CN105833908B - A kind of doping heteropolyacid catalyst and the under visible light method of photolysis water hydrogen gas - Google Patents
A kind of doping heteropolyacid catalyst and the under visible light method of photolysis water hydrogen gas Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 13
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of doping heteropolyacid catalyst and the method for photolysis water hydrogen gas, the preparation method of catalyst are under visible light：By Na4SiMo12O40·2H2O dissolves in deionized water, is heated to 80 85 DEG C, adds in HF in the solution and is filtered after stirring 1h at 200 rpm, obtains NaMoFOM filtrates；Ni (CH are added in filtrate3CO2)2Powder simultaneously dissolves, then mixed solution is heated to 80 85 DEG C, is filtered after stirring 1h at 200 rpm, obtains NaNiMoFOM filtrates；The NaNiMoFOM filtrates are mixed with acetic acid, mixed liquor is heated to 50 60 DEG C, stirs 30min at 200 rpm, and cooling is placed in evaporative crystallization 2 days at room temperature, obtains crystal i.e. nickel doping heteropolyacid catalyst H12NiMo17F6O55·20H2O.Present invention manufacture is at low cost, and doping method is simple, and the catalyst after doping is under visible light for water photodissociation hydrogen, H2Conversion ratio can be to more than 15%, efficient and conversion trend stability.
Description
Technical field
The present invention relates to the photocatalytic water catalyst and under visible light method of photolysis water hydrogen gas, refers specifically to a kind of doping
Heteropolyacid catalyst and the under visible light method of photolysis water hydrogen gas.
Background technology
It is gradual less with non-renewable energy resources, reasonable development and become a kind of trend using new energy.Hydrogen conduct
Unique reproducible energy has the characteristics that cleaning, efficient, high heating value, environmental-friendly.Traditional silicol process mainly has fossil fuel
Hydrogen manufacturing and water electrolysis hydrogen production, wherein fossil fuel hydrogen manufacturing and have become commercial scale using at most, but fossil fuel hydrogen manufacturing
There are technique is backward, deficiency in economic performance and it is seriously polluted the shortcomings of；Water electrolysis hydrogen production be it is a kind of completely it is clean and by electric energy turn
The hydrogen manufacturing mode of chemical energy is turned to, but its disadvantage is exactly that power consumption is excessive, financial cost is high.
Photolysis water hydrogen method is extensively studied as a kind of new hydrogen production method, and solar energy as it is a kind of it is most clean can
The renewable sources of energy.What people had found and developed so far can be used in the photochemical catalyst of photocatalytic water, be only capable of absorbing ultraviolet light, but
Ultraviolet light ratio shared in sunlight is less.Water can be decomposed under visible light also seldom to report, especially obstructed overload
Body TiO2Or SiO2The doping heteropolyacid catalyst of synthesis has not been reported, and the present invention provides a kind of doping of non-loading type is miscellaneous more
Acid catalyst and the under visible light method of photolysis water hydrogen gas.
The content of the invention
The technical problems to be solved by the invention be for the prior art present situation provide it is a kind of it is at low cost, preparation process is simple
The doping heteropolyacid catalyst for being used to be catalyzed photolysis water hydrogen gas under visible ray of single, hydrogen yield height and conversion trend stability.
Another technical problem to be solved by this invention be to provide it is a kind of it is at low cost, preparation process is simple, hydrogen conversion
Rate is high and converts the processing method for photolysis water hydrogen gas under visible ray of trend stability.
Technical solution is used by the present invention solves above-mentioned technical problem：The doping heteropolyacid catalyst, feature exist
It is as follows in the preparation method of the catalyst：
1) it is Na by mixing ratio4SiMo12O40·2H2O: the mixed liquor of deionized water=44g: 100mL is heated to 80-85
℃；Adding in 14mL 40%HF makes pH value maintain 4.5-5.0, which filters after stirring 1h at 200 rpm, obtains
NaMoFOM filtrates.
2) by the NaMoFOM filtrates and Ni (CH3CO2)2Mixing, mixing ratio is filtrate: Ni (CH3CO2)2=80mL: 7g,
Mixed liquor is heated to 80-85 DEG C, is filtered after stirring 1h at 200 rpm, obtains NaNiMoFOM filtrates.
3) the NaNiMoFOM filtrates 60mL is mixed with acetic acid, mixed volume ratio is filtrate: acetic acid=1: 2, heating is mixed
Liquid is closed to 50-60 DEG C, stirs 30min at 200 rpm, cools down, is placed in evaporative crystallization 2 days at room temperature, crystal i.e. nickel is obtained and adulterates
Heteropolyacid catalyst H12NiMo17F6O55·20H2O。
The method for carrying out photolysis water hydrogen gas using nickel doping heteropolyacid catalyst, it is characterised in that including following steps
Suddenly：
In the cylindrical quartz Photoreactor of a 50ml, it is put into reactant mixed proportion and adulterates heteropoly acid catalysis for nickel
Agent: methanol solution: then deionized water=0.5-0.7g: 6mL: 20mL is removed by bubbling ultrapure argon continuous bubbling 30min
Dissolved oxygen.After stirring 15min under 1MPa air pressures, 200rpm, pass through the cut-off that light source is the special xenon lamps of visible ray PL-X300D
The irradiation and reaction of visible ray are carried out in the photochemical reactor of glass filter, reacts 4h, 0.5ml gases are extracted every 1h,
The H of sample under quantitative determination different time is carried out by Japanese Shimadzu GC-2010 gas chromatographs2Burst size, determination sample
Photocatalytic activity.
Compared with prior art, the present invention provides a kind of brand-new doping heteropolyacid catalyst, which is manufactured into
This low, doping method simple possible, the catalyst after doping is to the conversion ratio of photolysis water hydrogen gas under visible light up to 15%
More than, and efficient, conversion trend stability.
Description of the drawings
Fig. 1 is the UV-Vis figures of nickel doping heteropolyacid catalyst
Fig. 2 is the SEM figures of nickel doping heteropolyacid catalyst
Fig. 3 is reaction time-hydrogen conversion figure of nickel doping heteropolyacid catalyst
Specific embodiment
Embodiment 1
It is as follows to prepare nickel doping heteropolyacid catalyst：
It is Na by mixing ratio4SiMo12O40·2H2O: the mixed liquor of deionized water=44g: 100mL is heated to 80-85 DEG C；
Adding in 14mL 40%HF makes pH value maintain 4.5-5.0, which filters after stirring 1h at 200 rpm, obtains NaMoFOM filters
Liquid.By the NaMoFOM filtrates and Ni (CH3CO2)2Mixing, mixing ratio is filtrate: Ni (CH3CO2)2=80mL: 7g, heating is mixed
Liquid is closed to 80-85 DEG C, is filtered after stirring 1h at 200 rpm, obtains NaNiMoFOM filtrates.By the NaNiMoFOM filtrates
60mL is mixed with acetic acid, and mixed volume ratio is filtrate: acetic acid=1: 2, heating mixed liquor stirs at 200 rpm to 50-60 DEG C
30min, cooling, is placed in evaporative crystallization 2 days at room temperature, crystal i.e. nickel doping heteropolyacid catalyst is obtained, by the catalyst upper
Analysis test is carried out in 2100 ultraviolet-uisible spectrophotometers of WFJ that Hai Younike Instrument Ltd. provides, Fig. 1 is that nickel is mixed
The UV-Vis figures of miscellaneous heteropolyacid catalyst.As shown in Figure 1, the nickel prepared by the present embodiment adulterates heteropolyacid catalyst in visible ray
There is absorption at wavelength, absorb peak position in 500nm or so, illustrate that the catalyst is active under visible light illumination.
Embodiment 2
The present embodiment is determined by experiment nickel doping heteropolyacid catalyst molecular formula：
The nickel doping heteropolyacid catalyst of embodiment 1 is subjected to analysis test in Thermo X-7ICP elemental analysers,
It the results are shown in Table 1.Separately the 2g photocatalyst crystals is taken to calcine 2h at 80 DEG C, obtain 1.764g powder, illustrate that the photocatalyst crystals contain
There are 20 crystallizations water.
1 nickel of table adulterates the icp analysis test result of heteropolyacid catalyst
| Element | H | Ni | Mo | F | O |
| Content (%) | 1.70 | 1.93 | 53.40 | 3.73 | 39.24 |
By the analysis test and experiment, it may be determined that the molecular formula of the doping heteropolyacid catalyst is：
H12NiMo17F6O55·20H2O。
Embodiment 3
The nickel doping heteropolyacid catalyst of embodiment 1 is carried out in the high-new scanning electron microscope SEM SU3500 of Hitachi
Analysis test, wherein each parameter is as follows, accelerating potential：20kV, enlargement ratio：25~200.000, resolution ratio：3.5nm, vacuum
Degree：6×10-6Pa.Fig. 2 is the SEM figures that nickel adulterates heteropolyacid catalyst, and nickel has been doped in layer structure as can be seen from Figure 2
Heteropoly acid group in, further confirm nickel be entrained in heteropolyacid catalyst.
Embodiment 4
In the cylindrical quartz Photoreactor of a 50ml, it is put into reactant mixed proportion and adulterates heteropoly acid catalysis for nickel
Agent: methanol solution: then deionized water=0.5-0.7g: 6mL: 20mL is removed by bubbling ultrapure argon continuous bubbling 30min
Dissolved oxygen.After stirring 15min under 1MPa air pressures, 200rpm, pass through the cut-off that light source is the special xenon lamps of visible ray PL-X300D
The irradiation and reaction of visible ray are carried out in the photochemical reactor of glass filter, reacts 4h, 0.5ml gases are extracted every 1h,
The H2 burst sizes of sample under quantitative determination different time are carried out by Japanese Shimadzu GC-2010 gas chromatographs, determination sample
Photocatalytic activity, Fig. 3 are reaction time-hydrogen conversion figures of nickel doping heteropolyacid catalyst.From figure 3, it can be seen that reaction
During to 4h, the conversion ratio of hydrogen is 15%, as time increases, H2Conversion ratio constantly increasing, reach more than 15%.
Claims (2)
1. a kind of doping heteropolyacid catalyst, it is characterised in that the preparation method of the catalyst is as follows：
1) it is Na by mixing ratio4SiMo12O40·2H2O: the mixed liquor of deionized water=44g: 100mL is heated to 80-85 DEG C；Add
Entering 14mL 40w%HF makes pH value maintain 4.5-5.0, which filters after stirring 1h at 200 rpm, obtains NaMoFOM filters
Liquid；
2) by the NaMoFOM filtrates and Ni (CH3COO)2Mixing, mixing ratio is filtrate: Ni (CH3COO)2=80mL: 7g, heating
Mixed liquor filters after stirring 1h at 200 rpm to 80-85 DEG C, obtains NaNiMoFOM filtrates；
3) the NaNiMoFOM filtrates 60mL is mixed with acetic acid, mixed volume ratio is filtrate: acetic acid=1: 2, heat mixed liquor
To 50-60 DEG C, 30min is stirred at 200 rpm, cools down, is placed in evaporative crystallization 2 days at room temperature, and it is miscellaneous more to obtain the i.e. nickel doping of crystal
Acid catalyst H12NiMo17F6O55·20H2O。
2. the method for carrying out photolysis water hydrogen gas using nickel as described in claim 1 doping heteropolyacid catalyst, feature exist
In comprising the following steps：
In the cylindrical quartz Photoreactor of a 50mL, it is put into reactant mixed proportion and adulterates heteropolyacid catalyst for nickel:
Methanol solution: then deionized water=0.5-0.7g: 6mL: 20mL is removed molten by bubbling ultrapure argon continuous bubbling 30min
Solve oxygen；After stirring 15min under 1MPa air pressures, 200rpm, pass through the cut-off glass that light source is the special xenon lamps of visible ray PL-X300D
The irradiation and reaction of visible ray are carried out in the photochemical reactor of glass filter, reacts 4h, 0.5mL gases is extracted every 1h, leads to
Cross the H2 burst sizes that Japan's Shimadzu GC-2010 gas chromatographs carry out sample under quantitative determination different time, the conversion ratio of hydrogen
Reach more than 15%.
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| CN112934262B (en) * | 2021-02-01 | 2021-10-26 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
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| EP2979757A1 (en) * | 2013-03-28 | 2016-02-03 | Nippon Kayaku Kabushiki Kaisha | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid |
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| EP2979757A1 (en) * | 2013-03-28 | 2016-02-03 | Nippon Kayaku Kabushiki Kaisha | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid |
| CN105032413A (en) * | 2015-01-07 | 2015-11-11 | 宁波工程学院 | Quick preparation method of Au-supported carbon nano-particles with visible light |
| CN105014093A (en) * | 2015-01-09 | 2015-11-04 | 宁波工程学院 | Preparation method for carbon nanoparticles with visible light loaded with Pt |
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