for the reduction of CO2 to solar fuels and chemicals.

Photocatalytic reduction of CO2 using solar energy to decrease CO2 emission is a promising clean renewable fuel production technology.  相似文献   

2.
A series of core@shell SrTiO3@NiFe LDH composites (STONFs) were synthesized and their photocatalytic CO2 reduction performance was studied. The photocatalyst STONF 2 exhibited enhanced CO2 reduction performance with CO yield of 7.9 μmol g−1 h−1. The yield was 25.7 times and 8.8 times higher than that of NiFe LDH and SrTiO3 respectively, and also higher than most LDH based photocatalysts. Compared with two individual components, STONFs exhibited their combined merits of widened absorption spectrum, higher transportation efficiency and alleviated recombination of e/h+ pairs. In addition, there were fewer oxygen vacancies in STONF 2 than as-prepared SrTiO3. Lower oxygen vacancies concentration would increase the opportunity of direct bonding between interface atoms of two components and successively increase the electron transportation and separation. These factors synergistically contributed to enhanced photocatalytic performance. This work will provide new insight for designing complementary multi-component photocatalysis systems.

A series of core@shell SrTiO3@NiFe LDH composites (STONFs) were synthesized and their photocatalytic CO2 reduction performance was studied.  相似文献   

3.
PS@TiO2@Ag spheres with triple-level core–shell nanostructures were prepared via a versatile coating procedure based on an electroless-plating-like solution deposition (EPLSD) method. A peroxo-titanium-complex (PTC) aqueous solution was used as the precursor to react with an aniline monomer in the EPLSD preparation. Aniline plays an important role in the TiO2 layer anchoring process through the swollen effects of the PS cores. As extended, peroxo-metal-complex (PMC) with the d0 configuration can be introduced onto PS spheres to form varieties of PS@metal oxide core–shell structures by this method under mild conditions. Ag layers were then modified onto the PS@TiO2 spheres via the photocatalytic method. By the extraction of the PS cores, hollow TiO2 and TiO2@Ag spheres could be obtained. The photochemical degradation of methylene blue (MB) under UV light irradiation was performed on the composite nanostructures.

PS@TiO2@Ag spheres with a core–shell nanostructure were prepared by electroless-plating-like solution deposition (EPLSD) method, which can be alternatively extended to prepare PS@metal(1) oxide@metal(2) composite spheres and their relative hollow spheres.  相似文献   

4.
A two component three degree simplex lattice experimental design was employed to evaluate the impact of different mixing fractions of TiO2 and ZnO on an ordered mesoporous SBA-15 support for CO2 photoreduction. It was anticipated that the combined advantages of TiO2 and ZnO: low cost, non-toxicity and combined electronic properties would facilitate CO2 photoreduction. The fraction of ZnO had a statistically dominant impact on maximum CO2 adsorption (β2 = 22.65, p-value = 1.39 × 10−4). The fraction of TiO2 used had a statistically significant positive impact on CO (β1 = 9.71, p-value = 2.93 × 10−4) and CH4 (β1 = 1.43, p-value = 1.35 × 10−3) cumulative production. A negative impact, from the interaction term between the fractions of TiO2 and ZnO, was found for CH4 cumulative production (β3 = −2.64, p-value = 2.30 × 10−2). The systematic study provided evidence for the possible loss in CO2 photoreduction activity from sulphate groups introduced during the synthesis of ZnO. The decrease in activity is attributed to the presence of sulphate species in the ZnO prepared, which may possibly act as charge carrier and/or radical intermediate scavengers.

A novel example using a systematic design of experiments mixture design for developing mixed metal oxide photocatalysts for CO2 photoreduction.  相似文献   

5.
An efficient photocatalyst of boron-doped titanium dioxide/titanium nanotube array-supported platinum particles (Pt–B/TiO2/Ti NTs) was fabricated for photocatalytic water splitting for hydrogen production through a two-step route. First, B/TiO2/Ti NTs were prepared by anodic oxidation using hydrofluoric acid as electrolyte and boric acid as a B source. Then, Pt particles were deposited on the surface of B/TiO2/Ti NTs by photo-assisted impregnation reduction. The structure and properties of Pt–B/TiO2/Ti NTs were characterized by various physical measurements which showed the successful fabrication of Pt–B/TiO2/Ti NTs. The Pt–B/TiO2/Ti NTs, with a B-doping content of 15 mmol L−1, showed the highest photocatalytic activity and exhibited a photocatalytic hydrogen-production rate of 384.9 μmol g−1 h−1, which was 9.2-fold higher than that of unmodified TiO2/Ti NTs (41.7 μmol g−1 h−1). This excellent photocatalytic performance was ascribed mainly to the synergistic effect of Pt and B, which could enhance the photocatalytic activity of TiO2/Ti NTs.

Pt–B/TiO2/Ti NTs, prepared by anodic oxidation and photo-deposition methods, showed excellent photocatalytic activity.  相似文献   

6.
We have succeeded in synthesizing meso-porous α-Ga2O3 which shows significantly high photocatalytic activity for CO2 reduction with water. The sample was synthesized by hydroxidation of liquid Ga metal in water to obtain GaOOH and Ga(OH)3, followed by the calcination of the mixed hydroxides at 773 K for 1 hour which converted them to meso-porous α-Ga2O3. The nano-pores remained as the trace of the evaporation of water produced by the oxidation of the hydroxides during the calcination. The photocatalytic activity of the synthesized meso-porous α-Ga2O3 for CO2 reduction with water was as high as or higher than previous studies using various types of Ga2O3 with and without cocatalysts.

Meso-porous α-Ga2O3 showing quite high photocatalytic activity for CO2 reduction with water is successfully synthesized from liquid Ga metal.  相似文献   

7.
CuO-based electrodes possess vast potential in the field of CO2 electrochemical reduction. Meantime, TiO2 supports show the advantages of being non-toxic, low-cost and having high chemical stability, which render it an ideal electrocatalytic support with CuO. However, different morphologies and structures of TiO2 supports can be obtained through various methods, leading to the discrepant electrocatalytic properties of CuO/TiO2. In this paper, three supports, named dense TiO2, TiO2 nanotube and TiO2 nanofiber, were applied to synthesize CuO/TiO2 electrodes by thermal decomposition, and the performances of the electrocatalysts were studied. Results show that the main product of the three electrocatalysts was ethanol, but the electrochemical efficiency and reaction characteristics are obviously different. The liquid product of CuO/Dense TiO2 is pure ethanol, however, the current efficiency is rather low owing to the higher resistance of the TiO2 film. CuO/TiO2 nanotube shows high conductivity and ethanol can be synthesized at low overpotential with high current efficiency, but the gas products cannot be restricted. CuO/TiO2 nanofiber has a larger specific surface area and more active sites, which is beneficial for CO2 reduction, and the hydrogen evolution reaction can be evidently restricted. The yield of ethanol reaches up to 6.4 μmol cm−2 at −1.1 V (vs. SCE) after 5 h.

Electrocatalytic reduction of CO2 on three different morphologies of CuO/TiO2.  相似文献   

8.
Three dimensional laminated structure anatase TiO2/nano-Fe0 with exposed (001) facets used as photocatalysts were synthesized by a two-step solvothermal route and a liquid phase reduction deposition method. The resulting samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy and selected-area electron diffraction. Characterization and experimental results indicated that the three dimensional laminated structure of anatase TiO2 was assembled by two dimensional TiO2-sheets with a thickness of approximately 30 nm. The three dimensional laminated structure anatase TiO2/nano-Fe0 photocatalysts with improved visible-light responsive capability, high charge-hole mobility, and low electron–hole recombination exhibited higher photocatalytic performance in the photocatalytic degradation of methylene blue. The composite of nano-Fe0 and TiO2 could effectively promote the generation of hydroxyl radicals (˙OH) with a synergistic effect and Photo-Fenton theory. This study provided new insights into the fabrication and practical application of high-performance photocatalysts in degrading organic pollutants.

Three dimensional laminated structure anatase TiO2/nano-Fe0 with exposed (001) facets were successfully synthesized, which exhibited higher photocatalytic performance in the photocatalytic degradation of methylene blue.  相似文献   

9.
TiO2 hollow fibers (THF) were prepared by a template method using kapok as a biotemplate and subsequently decorated by plasmonic Au nanoparticles using a solution plasma process. The THF exhibited an anatase phase and a hollow structure with a mesoporous wall. Au nanoparticles with a diameter of about 5–10 nm were uniformly distributed on the THF surface. Au nanoparticles-decorated TiO2 hollow fibers (Au/THF) have enhanced photocatalytic activity toward methylene blue degradation under visible light-emitting diode (Vis-LED) as compared to pristine THF and P25. This could be attributed to combined effects including effective light-harvesting by a hollow structure, large surface area due to a mesoporous wall of THF, and visible-light absorption and efficient charge separation induced by Au nanoparticles. The Au/THF also showed good recyclability and separation ability.

Plasmonic Au nanoparticles-decorated TiO2 hollow fibers with enhanced visible-light photocatalytic activity have been successfully prepared by a two-step process: (i) template method using kapok and (ii) solution plasma process.  相似文献   

10.
Selective photocatalytic reduction of CO2 has been regarded as one of the most amazing ways for re-using CO2. However, its application is still limited by the low CO2 conversion efficiency. This work developed a novel Pt/In2O3/g-C3N4 multifunctional catalyst, which exhibited high activity and selectivity to HCOOH during photocatalytic CO2 reduction under visible light irradiation owing to the synergistic effect between photocatalyst, thermocatalyst, and heterojunctions. Both In2O3 and g-C3N4 acted as visible photocatalysts, in which porous g-C3N4 facilitated H2 production from water splitting while the In2O3 nanosheets embedded in g-C3N4 pores favored CO2 fixation and H adsorption onto the Lewis acid sites. Besides, the In2O3/g-C3N4 heterojunctions could efficiently inhibit the photoelectron–hole recombination, leading to enhanced quantum efficiency. The Pt could act as a co-catalyst in H2 production from photocatalytic water splitting and also accelerated electron transfer to inhibit electron–hole recombination and generated a plasma effect. More importantly, the Pt could activate H atoms and CO2 molecules toward the formation of HCOOH. At normal pressure and room temperature, the TON of HCOOH in CO2 conversion was 63.1 μmol g−1 h−1 and could reach up to 736.3 μmol g−1 h−1 at 40 atm.

A multifunctional Pt/In2O3/g-C3N4 catalyst exhibited high activity and selectivity to HCOOH during CO2 reduction owing to the synergy between visible-light harvesting, CO2 activation, HER, and photoelectron–hole separation via heterojunctions.  相似文献   

11.
The interfacial contact between TiO2 and graphitic carbon in a hybrid composite plays a critical role in electron transfer behavior, and in turn, its photocatalytic efficiency. Herein, we report a new approach for improving the interfacial contact and delaying charge carrier recombination in the hybrid by wrapping short single-wall carbon nanotubes (SWCNTs) on TiO2 particles (100 nm) via a hydration-condensation technique. Short SWCNTs with an average length of 125 ± 90 nm were obtained from an ultrasonication-assisted cutting process of pristine SWCNTs (1–3 μm in length). In comparison to conventional TiO2–SWCNT composites synthesized from long SWCNTs (1.2 ± 0.7 μm), TiO2 wrapped with short SWCNTs showed longer lifetimes of photogenerated electrons and holes, as well as a superior photocatalytic activity in the gas-phase degradation of acetaldehyde. In addition, upon comparison with a TiO2–nanographene “quasi-core–shell” structure, TiO2-short SWCNT structures offer better electron-capturing efficiency and slightly higher photocatalytic performance, revealing the impact of the dimensions of graphitic structures on the interfacial transfer of electrons and light penetration to TiO2. The engineering of the TiO2–SWCNT structure is expected to benefit photocatalytic degradation of other volatile organic compounds, and provide alternative pathways to further improve the efficiency of other carbon-based photocatalysts.

The interfacial contact between TiO2 and graphitic carbon in a hybrid composite plays a critical role in electron transfer behavior, and in turn, its photocatalytic efficiency.  相似文献   

12.
Exploiting photocatalysts with characteristics of low cost, high reactivity and good recyclability is a great significance for environmental remediation and energy conversion. Herein, hollow TiO2 nanotubes were fabricated by a novel and efficient method via electrospinning and an impregnation calcination method. With the hydrothermal method, the CdS nanoparticles were modified on the surface and in walls of the TiO2 nanotubes. By changing the reaction conditions, the morphology of CdS nanoparticles presents a controllable three-dimensional (3D) structure. The morphology of the samples was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and components of samples were characterized by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS). The light absorption efficiency was detected using UV-vis diffuse reflectance spectroscopy (DRS) and photoluminescence (PL). The photocatalytic properties were evaluated by degradation of methyl orange (MO) and photocatalytic hydrogen evolution under visible light irradiation. From the results, the TiO2/CdS nanotubes exhibit better photocatalytic activity than the pure TiO2. The synthetic mechanism of TiO2/CdS heterostructures and a possible photocatalytic mechanism based on the experimental results were proposed.

Exploiting photocatalysts with characteristics of low cost, high reactivity and good circularity is a great significance for environmental remediation and energy conversion.  相似文献   

13.
Using polystyrene (PS) spheres as a template, three-dimensional ordered macroporous Pt/TiO2–ZrO2 (3DOM Pt/TiO2–ZrO2) composites were prepared by vacuum impregnation combined with photoreduction. The crystal structure, composition, morphology, optical absorption, and surface physicochemical properties of the as-synthetized samples were characterized by X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (UV-vis/DRS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and N2 adsorption–desorption analyses. The results showed that the 3DOM Pt/TiO2–ZrO2 composites were mainly composed of anatase TiO2 and tetragonal ZrO2 crystal phases, in which Pt mainly existed as a single species. In addition, the as-synthesized composites had open, three-dimensionally ordered macroporous structures that could enhance their multi-mode photocatalytic degradation performance under UV, visible light, simulated solar light, and microwave-assisted irradiation. Moreover, the 3DOM Pt/TiO2–ZrO2 composites exhibited the best photocatalytic water splitting performance as compared to other systems.

Using polystyrene spheres as templates, 3DOM Pt/TiO2–ZrO2 composites were prepared by the vacuum impregnation combined with photoreduction method, which exhibited an enhanced photodegradation and water splitting performance.  相似文献   

14.
Highly crystalline anatase titanium dioxide (TiO2) nanocuboids were synthesized via a hydrothermal method using ethylenediamine tetraacetic acid as a capping agent. The structural study revealed the nanocrystalline nature of anatase TiO2 nanocuboids. Morphological study indicates the formation of cuboid shaped particles with thickness of ∼5 nm and size in the range of 10–40 nm. The UV-visible absorbance spectra of TiO2 nanocuboids showed a broad absorption with a tail in the visible-light region which is attributed to the incorporation of nitrogen atoms into the interstitial positions of the TiO2 lattice as well as the formation of carbonaceous and carbonate species on the surface of TiO2 nanocuboids. The specific surface areas of prepared TiO2 nanocuboids were found to be in the range of 85.7–122.9 m2 g−1. The formation mechanism of the TiO2 nanocuboids has also been investigated. Furthermore, the photocatalytic activities of the as-prepared TiO2 nanocuboids were evaluated for H2 generation via water splitting under UV-vis light irradiation and compared with the commercial anatase TiO2. TiO2 nanocuboids obtained at 200 °C after 48 h exhibited higher photocatalytic activity (3866.44 μmol h−1 g−1) than that of commercial anatase TiO2 (831.30 μmol h−1 g−1). The enhanced photoactivity of TiO2 nanocuboids may be due to the high specific surface area, good crystallinity, extended light absorption in the visible region and efficient charge separation.

Highly crystalline TiO2 nanocuboids have been prepared and their photocatalytic hydrogen generation activity was evaluated via water splitting.  相似文献   

15.
TiO2-based materials for photocatalytic hydrogen (H2) evolution have attracted much interest as a renewable approach for clean energy applications. TiO2–Au composite nanofibers (NFs) with an average fiber diameter of ∼160 nm have been fabricated by electrospinning combined with calcination treatment. In situ reduced gold nanoparticles (NPs) with uniform size (∼10 nm) are found to disperse homogenously in the TiO2 NF matrix. The TiO2–Au composite NFs catalyst can significantly enhance the photocatalytic H2 generation with an extremely high rate of 12 440 μmol g−1 h−1, corresponding to an adequate apparent quantum yield of 5.11% at 400 nm, which is 25 times and 10 times those of P25 (584 μmol g−1 h−1) and pure TiO2 NFs (1254 μmol g−1 h−1), respectively. Furthermore, detailed studies indicate that the H2 evolution efficiency of the TiO2–Au composite NF catalyst is highly dependent on the gold content. This work provides a strategy to develop highly efficient catalysts for H2 evolution.

The H2 production rate of TiO2–Au nanofibers is dramatically improved to 12 440 μmol g−1 h−1, 10 times that of pure TiO2.  相似文献   

16.
Optimized photocatalytic conversion of CO2 requires new potent catalysts that can absorb visible light. The photocatalytic reduction of CO2 using rhenium(i) has been demonstrated but suffers from low turnover. Herein, we describe a [Re(CO)3(1-(1,10)phenanthroline-5-(4-nitro-naphthalimide))Cl] photocatalyst, which when combined with the sacrificial donor 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole, results in selective production of formic acid and a high turnover number of 533 and turnover frequency of 356 h−1. Single-crystal X-ray diffraction and DFT studies are also discussed.

Rhenium based photocatalytic conversion CO2 to formate in the visible region with excellent turnover.  相似文献   

17.
Carbon monoxide (CO) purification from syngas impurities is a highly energy and cost intensive process. Adsorption separation using metal–organic frameworks (MOFs) is being explored as an alternative technology for CO/nitrogen (N2) and CO/carbon dioxide (CO2) separation. Currently, MOFs'' uptake and selectivity levels do not justify displacement of the current commercially available technologies. Herein, we have impregnated a leading MOF candidate for CO purification, i.e. M-MOF-74 (M = Co or Ni), with Cu+ sites. Cu+ allows strong π-complexation from the 3d electrons with CO, potentially enhancing the separation performance. We have optimised the Cu loading procedure and confirmed the presence of the Cu+ sites using X-ray absorption fine structure analysis (XAFS). In situ XAFS and diffuse reflectance infrared Fourier Transform spectroscopy analyses have demonstrated Cu+–CO binding. The dynamic breakthrough measurements showed an improvement in CO/N2 and CO/CO2 separations upon Cu impregnation. This is because Cu sites do not block the MOF metal sites but rather increase the number of sites available for interactions with CO, and decrease the surface area/porosity available for adsorption of the lighter component.

We present an in situ study of CO adsorption on Cu impregnated MOF-74 and study the competitive adsorption of CO vs. CO2 and N2.  相似文献   

18.
To obtain high-efficiency, low-cost, environmentally friendly carbon-based photocatalytic material, we synthesized coal-based carbon dots with sp2 carbon structure and multilayer graphene lattice structure by the hydrogen peroxide (H2O2) oxidation method to strip nano-scale crystalline carbon in the coal structure and link with oxygen-containing groups such as the hydroxyl group. N, S co-doped aminated coal-based carbon nanoparticles (NH2-CNPs) were then obtained by thionyl chloride chlorination and ethylenediamine passivation. The physical properties and chemical structure of the synthesized NH2-CNPs were studied and the photocatalytic CO2 reduction performance was tested. The results show that NH2-CNPs are vesicle-type spherical particles with particle size of 42.16 ± 7.5 nm and have a mesoporous structure that is capable of adsorbing CO2. A defect structure was formed on the surface of the NH2-CNPs due to the doping of N and S elements, thereby significantly improving the ability to photogenerate electrons under visible light along with the ability to efficiently separate the photo-generated carriers. The photocatalytic reduction products of CO2 over NH2-CNPs were CH3OH, CO, C2H5OH, H2 and CH4. After 10 hours of reaction, the total amount of products was 807.56 μmol g−1 cat, the amount of CH3OH was 618.7 μmol g−1 cat, and the calculated selectivity for conversion of CO2 to CH3OH was up to 76.6%.

Aminated coal-based carbon nanoparticles (NH2-CNPs) was fabricated. The physical properties and chemical structure of the NH2-CNPs was studied. Photocatalytic CO2 reduction activity of NH2-CNPs were measured and the reaction mechanism was discussed.  相似文献   

19.
In order to promote the photosynthetic growth rate of Chlorella in the presence of flue gas CO2 from coal-fired power plants, spermidine was first used to enhance cellular resistance to a high CO2 concentration (15%) and high light intensity (30 000 lux). It was found that low concentrations (100–300 μM) of spermidine significantly enhanced the photosynthetic growth rate of Chlorella. The accelerated cell division decreased the cell diameter from 3.64 μm to 2.71 μm and the fractal dimension from 1.60 to 1.49, and the activity of total superoxide dismutase (T-SOD) increased from 0.48 U mL−1 to 5.33 U mL−1. Expression levels of key enzymes of photosystems I and II, ATP synthase and transportase markedly increased, thereby enhancing the electron transport and energy supply that reduced oxidative damage. Finally, an enhanced cellular resistance to the high CO2 concentration and high light intensity increased the biomass yield from 0.11 g L−1 to 1.71 g L−1 (300 μM).

Spermidine enhanced resistance of Chlorella to high levels of CO2 and light intensity.  相似文献   

20.
In the last few decades, TiO2 has been widely used in different types of photocatalytic applications. However, the relatively large optical band gap (∼3.2 eV), low charge carrier mobility and consequently its low quantum efficiency limit its photocatalytic activity. Herein, we construct a novel nanostructured heterojunction of WON/TiO2 nanofibers (NFs) by integration of TiO2 nanofibers synthesized by electrospinning of a polymer solution containing a titanium(iv) butoxide precursor with WON nanoparticles fabricated via annealing of a WO3 precursor in dry ammonia at 700 °C. The synthesized photocatalysts were characterized using different spectroscopic techniques. Their photocatalytic performance towards the degradation of methyl orange, methylene blue, and phenol as model contaminants was investigated and the charge transfer process was elucidated and compared to that of a TiO2/WO3 heterojunction.

Coupling of WON with TiO2 nanofibers creates a novel heterojunction with enhanced photocatalytic activity.  相似文献   

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