CN111333487A - Method for preparing methanol by photocatalytic oxidation of methane - Google Patents
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
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- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention belongs to the field of photocatalysis, and discloses a method for preparing methanol by photocatalytic oxidation of methane, which comprises the following steps: adding the Au/ZnO composite photocatalyst into water, stirring, and introducing CH4And O2Under the condition of light irradiation, carrying out photocatalysis on CH4Carrying out oxidation reaction to prepare methanol; the load capacity of Au in the photocatalyst is more than or equal to 0.3 wt%, and CH4The pressure is more than or equal to 15 bar. The invention utilizes Au-loaded ZnO as a photocatalyst, fully derives conduction band electrons in ZnO by accurately regulating and controlling the loading amount of Au nanoparticles, and promotes CH3Reduction of OOH to CH3And (5) OH. In addition, by replacing the light source, the irradiation of the ultraviolet region is replaced by the irradiation of the full spectrum, so that the requirement of energy in the reaction can be met, and the generated CH caused by too high light energy input can be avoided3OH is decomposed and oxidized into HCHAnd O. Finally, CH is realized4Selective oxidation to CH3OH, the selectivity reaches 100 percent.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a method for preparing methanol by photocatalytic oxidation of methane.
Background
CH4About 70% to 90% of the natural products are widely regarded as indispensable raw materials in industrial production. In particular CH4Capable of selective oxidation to valuable C1 organic products, such as CH3OH and HCHO, a modality that has attracted particular attention by researchers. However, CH4Two major challenges are always faced in the selective oxidation of4Is a nonpolar molecular structure and has high C-H bond energy (345kJ mol)-1) Making it difficult for chemical reactions to occur; second is the ideal product CH3OH and HCHO have low thermodynamic stability and are easily deeply oxidized into CO2. Industrial CH4The predominant process for conversion to valuable products is the indirect steam reforming technique, i.e. CH4And H2O is first oxidized by high energy to syngas (CO and H)2) Then converted into CH by a thermal catalytic reaction3OH or other hydrocarbons. Although the industrial route is well-established, the following disadvantages exist: high reaction temperatures result in economic waste; cumbersome multistep reaction procedures; the coke generated in the reaction process can easily deactivate the catalyst; large scale centralized facilities are expensive. Therefore, efficient, inexpensive, sustainable CH is sought4The oxidation catalysis mode is imperative.
CH can be realized under mild conditions by photocatalysis4Direct conversion, environmental protection, low cost, small-scale dispersion reaction and the like, and can be counted as CH4A breakthrough in utilization. Under the condition of illumination, the semiconductor photocatalyst can realize a plurality of reactions with insufficient thermodynamics by utilizing generated high-activity free radicals under mild conditions. In CH4In oxidation, the cleavage of the C-H bond is considered to be CH4And (3) determining the activation rate. And hydroxyl radicals (C) generated in the photocatalytic process·OH) is considered to be a key active for breaking C-H bonds. Up to now, photocatalytic CH4The conversion of (a) is mainly achieved by anaerobic oxidation. Wherein·OH is primarily oxidation of H by photogenerated holes2O is formed in low amounts, thus resulting in CH4The activation efficiency is low, seeSastre,F.；Fornés,V.；Corma,A.；
Journal of the American chemical Society 2011,133,17257. Or to increase CH under anaerobic conditions4On the one hand, researchers raise the reaction temperature (50 ℃ to 98 ℃) and promote CH by consuming extra energy4On the other hand, the injection of hydrogen peroxide (H) which is expensive2O2) To reduce it to form·OH for satisfying CH4Activating demand, increasing CH4Activation yield, see in particular vila, k.; Murcia-L Lopez, S.; andreu, t.; morate, J.R. applied Catalysis B, environmental2015,163, 150. However, H2O2The corrosiveness and instability of the catalyst cause the safety and economical limit of the practical application of the catalyst.
Currently, photocatalytic aerobic oxidation of CH4Preparation of CH3In the OH experiment, CH is present3Low OH selectivity. This is because O is used2Carrying out photocatalysis of CH4The oxidation route is as follows:
namely CH4Quilt O2Oxidation to methyl hydroperoxide (CH)3OOH) and then reduced to CH3OH, and CH formed3OH is easily oxidized into HCHO under the input of high-energy light, and a target product CH is generated3The selectivity of OH is low. Currently, the best photocatalytic CH4Aerobic oxidation for preparing CH3Work with OH (J.Am.chem.Soc.2019,141:20507-20515), in which CH3The OH selectivity was only 15.7%.
Disclosure of Invention
Based on the above problems, the present invention aims to construct an O-based catalyst2Photocatalytic CH enhancement for mild oxidants4Aerobic oxidation to CH3OH method. In the photocatalysis of CH4Adding O into the oxidation system2By adding a conduction bandAnd photocatalyst (ZnO) with proper valence band energy, and reaction conditions are controlled to realize the reduction of semiconductor conduction electrons to O2And valence band hole oxidation H2O two ways promote·Production of OH, increase of CH4And (4) activating efficiency.
The purpose of the invention is realized by the following technical scheme:
a method for preparing methanol by photocatalytic oxidation of methane comprises the following steps:
adding the Au/ZnO composite photocatalyst into water, stirring, and introducing CH4And O2Carrying out photocatalysis CH under the irradiation condition of a full-spectrum light source4Carrying out oxidation reaction to prepare methanol; the load capacity of Au in the photocatalyst is more than or equal to 0.3 wt%, and CH4The pressure is more than or equal to 15 bar.
Preferably, the CH4The pressure is more than or equal to 25 bar.
Preferably, the loading amount of Au in the photocatalyst is more than or equal to 0.75 wt%.
Preferably, said O is2The pressure of (2) is 0.5-8 bar.
Preferably, said O is2The pressure of (2) is 5 bar.
Preferably, the oxidation reaction temperature is 20-40 ℃, and the reaction time is 1-3 h.
Preferably, the oxidation reaction temperature is 30 +/-5 ℃, and the reaction time is 2 +/-0.5 h.
Preferably, the light source is sunlight or a xenon lamp.
Preferably, the preparation method of the Au/ZnO composite photocatalyst is as follows:
adding ZnO nanoparticles into water, ultrasonically dispersing, stirring, and adding HAuCl4Then NaBH is added dropwise in an ice bath4Carrying out reduction reaction; and centrifuging, washing, drying and calcining after reaction to obtain the Au/ZnO composite photocatalyst.
Preferably, the calcining condition is 500-600 ℃ and 1-2 h.
Preferably, the dispersion time is 0.5h and the stirring time is 6 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention is based on photocatalytic CH4Aerobic oxidation for preparing CH3In the OH reaction path, Au-loaded ZnO is used as a photocatalyst, and the conduction band electrons in the ZnO are fully led out by accurately regulating and controlling the loading amount of Au nanoparticles to promote CH3Reduction of OOH to CH3And (5) OH. In addition, by replacing the light source, the irradiation of the ultraviolet region is replaced by the irradiation of the full spectrum, so that the requirement of energy in the reaction can be met, and the generated CH caused by too high light energy input can be avoided3OH is decomposed and oxidized to HCHO. Finally, CH is realized4Selective oxidation to CH3OH, the selectivity reaches 100 percent.
Drawings
FIG. 1 is a TEM image of Au/ZnO composite photocatalyst of the present invention, wherein a is Au at 100nm scale0.75Representative TEM image of/ZnO, inset is the statistical distribution of the particle size of the Au nanoparticles, with an average size of about 7nm, b is Au at 5nm scale0.75Representative TEM image of/ZnO.
FIG. 2 is a crystal structure representation diagram of the Au/ZnO composite photocatalyst of the present invention, wherein a represents ZnO and Au0.75XRD pattern of/ZnO, b is Au0.75HRTEM image of/ZnO.
FIG. 3 shows the loading of Au versus CH generation3Graph of the effect of OH selectivity.
FIG. 4 shows different reaction conditions vs. CH3Influence of OH yield, a is O2B is the effect of pressure.
FIG. 5 shows a Au/ZnO composite photocatalyst pair·An OH forming capability effect graph, a UV-Vis diffuse reflection spectrum (a), a Mott-Schottky graph (c) and a transformed Kubelka-Munk function graph (b) as an accurate analysis graph (d) of the energy band structure of ZnO.
FIG. 6 shows ESR spectra under different reaction conditions, where a is the effect of the catalyst and b is O2The influence of (c).
FIG. 7(a) is a GC-MS diagram of the product obtained by isotopically labeling the carbon source, and FIG. 7(b) is a diagram showing that the concentration of the carbon source is 33%13CH4Observed in the system13CH3Of OH13C NMR peaks.
FIG. 8 is a GC-MS plot of the product of isotopically labeled O sources.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
1) Preparing a precursor by using the catalyst: ZnO, sodium borohydride, barium sulfate, sodium sulfate, chloroauric acid, 5-dimethyl-1-pyrrole-n-oxide (DMPO). All chemicals were used without further purification.
2) Preparing an Au/ZnO composite photocatalyst: the Au/ZnO composite photocatalyst is prepared by adopting a chemical reduction method. Commercial ZnO nanoparticles (alatin, 200mg) were dispersed in 50mL of deionized water and sonicated for 0.5 h. Stirred at room temperature for 6h and a volume of 50mM HAuCl was added4Then NaBH is added dropwise in an ice bath4Carrying out chemical reduction. The synthesized substrate was washed three times with deionized water by centrifugation and the water was removed from the substrate by evaporation in vacuo. In order to improve the crystallinity of the composite material, the composite material is calcined at 500 ℃ for 1h to prepare the Au/ZnO composite photocatalyst.
3) Photocatalytic CH4An aerobic oxidation reaction method comprises the following steps: CH (CH)4Photocatalytic activity measurement of the conversion was carried out in a 50mL stainless steel autoclave, 100mW cm-2The xenon lamp was used as the light source and illuminated through the quartz glass window on top. 10mg of the photocatalyst was suspended in 10mL of deionized water and stirred. The reactor was charged with CH at 15bar and 5bar4/O2Mixing the gases and sealing. During the light irradiation (2h), the reaction temperature was kept at 30 ℃ with a cooling water bath.
4) Instrument characterization TEM and HRTEM characterization on a 200kV FEI Tecnai G2F 20 Electron microscope 200kV HAADF STEM, EDX spectra and elemental mapping were studied on JEM-ARM 200F XRD tests were performed using copper K α radiation (λ 1.542) in XeussSAXS/WAXS and D/MAX-TTRIII (CBO) systems at 50kV and 300mA, with BaSO4As an internal reference sample, in Hitachi U-3010 type UV-visibleThe uv-vis diffuse reflectance spectrum was recorded on a spectrophotometer. 1M Na at 800 Hz and 1000Hz frequencies respectively2SO4In solution, mott-schottky plot testing was performed using the CHI 760E electrochemical workstation. Steady state photoluminescence spectra were collected and fluorescence lifetime decay curves were followed using Horiba Jobin Yvon NanoLog 200 fluorescence spectrometer.
5) Photocatalytic CH4The detection method of the aerobic oxidation products comprises the following steps: GC, GC-MS and NMR for CH as a liquid product3OH was detected both qualitatively and quantitatively. Quantitative determination of CH using Shimadu GC-2014C hydrogen flame ionization detector3The content of OH. Another Shimadu GC-MS QP2010 Ultra is used for monitoring CH3 18OH and13CH3generation of OH.13C-NMR and1H-NMR was recorded by Bruker AVANCE III HD 400mhz nuclear magnetic resonance spectrometer (NMR spectrometer).
6)·And (3) an OH detection method: electron spin resonance spectroscopy (ESR) for detection·Generation of OH. A certain amount of photocatalyst was dispersed in water and DMPO was added as a trapping agent. Monitoring with Bruker (E500) spectrometer under light irradiation·The OH signal.
7) And carrying out appearance analysis on the sample by using a TEM. TEM images (a, b) of Au/ZnO of FIG. 1 were obtained, showing that commercial ZnO has an irregular structure and Au nanoparticles are uniformly distributed on the surface of the ZnO substrate at a size of about 7 nm.
8) According to the peaks (100), (002), (101), (102) and (110) in FIG. 2a, the XRD pattern shows that the synthesized Au/ZnO is a wurtzite structure, which is completely consistent with JCPDS No. 36-1451. No peak of Au was detected on the Au/ZnO due to the low loading. However, in HRTEM, the Au (111) plane lattice fringe (b) with lattice spacing d of 0.24nm illustrates the successful deposition of Au, while the lattice fringe d of 0.26nm represents the ZnO (101) plane, whose crystallinity is consistent with XRD results.
9) Loading of Au to CH formation3Influence of OH selectivity: to evaluate the material pair CH3Selectivity of OH, ZnO with different Au loading ratios as photocatalyst to CH4Direct oxidation is carried out. In 10mg of catalyst, 10mL of H2O，5bar O2，15bar CH4The intensity density of the full-spectrum irradiation light of the xenon lamp is 100mW cm-2At the reaction temperature of 30 ℃, unsupported ZnO catalyzes CH4Generating CH3OOH and CH3OH as oxidation product (313. mu. mol g)-1) In which CH3The OH selectivity was 56.5%. When the loading of Au was increased from 0.08 wt% to 0.15 wt%, O2Under the atmosphere, CH3OOH and CH3The amount of OH was increased to 952. mu. molg, respectively-1And 1083. mu. mol g-1This may result from the addition of Au increasing·Generation of OH, thereby enhancing CH4The activation efficiency of (3). However, due to CH3OH formation Rate ratio CH3OOH is slow, so the selectivity is from 54.1% (Au)0.08The concentration of/ZnO is reduced to 46.8 percent (Au)0.15/ZnO). The loading of Au was further increased to 0.30% to obtain a maximum oxide yield of 2402. mu. mol g-1At the same time CH3The OH selectivity is raised to 83.1%, which benefits from the rise in the number of separated electrons, thereby increasing CH3And (4) OOH reduction. Further increase in the amount of Au more than 0.30 wt% found CH3OOH signal disappears, indicating CH3OOH is completely reduced, thus CH3The selectivity of OH reaches 100 percent. However, too much Au loading decreases ZnO exposure to active sites, resulting in CH3The OH number was reduced (1245. mu. mol g)-1). Finally, for the purpose of selective optimization, CH3Au with OH as a single product0.75The best catalyst choice is/ZnO.
10) Considering O2Influence of, e.g. O2Promotion of·Formation of OH, or CH3OH is provided as an O element, so in FIG. 4a, with or without O2When participating in CH3The level of OH formation was investigated. Using Au/ZnO as catalyst, O2Promoting the use of CH3OH yield was increased from 405 to 1228. mu. mol g-1Approximately 3-fold increase, indicating O2Participate in CH4The oxidation reaction is in the speed-determining step. In addition, in the absence of H2Control experiments were carried out in O or no light, and no CH was found3Trace of OH, which is illustrated in photocatalytic CH4Transformation ofIn process H2O and light are the necessary conditions for the reaction. In addition, CH is increased4Partial pressure of in CH3The OH formation is also promoted (b), the yield reaches 1934 mu mol g at 25bar-1This is due to the increase in pressure which increases CH4Solubility in water.
11) Study of Au/ZnO pairs by construction of band structures·OH-generating ability. The band structure of ZnO was accurately analyzed in FIG. 5(d) using UV-Vis diffuse reflectance spectrum 5(a), Mott-Schottky graph 5(c) and transformed Kubelka-Munk function graph 5(b), and the valence-leading positions of ZnO were-0.101 eV. NHE and 2.899 eV. Vs. NHE, respectively. Based on the fermi level of Au being 0.60eV vs. nhe, we can predict that conduction band electrons in ZnO (-0.101eV vs. nhe) have sufficiently high energy transfer to Au, thereby improving charge separation efficiency. Then the extracted electrons and the left holes respectively reduce O2(O2+2H++2e-→H2O2→·OH,O2/·OH 0.695 eV. vs. NHE) and H oxide2O(H2O+h+→·OH+h+，·OH/H2O2.380 eV vs. nhe) preparation·OH。
12) In fact, O is compared to undoped ZnO2The addition of (A) obviously improves the content of the Au/ZnO system·OH yields are shown in FIGS. 6a and b. Four characteristic peaks of 1:2:2:1 in ESR spectrum represent·The presence of OH. In FIG. 6a, the intensity of the metal Au after modification is increased by 1.6 times through ESR spectrum detection between Au/ZnO and ZnO, which indirectly proves that the charge separation is helpful to·Formation of OH. Furthermore, FIG. 6b depicts Au/ZnO with or without O2Bound reaction signal, where high ESR strength (1.8 fold) confirms O2Participate in·OH is generated. Since C-H cleavage is considered to be the rate determining step, it is increased·OH as activator inevitably increases CH4The conversion efficiency of (a).
13) To determine CH4As CH3OH is generated from raw material of 5bar13CH4And 10bar12CH4(13CH4In that12 CH 433%) as a carbon source, and the product was analyzed by GC-MS in fig. 7 (a). Evident at m/z 3313CH3OH Peak, which strongly suggests that the product source in the Au/ZnO system is CH4Rather than the incorporation of impurities. The utilization ratio is 100%12CH4A control experiment was performed in which only the product detected in GC-MS was12CH3OH (m/z ═ 32), confirming further the liquid phase CH3The carbon source of OH is CH4. Furthermore, at 48.88ppm, from 33% of13CH4Observed in the system13CH3Of OH13C NMR peak (b), at 100%12CH4There is no peak in the system, which can be taken as CH4Evidence of transformation.
14) To study CH3O source of OH, subjected to H2 18O+16O2Or H2 16O+18O2And (4) isotope experiments. As shown in FIG. 8, H2 18O+16O2And H2 16O+18O2All detected labeled CH in the system3 18OH (m/z ═ 34) indicating H2O and O2Can pass through·Participation of OH intermediates in CH3In OH.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing methanol by photocatalytic oxidation of methane is characterized by comprising the following steps:
adding the Au/ZnO composite photocatalyst into water, stirring, and introducing CH4And O2Carrying out photocatalysis CH under the irradiation condition of a full-spectrum light source4Carrying out oxidation reaction to prepare methanol; the loading capacity of Au in the photocatalyst is more than or equal to 0.3wt％，CH4The pressure is more than or equal to 15 bar.
2. The method of claim 1, wherein the CH is configured to perform4The pressure is more than or equal to 25 bar.
3. The method of claim 2, wherein the loading of Au in the photocatalyst is greater than or equal to 0.75 wt%.
4. The method of claim 3, wherein said O is2The pressure of (2) is 0.5-8 bar.
5. The method according to any one of claims 1 to 4, wherein the oxidation reaction temperature is 20 to 40 ℃ and the reaction time is 1 to 3 hours.
6. The method according to claim 5, wherein the oxidation reaction temperature is 30 + 5 ℃ and the reaction time is 2 + 0.5 h.
7. The method of claim 6, wherein the light source is sunlight or a xenon lamp.
8. The method as claimed in any one of claims 1 to 4, wherein the preparation method of the Au/ZnO composite photocatalyst is as follows:
adding ZnO nanoparticles into water, ultrasonically dispersing, stirring, and adding HAuCl4Then NaBH is added dropwise in an ice bath4Carrying out reduction reaction; and centrifuging, washing, drying and calcining after reaction to obtain the Au/ZnO composite photocatalyst.
9. The method according to claim 8, wherein the calcination is carried out at 500 to 600 ℃ for 1 to 2 hours.
10. The process according to claim 8, characterized in that the dispersion time is 0.5h and the stirring time is 6 h.
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| CN114618469A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Supported zinc oxide catalyst and preparation method and application thereof |
| CN116173950A (en) * | 2023-03-09 | 2023-05-30 | 华南理工大学 | Preparation method and application of gold nanoparticle-loaded zinc titanate/titanium dioxide composite material |
| CN116173950B (en) * | 2023-03-09 | 2024-07-16 | 华南理工大学 | Preparation method and application of gold nanoparticle-loaded zinc titanate/titanium dioxide composite material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114618469A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Supported zinc oxide catalyst and preparation method and application thereof |
| CN113101964A (en) * | 2021-04-26 | 2021-07-13 | 国家纳米科学中心 | Mesoporous cerium oxide photocatalyst and preparation method and application thereof |
| CN113101964B (en) * | 2021-04-26 | 2023-07-21 | 国家纳米科学中心 | Mesoporous cerium oxide photocatalyst and preparation method and application thereof |
| CN116173950A (en) * | 2023-03-09 | 2023-05-30 | 华南理工大学 | Preparation method and application of gold nanoparticle-loaded zinc titanate/titanium dioxide composite material |
| CN116173950B (en) * | 2023-03-09 | 2024-07-16 | 华南理工大学 | Preparation method and application of gold nanoparticle-loaded zinc titanate/titanium dioxide composite material |
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