CN114768801A - Preparation method and application of supported palladium-gold alloy nanosheet catalyst - Google Patents
Preparation method and application of supported palladium-gold alloy nanosheet catalyst Download PDFInfo
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- CN114768801A CN114768801A CN202210450504.8A CN202210450504A CN114768801A CN 114768801 A CN114768801 A CN 114768801A CN 202210450504 A CN202210450504 A CN 202210450504A CN 114768801 A CN114768801 A CN 114768801A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 86
- 229910001020 Au alloy Inorganic materials 0.000 title claims abstract description 58
- 239000003353 gold alloy Substances 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 67
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 3
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QVJDTKXZVZTKLX-UHFFFAOYSA-K trichlorogold;triphenylphosphane Chemical compound Cl[Au](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QVJDTKXZVZTKLX-UHFFFAOYSA-K 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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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
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method and application of a supported palladium-gold alloy nanosheet catalyst, wherein the method comprises the following steps: pouring the reaction liquid and the reaction powder into a thick-wall pressure-resistant bottle and uniformly stirring to obtain a precursor liquid; placing the precursor solution in an oil bath, uniformly stirring, and introducing carbon monoxide to generate palladium nanosheets; adding the palladium nanosheet into a mixed solution of N, N-dimethylformamide and hydrazine hydrate, uniformly mixing, and adding a gold element to generate a palladium-gold alloy nanosheet; mixing the palladium-gold alloy nanosheet with a load and carrying out dispersion treatment to generate a catalyst precursor; and sequentially carrying out drying treatment and annealing treatment on the catalyst precursor to obtain the supported palladium-gold alloy nanosheet catalyst. The preparation method and the application provided by the invention have the advantages of low cost, high conversion rate and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a preparation method and application of a supported palladium-gold alloy nanosheet catalyst.
Background
With the large consumption of fossil energy sources such as non-renewable coal, petroleum and ore, methane gradually occupies an important position in the world energy structure by virtue of the advantages of abundant reserves, low price and the like; methane can be directly used as clean fuel, and is a C1 raw material of olefin, aromatic hydrocarbon and small molecular alcohol with high added value in a plurality of industries. Methanol is an important chemical raw material for synthesizing various organic products, exists in a liquid state at normal temperature, and is easy to store and transport.
Because of the high stability and weak polarity of C-H bond in methane molecule and extremely high bond energy, the conversion from methane to methanol is mainly realized by a Fischer-Tropsch reaction indirect method in the current industry, the reaction time is too long, the conversion rate is low, and the production cost is high; in addition, the activated methane C-H bond is easily oxidized into a large amount of carbon dioxide, which causes adverse effects on the environment. Therefore, how to realize efficient direct conversion of methane into methanol under mild conditions has become one of the hot spots of research.
Disclosure of Invention
The invention provides a preparation method and application of a supported palladium-gold alloy nanosheet catalyst, which are used for overcoming at least one technical problem in the prior art.
According to a first aspect of embodiments of the present invention, there is provided a method of preparing a supported palladium-gold alloy nanosheet catalyst, comprising: pouring the reaction liquid and the reaction powder into a thick-wall pressure-resistant bottle and uniformly stirring to obtain a precursor liquid; placing the precursor solution in an oil bath, uniformly stirring, and introducing carbon monoxide to generate palladium nanosheets; adding the palladium nanosheet into a mixed solution of N, N-Dimethylformamide (DMF) and hydrazine hydrate, uniformly mixing, and adding a gold element to generate a palladium-gold alloy nanosheet; putting the palladium-gold alloy nanosheet into ultrasonic water for dispersion treatment, adding a load, mixing and then performing dispersion treatment to generate a catalyst precursor; and sequentially carrying out drying treatment and annealing treatment on the catalyst precursor to obtain the supported palladium-gold alloy nanosheet catalyst.
Optionally, the reaction solution comprises ionized water and N, N-Dimethylformamide (DMF); the reaction powder comprises palladium acetylacetonate, a precursor and an active agent.
Optionally, the precursor is acetylacetone salt or polyvinylpyrrolidone (PVP); the active agent is any one of long-chain bromine-containing anionic surfactant, sodium chloride (NaCl), sodium bromide (NaBr) and sodium iodide (NaI).
Optionally, the acetylacetone salt is a noble metal acetylacetone salt or a non-noble metal acetylacetone salt; the molecular weight of the polyvinylpyrrolidone (PVP) is comprised in the range of 3000-; the long-chain bromine-containing anionic surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB) or tetrabutylammonium bromide.
Optionally, the volume ratio of the mixed solution of N, N-Dimethylformamide (DMF) and hydrazine hydrate is 1: 3-10: 1.
optionally, the load is any one of a molecular sieve, a metal oxide, a metal sulfide and carbon.
Optionally, the step of dispersing the palladium-gold alloy nanosheet in ultrasonic water, adding a load, mixing, and then dispersing to generate a catalyst precursor specifically includes; and (3) placing the palladium-gold alloy nanosheet into ultrasonic water for dispersing for 30-60 minutes, adding a load, mixing, and dispersing for 30-60 minutes to obtain a catalyst precursor.
According to a second aspect of embodiments of the invention, a use of a supported palladium-gold alloy nanosheet catalyst comprises: adding a preset supported palladium-gold alloy nanosheet catalyst into water, and uniformly mixing by using ultrasound to generate a catalytic liquid; adding the catalytic liquid into a high-pressure reaction kettle, and flushing the reaction kettle for multiple times by using methane mixed gas until the pressure in the reaction kettle reaches 0.1-0.5MPa, so that the methane mixed gas is fully filled into the reaction kettle; and fully reacting the mixed gas containing the methane with the catalytic liquid, and obtaining the methanol after the temperature reaches the reaction temperature at a certain speed from room temperature.
Optionally, in the step of obtaining methanol after the temperature reaches the reaction temperature at a certain rate from room temperature, the reaction is continued for 0.1 to 48 hours after the temperature reaches the reaction temperature at a certain rate from room temperature, so as to obtain methanol.
Optionally, the ratio of the supported palladium-gold alloy nanosheet catalyst to water is in the range of 1: 1-1: 10.
the innovation points of the embodiment of the invention comprise that:
1. according to the embodiment of the invention, the precursor solution is stirred at high temperature to generate palladium nanosheets, the palladium nanosheets and gold elements react to generate palladium-gold alloy nanosheets, the palladium-gold alloy nanosheets are placed in ultrasonic water to be dispersed, and then a load is added to be mixed to obtain a catalyst precursor; then, carrying out drying annealing treatment on the catalyst precursor to finally obtain a supported palladium-gold alloy nanosheet catalyst; the preparation method has the advantages of simple operation, loose reaction conditions, easily obtained reaction equipment, less material consumption in the whole preparation process and environmental protection. Is one of the innovative points of the embodiment of the invention.
2. According to the embodiment of the invention, the catalyst is added into water to be mixed to generate the catalytic liquid, so that the methane mixed gas and the catalytic liquid are fully reacted to directly generate the methanol, the reaction time is low, the conversion rate is high, the production cost of the methanol is reduced, and the application is very high. Is one of the innovative points of the embodiment of the invention.
3. According to the embodiment of the invention, the methanol is directly generated from the methane mixed gas through the catalyst, the generated carbon dioxide amount is low, the energy consumption is low, and no adverse effect is caused on the natural environment. Is one of the innovative points of the embodiment of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow schematic of a method of preparing a supported palladium-gold alloy nanosheet catalyst of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of an ultrathin palladium nanosheet produced by an embodiment of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of an ultrathin Pd-Au nanosheet fabricated in an embodiment of the present invention;
fig. 4 is a schematic flow chart of the application of the supported palladium-gold alloy nanosheet catalyst of the present invention in the direct conversion of methane to methanol.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified. The materials, reagents and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1:
this example provides a preparation method of a supported palladium-gold alloy nanosheet catalyst, and referring to fig. 1, fig. 1 is a process flow diagram of the preparation method of the supported palladium-gold alloy nanosheet catalyst of the present invention. As shown in fig. 1, the preparation method of the supported palladium-gold alloy nanosheet catalyst comprises the following steps:
step 101, pouring the reaction liquid and the reaction powder into a thick-wall pressure-resistant bottle and uniformly stirring to obtain a precursor liquid.
And 102, placing the precursor solution in an oil bath, uniformly stirring, and introducing carbon monoxide to generate the palladium nanosheet.
103, adding the palladium nanosheet into a mixed solution of N, N-Dimethylformamide (DMF) and hydrazine hydrate, uniformly mixing, and adding a gold element to generate the palladium-gold alloy nanosheet.
And 104, putting the palladium-gold alloy nanosheet into ultrasonic water for dispersion treatment, adding a load, mixing, and then performing dispersion treatment to generate a catalyst precursor.
And 105, sequentially drying and annealing the catalyst precursor to obtain the supported palladium-gold alloy nanosheet catalyst.
According to the embodiment of the invention, the precursor solution is stirred at high temperature to generate palladium nanosheets, the palladium nanosheets and gold elements react to generate palladium-gold alloy nanosheets, the palladium-gold alloy nanosheets are placed in ultrasonic water to be dispersed, and then a load is added to be mixed to obtain a catalyst precursor; then, carrying out drying annealing treatment on the catalyst precursor to finally obtain a supported palladium-gold alloy nanosheet catalyst; the preparation method has the advantages of simple operation, loose reaction conditions, easily obtained reaction equipment, less material consumption in the whole preparation process and environmental protection.
Example 2:
the embodiment provides a preparation method of a supported palladium-gold alloy nanosheet catalyst, which comprises the following steps:
step 201, pouring reaction liquid and reaction powder into a thick-wall pressure-resistant bottle and uniformly stirring to obtain precursor liquid; and (3) placing the precursor solution in an oil bath, uniformly stirring, and introducing carbon monoxide to generate the palladium nanosheet.
Wherein the reaction liquid comprises ionized water and water; the reaction powder comprises palladium acetylacetonate, a precursor and an activator.
Further, the precursor is acetylacetone salt or polyvinylpyrrolidone (PVP); the acetylacetone salt is a noble metal acetylacetone salt or a non-noble metal acetylacetone salt, the noble metal acetylacetone salt is an acetylacetone salt containing platinum group metals (ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold), and the non-noble metal acetylacetone salt is an acetylacetone salt containing a metal of a subgroup element; the molecular weight of the polyvinylpyrrolidone (PVP) is comprised in the range of 3000-; the active agent can be any one of long-chain bromine-containing anionic surfactant, sodium chloride (NaCl), sodium bromide (NaBr) and sodium iodide (NaI), wherein the long-chain bromine-containing anionic surfactant can be Cetyl Trimethyl Ammonium Bromide (CTAB) or tetrabutylammonium bromide.
Further, the volume ratio of the ionized water to the N, N-Dimethylformamide (DMF) in the reaction solution is 1: 13-5: 1; the mass ratio of palladium acetylacetonate, precursor and active agent in the reaction powder is 1: 8: 12-5: 1: 1; the oil bath temperature is 45-200 ℃; the content of carbon monoxide makes the pressure of the thick-wall pressure-resistant bottle be 0.05-3 MPa.
Still further, the reaction solution further comprises a dispersant; the dispersant may be any one of N, N-Dimethylpropionamide (DMP), benzyl alcohol, and 2-phenylethylalcohol.
Step 203, adding the obtained palladium nanosheets into a mixed solution of N, N-Dimethylformamide (DMF) and hydrazine hydrate and uniformly mixing; alloy nanosheets with different molar ratios of palladium element to gold element are prepared by adding gold element.
And (3) carrying out the reaction at room temperature, wherein the volume ratio of the mixed solution of the N, N-Dimethylformamide (DMF) and the hydrazine hydrate is 1: 3-10: 1; wherein the molar ratio of the palladium element to the gold element is 1: 35-100: 1.
step 205, putting the palladium-gold alloy nanosheets into ultrasonic water for dispersing for 30-60 minutes, adding a load, mixing, and continuing to disperse for 30-60 minutes to obtain a catalyst precursor; and then drying the catalyst precursor for 6-12 hours, and then annealing the catalyst precursor to finally obtain the supported palladium-gold alloy nanosheet catalyst.
Specifically, the support may be any one of a molecular sieve, a metal oxide, a metal sulfide, and carbon.
The type of the molecular sieve can be any one of H-ZMS-5, SAPO-34, BEA and SBA-13; the metal oxide is various valence metal oxides containing any one element of IVB, VB, VIB, VIII, IB, IIB, IIIA or IVA groups; the metal sulfide is various valence state metal sulfide containing any one element of IVB, VB, VIB, VIII, IB, IIB, IIIA or IVA group; the carbon can be carbon powder or carbon rods, and the carbon powder can be XC-37 type carbon powder.
In the specific implementation process, the catalyst precursor is dried for 6-12 hours by placing the catalyst precursor into an air-blowing drying oven, and drying is performed at a temperature of 100-150 ℃.
In addition, the annealing treatment is carried out on the catalyst precursor, and in a specific implementation process, the dried catalyst is placed in a tubular furnace containing argon-hydrogen mixed gas for annealing; wherein the annealing temperature is 100-450 ℃, the annealing time is 1-12h respectively, and the volume percentage of argon and hydrogen in the argon-hydrogen mixed gas is 50: 30-99: 1.
according to the embodiment of the invention, the precursor solution is stirred at high temperature to generate palladium nanosheets, the palladium nanosheets and gold elements react to generate palladium-gold alloy nanosheets, and the palladium-gold alloy nanosheets are placed in ultrasonic water for dispersion and then added with a load for mixing to obtain a catalyst precursor; then, carrying out drying annealing treatment on the catalyst precursor to finally obtain a supported palladium-gold alloy nanosheet catalyst; the preparation method has the advantages of simple operation, loose reaction conditions, easily obtained reaction equipment, less material consumption in the whole preparation process and environmental protection.
Example 3:
the embodiment provides a preparation method of an ultrathin supported palladium-gold alloy nanosheet catalyst, as shown in fig. 2 and fig. 3, fig. 2 is a Transmission Electron Microscope (TEM) image of an ultrathin palladium nanosheet prepared in the embodiment of the present invention, and fig. 3 is a Transmission Electron Microscope (TEM) image of an ultrathin palladium-gold nanosheet prepared in the embodiment of the present invention; the preparation method comprises the following steps:
step 301, pouring the reaction liquid and the reaction powder into a thick-wall pressure-resistant bottle, and performing ultrasonic mixing uniformly for 0.5-2 hours to obtain a precursor liquid; placing the precursor liquid in an oil bath, uniformly stirring, introducing carbon monoxide, and reacting for 1-4 hours after the temperature of the oil bath is raised to 45-200 ℃; and generating ultrathin 45nm palladium nanosheets, wherein the palladium nanosheets are hexagonal palladium nanocrystals.
Wherein the reaction solution comprises ionized water and N, N-Dimethylformamide (DMF); the reaction powder comprises palladium acetylacetonate, polyvinylpyrrolidone (PVP) having a molecular weight of 29000, and tetrabutylammonium bromide.
Further, the volume ratio of the ionized water to the N, N-Dimethylformamide (DMF) in the reaction solution is 1: 13-5: 1; the mass ratio of palladium acetylacetonate, polyvinylpyrrolidone (PVP) and tetrabutylammonium bromide in the reaction powder is 1: 8: 12-5: 1: 1; the content of carbon monoxide is such that the pressure of the thick-walled pressure-resistant bottle is 0.05-3 MPa.
Still further, the reaction solution further comprises a dispersant; the dispersant can be N, N-dimethyl propionamide (DMP), or benzyl alcohol, or 2-phenethyl alcohol.
Step 303, adding the obtained palladium nanosheet into a mixed solution of N, N-Dimethylformamide (DMF) and hydrazine hydrate for ultrasonic uniform mixing; and finally, adding (triphenylphosphine) gold chloride to prepare the alloy nanosheets with different molar ratios of palladium element to gold element.
Specifically, the amount of the substance of the palladium nanosheet may first be determined by weighing with a balance; the amount of the (triphenylphosphine) gold chloride substance can be weighed by a balance, so that the content of the gold element can be finally determined through conversion; thus, alloy nanoplates of different molar ratios of palladium element to gold element can be prepared by adding different masses of (triphenylphosphine) gold chloride.
The reaction conditions in this step are to allow the mixture to stand at room temperature for 5 to 24 hours.
Wherein the volume ratio of the mixed solution of DMF and hydrazine hydrate is 1: 3-10: 1; wherein the molar ratio of the palladium element to the gold element is 1: 35-100: 1.
305, weighing 1-100mg of palladium-gold alloy nanosheets, dispersing in ultrasonic water for 30-60 minutes, then adding 25-800mg of SAPO-34 molecular sieve, mixing, and continuously dispersing in ultrasonic water for 30-60 minutes to obtain a catalyst precursor; then transferring the catalyst precursor to an air drying box with the preset temperature of 100-150 ℃ for drying treatment for 6-12 hours; and then annealing the catalyst precursor to finally obtain the supported palladium-gold alloy nanosheet catalyst.
In the annealing treatment of the catalyst precursor, in a specific implementation process, the dried catalyst is placed in a tube furnace containing argon-hydrogen mixed gas for annealing; wherein the annealing temperature is 100-450 ℃, and the annealing time is 1-12h respectively; in the argon-hydrogen mixed gas, the volume percentage of argon to hydrogen is 50: 30-99: 1.
according to the embodiment of the invention, the precursor solution is stirred at high temperature to generate palladium nanosheets, the palladium nanosheets and gold elements react to generate palladium-gold alloy nanosheets, and the palladium-gold alloy nanosheets are placed in ultrasonic water to be dispersed and then added with a load to be mixed to obtain a catalyst precursor; then, carrying out drying annealing treatment on the catalyst precursor to finally obtain a supported palladium-gold alloy nanosheet catalyst; the preparation method has the advantages of simple operation, loose reaction conditions, easily obtained reaction equipment, less material consumption in the whole preparation process and environmental protection.
Example 4:
the present embodiment provides an application process of a supported palladium-gold alloy nanosheet catalyst in the preparation of methanol through direct methane conversion, and referring to fig. 4, fig. 4 is a schematic flow chart of the application of the supported palladium-gold alloy nanosheet catalyst in the preparation of methanol through direct methane conversion. The application process of the supported palladium-gold alloy nanosheet catalyst in the direct conversion of methane to methanol as shown in fig. 4 comprises the following steps:
step 401, adding a preset supported palladium-gold alloy nanosheet catalyst into water, and uniformly mixing the catalyst with ultrasound to generate a catalytic liquid.
Wherein the proportion range of the supported palladium-gold alloy nanosheet catalyst to water is 1: 1-1: 10.
step 402, adding the catalytic liquid into a high-pressure reaction kettle, and flushing the reaction kettle for multiple times by using the methane mixed gas until the air pressure in the reaction kettle reaches 0.1-0.5 MPa; so that the methane mixed gas is fully filled into the reaction kettle.
In this step, the number of washing times is 2 to 5.
And 403, fully reacting the mixed gas containing the methane with the catalytic liquid, and obtaining the methanol after the temperature reaches the reaction temperature at a certain rate from room temperature.
In the step, after the temperature reaches the reaction temperature from room temperature at a certain rate, the reaction is continued for 0.1 to 48 hours to obtain methanol; in order to ensure that the methane mixed gas and the catalytic liquid are fully reacted, the reaction kettle can be rotated at a high speed, and the rotating speed is 800-1500/rpm; so that the catalyst solution kettle and the catalyst solution can be fully mixed under high-speed stirring.
Wherein the methane mixed gas consists of 1-60% hydrogen (H)2) 1-60% oxygen (O)2) 10-96% methane (CH)4) 1-60% argon (Ar) and 1-60% helium (He); the reaction temperature is 0-250 ℃.
As shown in table 1, the table shows the relationship between the content of a portion of the supported palladium-gold alloy nanosheet catalyst and the performance of the direct conversion of methane to methanol.
TABLE 1
| Serial number | Catalyst and process for producing the same | CH3OH(mmol) | Yield (mmoleh)-1) | Selectivity (%) | Methane conversion (%) |
| 1 | 1mg | 0.12 | 0.225 | 97 | 15 |
| 2 | 3mg | 0.17 | 0.33 | 97.5 | 20 |
| 3 | 5mg | 0.46 | 0.91 | 98.5 | 50 |
| 4 | 8mg | 0.49 | 0.97 | 99 | 60 |
| 5 | 10mg | 0.32 | 0.63 | 98 | 40 |
According to the embodiment of the invention, the catalyst is added into water to be mixed to generate the catalytic liquid, so that the methane mixed gas and the catalytic liquid are fully reacted to directly generate the methanol, the reaction time is low, the conversion rate is high, the production cost of the methanol is reduced, and the application is very high; the catalyst enables the methane mixed gas to directly generate the methanol, the generated carbon dioxide amount is low, the energy consumption is low, and no adverse effect is caused on the natural environment.
The foregoing describes the general principles of the present application in conjunction with specific embodiments, however, it is noted that the advantages, effects, etc. mentioned in the present application are merely examples and are not limiting, and they should not be considered essential to the various embodiments of the present application. Furthermore, the foregoing disclosure of specific details is for the purpose of illustration and description and is not intended to be limiting, since the foregoing disclosure is not intended to be exhaustive or to limit the disclosure to the precise details disclosed.
The block diagrams of devices, apparatuses, devices, systems referred to in this application are only used as illustrative examples and are not intended to require or imply that they must be connected, arranged, or configured in the manner shown in the block diagrams. These devices, apparatuses, devices, systems may be connected, arranged, configured in any manner, as will be appreciated by those skilled in the art. Words such as "including," "comprising," "having," and the like are open-ended words that mean "including, but not limited to," and are used interchangeably therewith. The words "or" and "as used herein mean, and are used interchangeably with, the word" and/or, "unless the context clearly dictates otherwise. The word "such as" is used herein to mean, and is used interchangeably with, the phrase "such as but not limited to".
It should also be noted that in the devices, apparatuses, and methods of the present application, each component or step can be decomposed and/or re-combined. These decompositions and/or recombinations are to be considered as equivalents of the present application.
The previous description of the disclosed aspects is provided to enable any person skilled in the art to make or use the present application. Various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects without departing from the scope of the application. Thus, the present application is not intended to be limited to the aspects shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The foregoing description has been presented for purposes of illustration and description. Furthermore, the description is not intended to limit embodiments of the application to the form disclosed herein. While a number of example aspects and embodiments have been discussed above, those of skill in the art will recognize certain variations, modifications, alterations, additions and sub-combinations thereof.
Claims (10)
1. A preparation method of a supported palladium-gold alloy nanosheet catalyst is characterized by comprising the following steps:
pouring the reaction liquid and the reaction powder into a thick-wall pressure-resistant bottle and uniformly stirring to obtain a precursor liquid;
placing the precursor solution in an oil bath, uniformly stirring, and introducing carbon monoxide to generate palladium nanosheets;
adding the palladium nanosheet into a mixed solution of N, N-Dimethylformamide (DMF) and hydrazine hydrate, uniformly mixing, and adding a gold element to generate a palladium-gold alloy nanosheet;
putting the palladium-gold alloy nanosheet into ultrasonic water for dispersion treatment, adding a load, mixing and then performing dispersion treatment to generate a catalyst precursor;
and sequentially carrying out drying treatment and annealing treatment on the catalyst precursor to obtain the supported palladium-gold alloy nanosheet catalyst.
2. The method of claim 1,
the reaction solution comprises ionized water and N, N-Dimethylformamide (DMF);
the reaction powder comprises palladium acetylacetonate, a precursor and an active agent.
3. The method of claim 2,
the precursor is acetylacetone salt or polyvinylpyrrolidone (PVP);
the active agent is any one of long-chain bromine-containing anionic surfactant, sodium chloride (NaCl), sodium bromide (NaBr) and sodium iodide (NaI).
4. The method of claim 3,
the acetylacetone salt is a noble metal acetylacetone salt or a non-noble metal acetylacetone salt;
the molecular weight of the polyvinylpyrrolidone (PVP) comprises a range of 3000-;
the long-chain bromine-containing anionic surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB) or tetrabutylammonium bromide.
5. The method of claim 1,
the volume ratio of the mixed solution of the N, N-Dimethylformamide (DMF) and the hydrazine hydrate is 1: 3-10: 1.
6. the method of claim 1,
the load is any one of molecular sieve, metal oxide, metal sulfide and carbon.
7. The method according to claim 1, wherein the step of dispersing the palladium-gold alloy nanosheets in ultrasonic water and after adding a support and mixing, generating a catalyst precursor comprises;
and (3) placing the palladium-gold alloy nanosheet into ultrasonic water for dispersing for 30-60 minutes, adding a load, mixing, and dispersing for 30-60 minutes to obtain a catalyst precursor.
8. Use of a supported palladium-gold alloy nanosheet catalyst, comprising:
adding a preset supported palladium-gold alloy nanosheet catalyst into water, and uniformly mixing by using ultrasound to generate a catalytic liquid;
adding the catalytic liquid into a high-pressure reaction kettle, and flushing the reaction kettle for multiple times by using methane mixed gas until the pressure in the reaction kettle reaches 0.1-0.5MPa, so that the methane mixed gas is fully filled into the reaction kettle;
and fully reacting the mixed gas containing the methane with the catalytic liquid, and obtaining the methanol after the temperature reaches the reaction temperature at a certain speed from room temperature.
9. The use according to claim 8, wherein in the step of reacting the mixed gas containing methane with the catalytic liquid sufficiently to obtain methanol after the temperature reaches the reaction temperature from room temperature at a certain rate,
after the temperature reached the reaction temperature at a certain rate from room temperature, the reaction was continued for 0.1 to 48 hours to obtain methanol.
10. Use according to claim 8,
the proportion range of the supported palladium-gold alloy nanosheet catalyst to water is 1: 1-1: 10.
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