CN113509929A - Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof - Google Patents
Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof Download PDFInfo
- Publication number
- CN113509929A CN113509929A CN202110401258.2A CN202110401258A CN113509929A CN 113509929 A CN113509929 A CN 113509929A CN 202110401258 A CN202110401258 A CN 202110401258A CN 113509929 A CN113509929 A CN 113509929A
- Authority
- CN
- China
- Prior art keywords
- formic acid
- catalyst
- preparation
- catalyzing
- porous palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 25
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 22
- 239000012498 ultrapure water Substances 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000002077 nanosphere Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 6
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 palladium ions Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
-
- 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
- C01B2203/1064—Platinum group metal 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
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and a preparation method thereof, wherein the chemical structural formula of the catalyst is xPd CeO2(x is more than or equal to 0 and less than or equal to 10). The catalyst is chloropalladic acid, cerium chloride and propanetriolAlcohol is used as raw material. The method has the advantages of cheap and easily-obtained raw materials, mild experimental conditions, simple preparation process, environmental protection, and good scientific significance and important application prospect. The palladium-based nano-spherical catalyst prepared by the method has a uniform nano-spherical structure. The catalyst can effectively catalyze the liquid-phase formic acid to decompose and generate hydrogen at 40 ℃, and simultaneously shows higher hydrogen selectivity, and no secondary pollution is caused by CO generation in the reaction process.
Description
Technical Field
The invention belongs to the field of nano material preparation and catalytic application, and particularly relates to a porous palladium-based nano spherical catalyst for catalyzing formic acid to generate hydrogen and a preparation method thereof.
Background
With the increase of the world population and the improvement of the living standard of people, the consumption of energy also increases sharply. Under the current situation of energy shortage, various renewable energy sources such as nuclear power, wind energy, solar energy, hydroelectric power and the like are developed and utilized on a large scale. However, the effective utilization of the above energy has strong regional diversity due to the imbalance of regional climate, production cost, economic development level, etc. in different countries. As the most abundant element in the universe, the hydrogen has very high mass energy density and can be used as an ideal novel energy carrier. Hydrogen has the following remarkable characteristics: (1) the combustion heat value is up to 143.5MJ/kg, which is 3 times of gasoline, 4 times of ethanol and 4.5 times of coke; (2) the combustion of hydrogen is a clean process, the only combustion product of which is water; (3) rich resources and wide sources, and conforms to the characteristics of sustainable development. The hydrogen can generate renewable energy sources such as hydroelectric energy, wind energy, solar energy, biomass energy and the like or non-renewable energy sources such as coal, crude oil, natural gas and the like from various energy sources; (4) the hydrogen storage device is easy to store, and hydrogen can be obtained by the traditional modes of low-temperature liquid hydrogen storage, high-pressure tank hydrogen storage and the like and also by the modes of absorbing and storing hydrogen by novel materials such as MOFs and the like.
Formic acid is the simplest carboxylic acid, is a colorless transparent liquid with strong pungent odor at room temperature, and can be mutually dissolved with most organic solvents such as water, ethylene, benzene and the like. Although the available net hydrogen content (4.4 wt%) of formic acid is low, formic acid has the characteristics of difficult volatilization, no toxicity, difficult combustion, simple combustion product, no pollution to the environment and the like, and is an ideal chemical hydrogen storage material. In theory, formic acid can be decomposed in two ways:
HCOOH(l)→H2(g)+CO2(g),ΔG298＝-48.4kJ/mol (1)
HCOOH(l)→H2O(l)+CO(g),ΔG298＝-28.5kJ/mol (2)
dehydrogenation of formic acid to H2And CO2(mode 1) dehydration to H2O and CO (mode 2). CO formed during dehydrogenation2The formic acid can be converted again through reversible hydrogenation reaction, so that a carbon neutralization energy storage system is established, and the effective circulation and utilization of energy are realized.
Catalyst systems for catalyzing liquid-phase formic acid to generate hydrogen are multiple, and noble metal catalysts (Pd, Pt and Au) and metal oxides thereof show excellent performance in the process of catalyzing formic acid to generate hydrogen. Based on the strong interaction between the metal and the carrier between the palladium and the cerium and the rich lattice oxygen in the cerium oxide, Pd/CeO2The catalyst shows excellent stability and catalytic activity. The high catalytic activity of noble metal systems is mainly determined by the mode of interaction (encapsulation, doping, loading, etc.) between the metal and the support, which directly affects the highly dispersed noble metal ions on the surface and in the bulk of the support. In addition, the acidity and basicity of the support also have a large influence on the reactivity and selectivity of the catalyst. Acidic oxides favor the dehydration of formic acid, while basic oxides favor the evolution of hydrogen from formic acid. Therefore, the basic oxide cerium oxide is used as a noble metal carrier to promote hydrogen evolution from formic acid.
Disclosure of Invention
The invention aims to provide a porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and a preparation method thereof.
The invention is realized by adopting the following technical scheme:
a preparation method of a porous palladium-based nanosphere catalyst for catalyzing formic acid to evolve hydrogen comprises the following steps:
1) in 5mL of ultrapure water, the proportion is (0.5-2) mol: (0.3-1) mol: (20-80) mL CeCl was added successively3·6H2O, PVP and glycerol, transferring the sample to a high-pressure reaction kettle, reacting at 180 ℃ and 200 ℃ for 3-5h, and finally cooling to room temperature to obtain a light purple product;
2) collecting the light purple product obtained in the step 1) by using a high-speed centrifuge, cleaning and drying to obtain a cerium-based nano spherical material;
3) grinding the cerium-based nano spherical material obtained in the step 2), putting the ground powder solid into ultrapure water for mixing and dissolving, and adding 0.8-2mol/L H2PdCl4Water solution to obtain mixed solution;
4) dropwise adding 1-3mol/L Na into the mixed solution obtained in the step 3) under the condition of continuous stirring2CO3Controlling the pH value of the aqueous solution to be 7-10, and standing to room temperature to obtain precipitate mixed liquor;
5) filtering the mixed solution of the precipitate obtained in the step 4), washing, drying, and calcining at the high temperature of 400-650 ℃ to obtain the porous palladium-based nanosphere catalyst for catalyzing formic acid to separate hydrogen.
The further improvement of the invention is that in the step 1), magnetic stirring is carried out for 10-20 min.
The further improvement of the invention is that in the step 2), ultrapure water and absolute ethyl alcohol are adopted for washing for 3 times in sequence during cleaning, and the obtained product is dried in a drying oven at the temperature of 60-80 ℃ for later use.
A further development of the invention is that drying is carried out using a forced air drying cabinet.
The invention is further improved in that, in the step 3), the cerium-based nano material is ground to 40-80 meshes.
A further development of the invention is that, in step 3), H is added2PdCl4In the case of an aqueous solution, Pd: the molar ratio of Ce is 1-10.
The invention further relates toIn step 3), Na2CO3The concentration of the aqueous solution is 1 to 3 mol/L.
The further improvement of the invention is that in the step 5), when the precipitate is washed, ultrapure water and absolute ethyl alcohol are adopted to wash for 3 times in sequence so as to achieve the purpose of removing impurities on the surface of the catalyst; the washed precipitated product was dried for at least 5h while drying the precipitated product at 150 ℃.
The porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen is prepared by the preparation method.
Compared with the prior art, the invention has at least the following beneficial technical effects:
the invention provides a porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and a preparation method thereof, and palladium particles can be selectively loaded and deposited. 10Pd CeO prepared during heating in a water bath at 40 DEG C2The gas production of the catalyst reached 102mL at 15 min. Accompanied by the increase of the loading of the noble metal palladium, Pd CeO2The amount of hydrogen evolution of the formic acid catalyzed by the catalyst increases. Meanwhile, no CO is generated in the whole reaction process, and high hydrogen selectivity is shown.
The invention provides a porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and a preparation method thereof3+Reduction to Ce4+Meanwhile, high valence metal palladium ions in the solution are reduced into palladium particles, so that the reaction activity of the catalyst is improved. The method is simple and easy to implement, the preparation conditions are mild, the raw materials are cheap and easy to obtain, and no toxic reaction raw materials exist in the preparation process, so that the catalyst is an environment-friendly green synthetic catalyst.
Drawings
FIG. 1 is a diagram of a catalyst prepared according to the present invention 2xPd*CeO(x＝0,510) XRD pattern of the catalyst;
FIG. 2 is a diagram of a catalyst prepared according to the present invention 2xPd*CeO(x＝0,510) pore volume distribution profile of the catalyst;
FIG. 3 is a graph of a polymer prepared according to the present invention 20Pd*CeOTransmission electron micrograph of catalyst;
FIG. 4 is a graph of a polymer prepared according to the present invention 2xPd*CeO(x＝0,5And 10) catalyzing the hydrogen evolution pattern of the formic acid by the catalyst.
Detailed Description
The present invention is further illustrated by the following examples and figures, including but not limited to the following examples.
The invention relates to a preparation method of a porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen, which comprises the following steps:
(1) 0.5mol of CeCl is weighed out3·6H2Dissolving 0.3mol of polyvinylpyrrolidone (PVP) and 80mL of glycerol in 5mL of ultrapure water, stirring to prepare a mixed solution, and magnetically stirring for 10 min; (2) transferring the mixed solution obtained in the step (1) to a 100mL high-pressure reaction kettle, sealing, and reacting for 3h at 180 ℃; (3) washing the precipitation product obtained in the step (2) with ultrapure water for 3 times, and drying in a drying oven at 60 ℃ overnight; (4) grinding the product obtained in the step (3) to 60 meshes by using an agate mortar, putting the ground product into ultrapure water, mixing and dissolving the ground product, and adding a proper amount of H2PdCl4A solution; (5) slowly adding Na into the mixed solution obtained in the step (4) under the condition of continuous stirring2CO3Controlling the pH value of the solution to be 7; (6) and (3) filtering the precipitate mixed liquor obtained in the step (5), then filtering with ultrapure water and absolute ethyl alcohol, washing, drying, and calcining at a high temperature of 400 ℃ to obtain the material, namely the porous palladium-based nanosphere catalyst for catalyzing formic acid to generate hydrogen.
The first embodiment is as follows:
(1) weighing 2mol of CeCl3·6H2Dissolving 1mol of polyvinylpyrrolidone (PVP) and 20mL of glycerol in 5mL of ultrapure water, stirring until the PVP and the glycerol are completely dissolved, and magnetically stirring for 20 min; transferring the mixed solution into a 100mL high-pressure reaction kettle, sealing, and reacting for 5h at 200 ℃; then washed 3 times with ultrapure water and dried in a drying oven at 80 ℃ for later use.
(2) Grinding the product obtained in the step (1) to 40 meshes by using an agate mortar, putting the product into ultrapure water for mixing and dissolving, and then slowly adding 1mol/L Na into the mixed solution2CO3Controlling the pH value of the solution to be 7.
(3) Standing to room temperature, and obtaining the product in the step (2)The obtained solution is filtered by a vacuum pump, washed, dried, calcined at 650 ℃ and cooled to room temperature, and then taken out, and the obtained sample is the porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen, which is called 0Pd CeO for short2. FIG. 3 is a transmission electron micrograph of the prepared sample, from which it can be seen that the diameter of the synthetic nanospheres is about 80-200 nm.
Example two:
(1) 0.5mol of CeCl is weighed out3·6H2Dissolving 0.3mol of polyvinylpyrrolidone (PVP) and 80mL of glycerol in 5mL of ultrapure water, and then stirring until the mixture is completely dissolved; transferring the mixed solution into a 100mL high-pressure reaction kettle, sealing, and reacting for 3h at 200 ℃; then washed 3 times with ultrapure water and dried in a drying oven at 60 ℃ for later use.
(2) Grinding the product obtained in the step (1) to 80 meshes by using an agate mortar, putting the ground product into ultrapure water, mixing and dissolving the ground product, and adding a proper amount of H2PdCl4An aqueous solution (Ce: Pd ═ 5: 1), and then 3mol/L Na was slowly added to the mixed solution2CO3Controlling the pH value of the solution to be 10.
(3) Standing to room temperature, performing suction filtration on the solution obtained in the step (2) by using a vacuum pump, filtering, washing, drying, calcining at the high temperature of 500 ℃ to reduce the temperature to room temperature, and taking out the solution to obtain a sample, namely the porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen, namely 5Pd (CeO) for short2. FIG. 1 is an XRD pattern of the prepared sample, from which it can be seen that Pd enters CeO2Porous palladium-based nano-spherical composite oxide materials are formed in the crystal lattices.
Example three:
(1) weighing 2mol of CeCl3·6H2Dissolving 1mol of polyvinylpyrrolidone (PVP) and 50mL of glycerol in 5mL of ultrapure water, and then stirring until the mixture is completely dissolved; transferring the mixed solution into a 100mL high-pressure reaction kettle, sealing, and reacting for 4h at 200 ℃; then washed 3 times with ultrapure water and dried in a drying oven at 80 ℃ for later use.
(2) Grinding the product obtained in the step (1) to 50 meshes by using an agate mortar, putting the ground product into ultrapure water, mixing and dissolving the ground product, and adding a proper amount of H2PdCl4An aqueous solution (Ce: Pd: 10: 1) was added to the mixed solution graduallySlowly adding 1.5mol/L Na2CO3Controlling the pH value of the solution to be 9.
(3) Standing to room temperature, performing suction filtration on the solution obtained in the step (2) by using a vacuum pump, filtering, washing, drying, calcining at the high temperature of 500 ℃ to reduce the temperature to room temperature, and taking out the solution to obtain a sample, namely the porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen, which is called 10Pd (CeO) for short2. Fig. 2 is a graph of pore volume distribution curve of the prepared sample, from which it can be seen that the prepared sample has uniform distribution of macropores, mesopores and micropores.
Example four:
the porous palladium-based nano-sphere catalysts prepared in the first, second and third examples are respectively used for catalyzing the hydrogen evolution reaction of liquid-phase formic acid, a proper amount of catalyst and ultrapure water are poured into a 100mL round-bottom flask, and the flask is placed into a water bath kettle with the reaction temperature of 40 ℃. The round-bottom flask was connected to a reflux tube and a gas burette, and the generated gas was collected to measure the gas volume. Finally, an appropriate amount of formic acid solution was injected into the flask via syringe. The gas generated after the reaction is used for detecting gas components by a gas chromatograph, the selectivity of hydrogen reaches 100 percent, and no secondary pollution is caused by CO generation. FIG. 4 shows a hydrogen evolution diagram of a prepared sample, catalyst 10Pd CeO2The catalytic activity of (2) is the best, and the gas production (CO) is within 15min2+H2) Up to 102mL, which is associated with Pd and CeO2The synergistic promotion effect of the carrier, rich Pd active sites and the Pd-based nano spherical structure are related.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A preparation method of a porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen is characterized by comprising the following steps:
1) in 5mL of ultrapure water, the proportion is (0.5-2) mol:(0.3-1) mol: (20-80) mL CeCl was added successively3·6H2O, PVP and glycerol, transferring the sample to a high-pressure reaction kettle, reacting at 180 ℃ and 200 ℃ for 3-5h, and finally cooling to room temperature to obtain a light purple product;
2) collecting the light purple product obtained in the step 1) by using a high-speed centrifuge, cleaning and drying to obtain a cerium-based nano spherical material;
3) grinding the cerium-based nano spherical material obtained in the step 2), putting the ground powder solid into ultrapure water for mixing and dissolving, and adding 0.8-2mol/L H2PdCl4Water solution to obtain mixed solution;
4) dropwise adding 1-3mol/L Na into the mixed solution obtained in the step 3) under the condition of continuous stirring2CO3Controlling the pH value of the aqueous solution to be 7-10, and standing to room temperature to obtain precipitate mixed liquor;
5) filtering the mixed solution of the precipitate obtained in the step 4), washing, drying, and calcining at the high temperature of 400-650 ℃ to obtain the porous palladium-based nanosphere catalyst for catalyzing formic acid to separate hydrogen.
2. The preparation method of the porous palladium-based nanosphere catalyst for catalyzing hydrogen evolution from formic acid according to claim 1, wherein in the step 1), the magnetic stirring is carried out for 10-20 min.
3. The preparation method of the porous palladium-based nanosphere catalyst for catalyzing formic acid to evolve hydrogen according to claim 1, wherein in the step 2), ultrapure water and absolute ethyl alcohol are adopted for washing for 3 times in sequence during cleaning, and the obtained product is dried in a drying oven at 60-80 ℃ for later use.
4. The preparation method of the porous palladium-based nanosphere catalyst for catalyzing hydrogen evolution from formic acid according to claim 3, wherein drying is performed by using an air-blast drying oven.
5. The method for preparing the porous palladium-based nanosphere catalyst for catalyzing hydrogen evolution from formic acid as defined in claim 1, wherein in the step 3), the cerium-based nanomaterial is ground to 40-80 mesh.
6. The preparation method of the porous palladium-based nanosphere catalyst for catalyzing hydrogen evolution from formic acid according to claim 1, wherein in the step 3), H is added2PdCl4In the case of an aqueous solution, Pd: the molar ratio of Ce is 1-10.
7. The preparation method of the porous palladium-based nanosphere catalyst for catalyzing hydrogen evolution from formic acid as claimed in claim 1, wherein in step 3), Na is added2CO3The concentration of the aqueous solution is 1 to 3 mol/L.
8. The preparation method of the porous palladium-based nanosphere catalyst for catalyzing formic acid to evolve hydrogen according to claim 1, wherein in the step 5), when precipitates are washed, ultrapure water and absolute ethyl alcohol are adopted to wash for 3 times in sequence so as to achieve the purpose of removing impurities on the surface of the catalyst; the washed precipitated product was dried for at least 5h while drying the precipitated product at 150 ℃.
9. The porous palladium-based nanosphere-type catalyst for catalyzing hydrogen evolution from formic acid prepared by the preparation method of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110401258.2A CN113509929A (en) | 2021-04-14 | 2021-04-14 | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110401258.2A CN113509929A (en) | 2021-04-14 | 2021-04-14 | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113509929A true CN113509929A (en) | 2021-10-19 |
Family
ID=78062550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110401258.2A Pending CN113509929A (en) | 2021-04-14 | 2021-04-14 | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113509929A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115069267A (en) * | 2022-06-02 | 2022-09-20 | 厦门固洛璞科技有限公司 | Perovskite-based catalyst for hydrogen production from formic acid and preparation method and application thereof |
| CN115888740A (en) * | 2022-11-10 | 2023-04-04 | 西安交通大学 | Spherical iron-based metal catalyst for catalyzing ammonia gas to produce hydrogen and preparation method thereof |
| CN115069267B (en) * | 2022-06-02 | 2024-06-07 | 厦门固洛璞科技有限公司 | Perovskite-based formic acid hydrogen production catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071492A (en) * | 2012-12-07 | 2013-05-01 | 内蒙古大学 | Preparation method of efficient formaldehyde catalytic conversion catalyst |
| CN107456965A (en) * | 2017-06-21 | 2017-12-12 | 浙江大学 | It is a kind of using cerium oxide as load type palladium catalyst of carrier and preparation method thereof |
| CN108126695A (en) * | 2017-12-29 | 2018-06-08 | 吉林大学 | A kind of functionalized carbon nano-tube supported palladium nanocatalyst and its preparation and application |
| CN108465466A (en) * | 2018-03-20 | 2018-08-31 | 福州大学 | A kind of spheric catalyst and preparation method thereof of ceria package Pd |
| CN111054333A (en) * | 2020-02-14 | 2020-04-24 | 郑州轻工业大学 | Hydrotalcite-supported palladium catalyst for preparing styrene by selective hydrogenation of phenylacetylene, and preparation method and application thereof |
| CN111346677A (en) * | 2020-01-09 | 2020-06-30 | 西南民族大学 | Preparation method of palladium/amino-rich porous polymer catalyst for preparing hydrogen by catalyzing self-decomposition of formic acid |
| CN112547094A (en) * | 2021-01-04 | 2021-03-26 | 济南大学 | Preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres |
-
2021
- 2021-04-14 CN CN202110401258.2A patent/CN113509929A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071492A (en) * | 2012-12-07 | 2013-05-01 | 内蒙古大学 | Preparation method of efficient formaldehyde catalytic conversion catalyst |
| CN107456965A (en) * | 2017-06-21 | 2017-12-12 | 浙江大学 | It is a kind of using cerium oxide as load type palladium catalyst of carrier and preparation method thereof |
| CN108126695A (en) * | 2017-12-29 | 2018-06-08 | 吉林大学 | A kind of functionalized carbon nano-tube supported palladium nanocatalyst and its preparation and application |
| CN108465466A (en) * | 2018-03-20 | 2018-08-31 | 福州大学 | A kind of spheric catalyst and preparation method thereof of ceria package Pd |
| CN111346677A (en) * | 2020-01-09 | 2020-06-30 | 西南民族大学 | Preparation method of palladium/amino-rich porous polymer catalyst for preparing hydrogen by catalyzing self-decomposition of formic acid |
| CN111054333A (en) * | 2020-02-14 | 2020-04-24 | 郑州轻工业大学 | Hydrotalcite-supported palladium catalyst for preparing styrene by selective hydrogenation of phenylacetylene, and preparation method and application thereof |
| CN112547094A (en) * | 2021-01-04 | 2021-03-26 | 济南大学 | Preparation method of palladium in-situ modified copper-cobalt doped cerium dioxide nanospheres |
Non-Patent Citations (1)
| Title |
|---|
| A. GAZSI ET AL.: "Decomposition and Reforming of Formic Acid on Supported Au Catalysts: Production of CO-Free H2", 《THE JOURNAL OF PHYSICAL CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115069267A (en) * | 2022-06-02 | 2022-09-20 | 厦门固洛璞科技有限公司 | Perovskite-based catalyst for hydrogen production from formic acid and preparation method and application thereof |
| CN115069267B (en) * | 2022-06-02 | 2024-06-07 | 厦门固洛璞科技有限公司 | Perovskite-based formic acid hydrogen production catalyst and preparation method and application thereof |
| CN115888740A (en) * | 2022-11-10 | 2023-04-04 | 西安交通大学 | Spherical iron-based metal catalyst for catalyzing ammonia gas to produce hydrogen and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110752380A (en) | ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof | |
| CN103566934A (en) | Carbon dioxide electrochemical-reduction catalyst, and preparation and application thereof | |
| CN111151285B (en) | Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof | |
| CN114570429B (en) | Single-atom-loaded covalent organic framework material, preparation thereof and application thereof in hydrogen production by photolysis of water | |
| CN112495401A (en) | Mo-doped MoO3@ZnIn2S4Z-system photocatalyst and preparation method and application thereof | |
| CN109046431A (en) | Spherical N doping zinc sulphide compound carbonizing titanium photochemical catalyst and preparation method thereof and the application in hydrogen is prepared in photochemical catalyzing | |
| Wang et al. | Noble‐metal‐free MOF derived ZnS/CeO2 decorated with CuS cocatalyst photocatalyst with efficient photocatalytic hydrogen production character | |
| CN111041508A (en) | Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof | |
| WO2012109846A1 (en) | Methods for preparation and use of catalyst for hydrazine degradation | |
| CN113509929A (en) | Porous palladium-based nano spherical catalyst for catalyzing formic acid to evolve hydrogen and preparation method thereof | |
| CN113578387B (en) | Method for electrostatic spinning self-assembled lignin-loaded zirconium hybrid material and application | |
| CN111203219B (en) | Copper-based catalyst for preparing formic acid from carbon dioxide, preparation method and application | |
| CN113265061A (en) | Preparation method and application of Ru/Cu-BTC metal organic framework material | |
| CN110508324B (en) | Co-Zn bimetal organic skeleton electrocatalytic oxygen evolution material and preparation method thereof | |
| CN115463667B (en) | Preparation method of composite photocatalytic nitrogen fixation material with iridium loaded by cuprous oxide of different crystal planes | |
| CN116173987A (en) | CdIn 2 S 4 /CeO 2 Heterojunction photocatalyst, preparation method and application thereof | |
| CN103252248A (en) | Preparation method of ordered mesoporous non-noble-metal-nitrogen-graphitized carbon material | |
| CN112760674B (en) | System and method for synthesizing ammonia and acetone in one step by electrochemical reduction at normal temperature and normal pressure | |
| CN113070062B (en) | Cerium-based nano-sphere catalyst for catalyzing formic acid to produce hydrogen and preparation method thereof | |
| CN115301294A (en) | Indium-zinc sulfide modified iron-based metal organic framework, preparation method thereof and application thereof in adsorption-photocatalyst | |
| CN114602512A (en) | Preparation method of esterification reaction catalyst | |
| CN110975860B (en) | Chromium-doped titanium-oxygen cluster nano catalytic material, preparation method and application | |
| CN110721743B (en) | Methane-producing atomic-level dispersed copper @ covalent triazine organic polymer composite photocatalyst and preparation and application thereof | |
| CN108465464B (en) | Preparation method and application of barium strontium titanate/bismuth vanadate | |
| CN112570030A (en) | Bi4O5Br2Preparation method and application of/Fe-MIL composite material photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211019 |