CN117282425A - Carbon-supported palladium gold nano heterogeneous catalyst, preparation method and application - Google Patents
Carbon-supported palladium gold nano heterogeneous catalyst, preparation method and application Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 81
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 60
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000000725 suspension Substances 0.000 claims abstract description 62
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 34
- 235000019253 formic acid Nutrition 0.000 claims abstract description 31
- 239000001509 sodium citrate Substances 0.000 claims abstract description 30
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 30
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000012696 Pd precursors Substances 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- BCEOEOBICHVYDJ-UHFFFAOYSA-M sodium;formic acid;formate Chemical compound [Na+].OC=O.[O-]C=O BCEOEOBICHVYDJ-UHFFFAOYSA-M 0.000 claims 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 239000004280 Sodium formate Substances 0.000 claims 1
- 239000006229 carbon black Substances 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims 1
- 235000019254 sodium formate Nutrition 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 11
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract description 2
- 229910001020 Au alloy Inorganic materials 0.000 abstract 1
- 239000003353 gold alloy Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 210000000056 organ Anatomy 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000037361 pathway Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005230 valence electron density Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WERQQWICVQUZHF-UHFFFAOYSA-M sodium formate dihydrate Chemical compound O.O.[Na+].[O-]C=O WERQQWICVQUZHF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a carbon-supported palladium-gold nano heterogeneous catalyst, a preparation method and application thereof, wherein the catalyst consists of a carbon carrier and active component palladium-gold alloy nano particles, the total metal loading amount is 3.0-15.0 wt%, wherein the palladium is 0.46-9.28 wt% and the gold is 1.14-12.71 wt%. The method comprises the following steps: 1) Dispersing a carbon carrier in water to obtain a suspension A; 2) Adding chloroauric acid into a sodium citrate solution to prepare a suspension B; 3) Adding chloropalladate into the sodium citrate solution to prepare solution C; 4) Adding the suspension B and the solution C into the suspension A at the same time to obtain a suspension D; 5) Ultrasonic treatment of the suspension D, heat preservation, stirring and soaking; 6) Adding sodium carbonate solution containing sodium borohydride for reduction, filtering, washing and drying to obtain the catalyst. The method is simple, the condition is mild, the proportion of catalytic components is adjustable, and the catalyst has the advantages of high catalytic activity, high conversion rate, easy recovery, repeated use and the like when being used for producing hydrogen by formic acid decomposition.
Description
Technical Field
The invention relates to a heterogeneous catalyst taking a series of carbon as a carrier and palladium-gold nanoparticles formed by different molar ratios as active centers, a preparation method and application of the catalyst in a formic acid decomposition hydrogen production reaction.
Background
The quality energy density of hydrogen is very high and is almost three times that of gasoline, the combustion product of hydrogen is water, zero carbon emission can be truly realized, and the hydrogen is an important energy source for replacing fossil fuel and has become an important component of energy layout in China. However, the hydrogen has low volume energy density, and the defects of inflammability, explosiveness and difficult storage and transportation prevent the popularization of hydrogen energy, and the hydrogen energy is mainly characterized by high technical barriers and high economic cost. Research and development of "hydrogen carriers" that efficiently store and transport hydrogen is a research goal for many researchers.
Formic Acid (HCOOH, formic Acid, FA) is the simplest carboxylic Acid, has low toxicity and very high hydrogen-containing density (4.4 wt.%,53.4 g.L) -1 ) The price is low. And is liquid at room temperature, has low volatility and is not easy to burn, can be safely stored and transported, and is considered as an organic liquid hydrogen storage material with great application potential. Compared with other hydrogen storage technologies, the formic acid hydrogen storage technology has the advantages of very low cost, high safety and incomparable advantages in storage and transportation. Formic acid can be decomposed under normal temperature and pressure only under the action of catalystHydrogen. Under the action of the catalyst, formic acid can be decomposed in two ways: a dehydrogenation path (HCOOH.fwdarw.H) 2 +CO 2 ) The products are carbon dioxide and hydrogen; the two dehydration pathway (HCOOH.fwdarw.H) 2 O+co), the product is water and carbon monoxide. Both pathways are thermodynamically favored reactions (standard gibbs free energy becomes less than 0), with the dehydration pathway being a side reaction.
Compared with a homogeneous catalyst, the heterogeneous catalyst has the advantages of easy recovery, recycling, higher resistance to carbon monoxide (CO) poisoning, long service life, capability of avoiding using a large amount of organic solvents in the preparation process, easy control of the reaction process and the like, and has a relatively wide development prospect. The heterogeneous catalyst consists of a carrier and an active component supported on the carrier, and the heterogeneous catalyst consists of the active component and the carrier and can be classified into a single metal catalyst and a binary/multi-element alloy catalyst according to the active component. Among the single metal catalysts, palladium is the most active catalyst for catalyzing the decomposition of formic acid to produce hydrogen. However, since carbon monoxide can be stably adsorbed on the noble metal surface, a very small amount of carbon monoxide gas may cause the catalyst to be poisoned and deactivated, and thus side reactions must be avoided. Although some single palladium catalysts perform well, most single palladium catalysts are not stable because they are susceptible to poisoning by carbon monoxide, a by-product of formic acid decomposition. Through alloying or doping of Pd, ag, au, ni, co, cr, B and other elements, the valence electron density of Pd can be regulated, so that the adsorption of Pd on carbon monoxide is reduced or the adsorption of formate is facilitated. Wherein the Au atom pair is CO and H 2 Weak adsorption of molecules is not only beneficial to H 2 And the stable complex is difficult to form on the surface of Au due to the difficulty of CO, which is beneficial to alleviating the poisoning phenomenon of Pd/C, thereby improving the stability of the catalyst.
The prior report on palladium-gold nano heterogeneous catalysts for catalyzing formic acid to decompose and prepare hydrogen has the following problems:
(1) Part of the catalyst can be catalyzed at a higher temperature and cannot meet the actual requirements (DOI: 10.1016/j.jcat.2012.12.009); (2) The preparation method of the carrier of the catalyst with higher activity is often complicated, which leads to high catalyst cost and is not beneficial to popularization (DOI: 10.1021/acsan.1c00266); (3) The preparation method of part of the catalyst adopts a high-temperature hydrogen/hydrogen argon gas reduction process, and the reduction conditions are more severe, etc. (DOI: 10.1016/j.cattod.2020.08.009).
Therefore, the development of a method for preparing the palladium-gold nano heterogeneous nano catalyst which has the advantages of simple preparation process, low cost, mild condition, uniform dispersion of active components, high catalytic activity and good stability and can realize large-scale preparation is a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects and provide the carbon-supported palladium-gold nano heterogeneous catalyst for catalyzing the decomposition of formic acid to prepare hydrogen and a preparation method thereof. The catalyst consists of a carbon carrier and active component palladium gold nanoparticles loaded on the carbon carrier, wherein the total metal loading is 3.0-15.0 wt.%, the content of palladium is 0.46-9.28 wt.%, and the content of gold is 1.14-12.71 wt.%, the preparation method is simple in process and mild in preparation conditions, the catalyst is applicable to various carbon carriers, the proportion of the active components is adjustable, and the catalyst can be applied to catalyzing formic acid to quickly decompose and prepare hydrogen.
Specifically, the preparation method can be used for preparing a series of catalysts by fixing metal load, adjusting the molar ratio between active components (palladium and gold) and replacing carbon carrier types; when the catalyst is used for producing hydrogen by decomposing formic acid, side reactions can be effectively avoided, and the catalyst has the advantages of high catalytic activity, high conversion rate, easiness in recovery, repeated use and the like, is suitable for industrial large-scale production, and has popularization value.
The preparation method adopts the following technical scheme:
(1) Step 1, preparation of a carrier suspension A: firstly, weighing 190.2mg of carbon carrier (such as ECP, ECP600JD, XC-72, SAC-02 and other carbon carriers) and dispersing in 20mL of deionized water, performing ultrasonic dispersion for 30min, and stirring for 30min to form a uniformly dispersed carrier suspension A; and finally, waiting for adding the gold nanoparticle suspension B and the palladium precursor solution C under the stirring state.
(2) Step 2, gold nanoparticlesPreparation of particle suspension B: firstly, 78.4mg of sodium citrate is weighed and dissolved in 4mL of water, and then 1.65mL of 0.02M chloropalladate H is added 2 PdCl 4 And (3) after the solution is quickly and uniformly mixed, standing for 15min at room temperature, changing the color of the solution from yellow to black to form gold nanoparticle suspension B, and finally adding the gold nanoparticle suspension B and palladium precursor solution C into the carrier suspension A in a stirring state.
(3) Step 3, preparing a palladium precursor solution C: sodium citrate 78.4mg was first weighed and dissolved in 2.6mL of water, followed by the addition of palladium salt (chloropalladate H) 2 PdCl 4 Sodium chloropalladate Na 2 PdCl 4 Potassium chloropalladate K 2 PdCl 4 Palladium nitrate Pd (NO) 3 ) 2 Pd (CH) palladium acetate 3 COO) 2 Etc.) solution, mixing uniformly, standing at room temperature for 15min to form palladium precursor solution C, and finally adding the palladium precursor solution C and suspension B into carrier suspension A under stirring.
(4) Step 4, mixing the suspension D: and adding the gold nanoparticle suspension B and the palladium precursor solution C into the carrier suspension A in a stirring state, and stirring for 5min at room temperature to form a mixed suspension D.
(5) Step 5, ultrasonic mixing: and (5) ultrasonically mixing the mixed suspension D for 20min.
(6) Step 6, stirring and dipping: transferring the mixed suspension D into a low-temperature reaction bath, stirring and soaking for 1-4 h under the condition of controlling the temperature (0-50 ℃).
(7) Step 7, reduction: 6.4mL of ice, 0.05mol/L sodium carbonate Na, was added dropwise at a rate of 0.5mL/min 2 CO 3 Aqueous solution (containing 25.5mg sodium borohydride NaBH) 4 ) And continuing to stir at the temperature of 0-50 ℃ for 2-16 h.
(8) Step 8, filtering and drying: suction filtering, washing filter cake with a large amount of deionized water, drying filter cake in vacuum oven at 50deg.C for 12h, grinding to obtain Pd x Au 1-x catalyst/C. The catalyst is named Pd x Au 1-x Name of carbon support, for example, catalyst prepared by using ECP as support and having molar ratio of palladium to gold of 1:1 is named Pd 0.5 Au 0.5 /ECP。
The application of a carbon-supported palladium-gold nano heterogeneous catalyst in catalyzing formic acid to decompose and prepare hydrogen.
Catalytic performance test: firstly, weighing 32mg of catalyst, putting the catalyst into a 25mL reaction tube with a branch, which is filled with magnetons, then adding 0.5mL of deionized water, and putting the mixture into a water bath for heat preservation and stirring for 10min; 1.5mL [ containing 84. Mu.L formic acid (AR, 99%) and 502mg sodium formate dihydrate (AR, 99.5%)]The solution of (2) was rapidly injected into the reaction tube, timing was started, and the volume of gas was recorded by a drainage method. Using the deformation formula pv=nrt:calculating the total volume of gas which can be generated according to 100% decomposition of formic acid under the conditions of the ambient temperature and the air pressure during the test, and then calculating 25% of total volume of gas; finally use the formula->Calculating a conversion frequency (Turn over Frequency, TOF for short), wherein P is the local atmospheric pressure (units, pa); v (V) 25％ Means that under the test conditions, formic acid is 100% decomposed to produce 25% of the total volume of the gases (carbon dioxide and hydrogen, unit, L); r is the gas constant 8.314; t is the reaction temperature (in units, K); n is n metal Refers to the total molar amount (units, mol) of palladium and gold in the catalyst used; t is the reaction time (in h).
Catalyst reusability test: after the first catalytic formic acid decomposition hydrogen production reaction is finished, the reacted catalyst is recovered through filtration, washing and drying; the catalyst recovered was then tested for its catalytic performance according to the same procedure as described above.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with a pure palladium-carbon catalyst, the carbon-supported palladium-gold nano heterogeneous catalyst prepared by the method has basically the same catalytic activity as the pure palladium-carbon catalyst under the condition that the molar amount of active components is the same, but the carbon-supported palladium-gold nano heterogeneous catalyst prepared by the stepwise reduction method has better stability;
2. compared with a carbon-supported palladium-gold catalyst prepared by using the same raw materials but changing the feeding sequence (a co-reduction method or a one-pot method), the palladium-gold nano heterogeneous catalyst prepared by the step-by-step reduction method has higher catalytic activity;
3. compared with palladium-gold catalysts prepared by other methods, the catalyst prepared by the method can realize the preparation of hydrogen under mild conditions, has high catalytic activity and good selectivity, and can be recycled.
4. Compared with other palladium-gold catalyst preparation methods, the preparation method has the advantages of simple process, convenient operation, short preparation time, low cost, good reproducibility and the like, and is more suitable for industrial scale-up production.
Drawings
Fig. 1: schematic diagram of the preparation process flow of the carbon-supported palladium gold nano heterogeneous catalyst.
Fig. 2: example 1 Pd prepared 0.5 Au 0.5 TEM image of ECP and particle size distribution.
Fig. 3: example 1 Pd prepared 0.5 Au 0.5 Element Mapping graph of/ECP.
Fig. 4: example 1 Pd prepared 0.5 Au 0.5 XPS map of Pd 3d and Au 4f in ECP.
Fig. 5: example 1 Pd prepared 0.5 Au 0.5 XRD pattern of ECP.
Fig. 6: example 1 Pd prepared 0.5 Au 0.5 Catalytic performance diagram of ECP for catalyzing formic acid to decompose to prepare hydrogen at different temperatures.
Detailed Description
The invention will be further described with reference to specific examples, illustrative examples and illustrations of which are provided herein to illustrate the invention, but are not to be construed as limiting the invention.
Example 1
185.7mg of superconducting carbon organ black ECP is dispersed by 20mL of deionized water, and is evenly dispersed by ultrasonic treatment for 30min to form carrier suspension A for later use. 111.7mg of sodium citrate (AR, 99%) was weighed out with 3.75mL of deionized waterDissolving, adding the solution into 2.35mL 0.02M chloroauric acid, uniformly mixing, and standing at room temperature for 10-15 min until the solution is completely yellow to black, thereby forming gold nanoparticle suspension B; meanwhile, 0.94mL of 0.05M palladium chloride acid, 111.7mg of sodium citrate and 3.75mL of deionized water are taken and mixed to form orange-yellow palladium precursor solution C; and finally, adding the black gold nanoparticle suspension B and the orange palladium precursor solution C into the carrier suspension A at the same time. Stirring for 1h at 0 ℃, dropwise adding 7.25mL of 0.05M sodium carbonate aqueous solution containing 29mg of sodium borohydride at 0.5mL/min, continuously stirring for 4h at the constant temperature after the dropwise adding is finished, filtering, washing a filter cake with a large amount of deionized water, and vacuum drying at 50 ℃ for 12h to obtain the target catalyst Pd with the total load of palladium and gold of 5 wt% 0.5 Au 0.5 ECP. According to the test method of the catalytic performance of the catalyst, n is tested under 303K, 313K, 323K and 333K FA ：n SF Catalytic performance at=1.1m:2.4m, the results are shown in fig. 6. The method is repeated for 4 times according to the repeated utilization test of the catalyst, the result is shown in table 2, the prepared catalyst has good circulation stability for catalyzing the dehydrogenation reaction of formic acid, and after 3 times of reaction, the conversion rate and hydrogen selectivity of the catalyst for preparing hydrogen by decomposing formic acid can still reach 100 percent.
Example 2
185.7mg of conductive carbon black XC-72 is dispersed by 20mL of deionized water, and is evenly dispersed by ultrasonic treatment for 30min to form carrier suspension A for standby. Weighing 111.7mg of sodium citrate (AR, 99%) and dissolving the sodium citrate in 3.75mL of deionized water, adding the solution into 2.35mL of 0.02M chloroauric acid, uniformly mixing, and standing at room temperature for 10-15 min until the solution is completely yellow to black, thereby forming gold nanoparticle suspension B; meanwhile, 0.94mL of 0.05M palladium chloride acid, 111.7mg of sodium citrate and 3.75mL of deionized water are taken and mixed to form orange-yellow palladium precursor solution C; and finally, adding the black gold nanoparticle suspension B and the orange palladium precursor solution C into the carrier suspension A at the same time. Stirring at 0deg.C for 1 hr, dripping 7.25mL0.05M sodium carbonate aqueous solution containing 29.0mg sodium borohydride at 0.5mL/min, stirring for 4 hr, filtering, washing the filter cake with large amount of deionized water, and vacuum drying at 50deg.C for 12 hrh, obtaining the target catalyst Pd 0.5 Au 0.5 /XC-72。
Example 3
185.7mg of high-purity coconut shell carbon powder SAC-02 is dispersed by 20mL of deionized water, and is evenly dispersed by ultrasound for 30min to form carrier suspension A for later use. Weighing 111.7mg of sodium citrate (AR, 99%) and dissolving the sodium citrate in 3.75mL of deionized water, adding the solution into 2.35mL of 0.02M chloroauric acid, uniformly mixing, and standing at room temperature for 10-15 min until the solution is completely yellow to black, thereby forming gold nanoparticle suspension B; meanwhile, 0.94mL of 0.05M palladium chloride acid, 111.7mg of sodium citrate and 3.75mL of deionized water are taken and mixed to form orange-yellow palladium precursor solution C; and finally, adding the black gold nanoparticle suspension B and the orange palladium precursor solution C into the carrier suspension A at the same time. Stirring at 0deg.C for 1 hr, dripping 7.25mL of 0.05M sodium carbonate aqueous solution containing 29.0mg sodium borohydride at 0.5mL/min, keeping warm, stirring for 4 hr, filtering, washing filter cake with large amount of deionized water, vacuum drying at 50deg.C for 12 hr to obtain target catalyst Pd 0.5 Au 0.5 /SAC-02。
Example 4
185.7mg of superconducting carbon organ black ECP600JD is dispersed by 20mL of deionized water, and is evenly dispersed by ultrasound for 30min to form carrier suspension A for later use. Weighing 111.7mg of sodium citrate (AR, 99%) and dissolving the sodium citrate in 3.75mL of deionized water, adding the solution into 2.35mL of 0.02M chloroauric acid, uniformly mixing, and standing at room temperature for 10-15 min until the solution is completely yellow to black, thereby forming gold nanoparticle suspension B; meanwhile, 0.94mL of 0.05M palladium chloride acid, 111.7mg of sodium citrate and 3.75mL of deionized water are taken and mixed to form orange-yellow palladium precursor solution C; and finally, adding the black gold nanoparticle suspension B and the orange palladium precursor solution C into the carrier suspension A at the same time. Stirring at 0deg.C for 1 hr, dripping 7.25mL0.05M sodium carbonate aqueous solution containing 29.0mg sodium borohydride at 0.5mL/min, maintaining the temperature and stirring for 4 hr, filtering, washing filter cake with a large amount of deionized water, vacuum drying at 50deg.C for 12 hr to obtain target catalyst Pd 0.5 Au 0.5 /ECP600JD。
Example 5
187.9mg of superconducting carbon organ black ECP is dispersed by 20mL of deionized water, and is subjected to ultrasonic treatment for 30min to uniformly disperse the ECP to form a carrier suspension A for later use. Weighing 55.8mg of sodium citrate, dissolving with 1.9mL of deionized water, adding the solution into 1.175mL of 0.02M chloroauric acid, uniformly mixing, and standing at room temperature for 10-15 min until the solution is completely yellow to black, thereby forming gold nanoparticle suspension B; meanwhile, 1.41mL of 0.05M palladium chloride acid, 167.5mg of sodium citrate and 5.6mL of deionized water are taken and mixed to form orange-yellow palladium precursor solution C; and finally, adding the black gold nanoparticle suspension B and the orange palladium precursor solution C into the carrier suspension at the same time. Stirring at 0deg.C for 1 hr, dripping 7.25mL of 0.05M sodium carbonate aqueous solution containing 29mg of sodium borohydride at 0.5mL/min, stirring for 4 hr, filtering, washing with a large amount of water, and vacuum drying at 50deg.C for 12 hr to obtain target catalyst Pd 0.75 Au 0.25 /ECP。
Example 6
183.6mg of superconducting carbon organ black ECP is dispersed by 20mL of deionized water, and is evenly dispersed by ultrasonic treatment for 30min to form carrier suspension A for later use. Weighing 167.5mg of sodium citrate, dissolving with 5.6mL of deionized water, adding the solution into 3.52mL of 0.02M chloroauric acid, uniformly mixing, and standing at room temperature for 10-15 min until the solution is completely yellow to black, thereby forming gold nanoparticle suspension B; meanwhile, 0.47mL of 0.05M chloropalladate, 55.8mg of sodium citrate and 1.9mL of deionized water are taken and mixed to form yellow palladium precursor solution C; and finally, adding the black gold nanoparticle suspension B and the yellow palladium precursor solution C into the carrier suspension at the same time. Stirring at 0deg.C for 1 hr, dripping 7.25mL of 0.05M sodium carbonate aqueous solution containing 29mg of sodium borohydride at 0.5mL/min, stirring for 4 hr, filtering, washing with a large amount of water, and vacuum drying at 50deg.C for 12 hr to obtain target catalyst Pd 0.25 Au 0.75 /ECP。
Comparative example 1
Weighing 318mg of superconducting carbon organ black ECP and 370.6mg of sodium citrate, dissolving in 40mL of water, dispersing for 30min by ultrasonic, adding 3.15mL of 0.05M chloropalladite solution, continuing ultrasonic treatment for 20min, transferring to a low-temperature reaction bath, stirring for 1h at 0 ℃, then dropwise adding 10mL of sodium carbonate solution (containing 40mg of sodium borohydride) at a speed of 0.5mL/min, continuing to keep warm and stir for 4h after the dropwise adding is completed, filtering, washing a filter cake by a large amount of water, and drying in vacuum at 50 ℃ for 12h to obtain the Pd/ECP catalyst.
Comparative example 2
318mg of conductive carbon black XC-72 and 370.6mg of sodium citrate are weighed, dissolved in 40mL of water, dispersed for 30min by ultrasonic, then 3.15mL of 0.05M chloropalladite solution is added, ultrasonic is continued for 20min, transferred to a low-temperature reaction bath, stirred for 1h at 0 ℃, then 10mL of sodium carbonate solution (containing 40mg of sodium borohydride) is added dropwise at the speed of 0.5mL/min, the stirring is continued for 4h after the dropwise addition, the filter cake is washed by a large amount of water, and the Pd/XC-72 catalyst is prepared after the filter cake is dried for 12h in vacuum at 50 ℃.
Comparative example 3
Weighing 318mg of high-purity coconut shell carbon powder SAC-02 and 370.6mg of sodium citrate, dissolving in 40mL of water, dispersing for 30min by ultrasonic, adding 3.15mL of 0.05M chloropalladite acid solution, continuing ultrasonic treatment for 20min, transferring into a low-temperature reaction bath, stirring for 1h at the temperature of 0 ℃, then dropwise adding 10mL of sodium carbonate solution (containing 40mg of sodium borohydride) at the speed of 0.5mL/min, continuing to keep the temperature and stir for 4h after the dropwise adding is finished, filtering, washing a filter cake by a large amount of water, and drying in vacuum at the temperature of 50 ℃ for 12h to obtain the Pd/SAC-02 catalyst.
Comparative example 4
Weighing 318mg of superconducting carbon organ black ECP600JD and 370.6mg of sodium citrate, dissolving in 40mL of water, dispersing for 30min by ultrasonic, adding 3.15mL of 0.05M chloropalladite acid solution, continuing ultrasonic treatment for 20min, transferring into a low-temperature reaction bath, stirring for 1h at the temperature of 0 ℃, then dropwise adding 10mL of sodium carbonate solution (containing 40mg of sodium borohydride) at the speed of 0.5mL/min, continuing to keep the temperature and stir for 4h after the dropwise adding is finished, filtering, washing a filter cake by a large amount of water, and drying in vacuum at the temperature of 50 ℃ for 12h to obtain the Pd/ECP600JD catalyst.
Comparative example 5
Dispersing 318mg of superconducting carbon organ black ECP with 20mL of deionized water, and performing ultrasonic treatment for 30min to uniformly disperse the ECP to form a carrier suspension A for later use. Weighing 202mg of sodium citrate, dissolving with 6.4mL of deionized water, adding the solution into 4.25mL of 0.02M chloroauric acid, uniformly mixing, and standing at room temperature for 10-15 min until the solution is completely yellow to black, thereby forming gold nanoparticle suspension B; and then added to the carrier suspension a. After stirring at 0℃for 1 hour, a 6.6mL of 0.05M aqueous sodium carbonate solution containing 26.3mg of sodium borohydride was added dropwise at 0.5mL/min, and stirring was continued for 4 hours after the completion of the addition, and the mixture was filtered and washed with a large amount of water, and dried under vacuum at 50℃for 12 hours to obtain the objective catalyst Au/ECP.
Comparative example 6
185.7mg of superconducting carbon organ black ECP is dispersed by 20mL of deionized water, and is evenly dispersed by ultrasonic treatment for 30min to form carrier suspension A for later use. 223.4mg of sodium citrate (AR, 99%) is weighed and dissolved in 7.25mL of deionized water, 0.94mL of 0.05M chloropalladate is added to the solution to be mixed uniformly, then 2.35mL of 0.02M chloropalladate is added to the solution to be mixed uniformly, and the solution is added to the carrier suspension A rapidly, and the solution is subjected to ultrasonic treatment for 20min. Stirring for 1h at 0 ℃, dropwise adding 7.25mL of 0.05M sodium carbonate aqueous solution containing 29mg of sodium borohydride at 0.5mL/min, continuously stirring for 4h at the constant temperature after the dropwise adding is finished, filtering, washing a filter cake with a large amount of deionized water, and vacuum drying at 50 ℃ for 12h to obtain the target catalyst Pd 0.5 Au 0.5 ECP (one pot method).
The catalysts prepared in examples 1 to 6 and comparative examples 1 to 6 were evaluated for their catalytic performance in catalyzing the dehydrogenation of formic acid (Formic acid dehydrogenation, FAD) reaction, and the results are shown in table 1. To examine the stability of examples and comparative examples, reusable tests were conducted on example 1, comparative example 5, comparative example 6, and the results are shown in table 2. It can be seen that the valence electron density of Pd can be adjusted by alloying or doping Pd with Au element, thereby reducing the adsorption of Pd to carbon monoxide or facilitating the adsorption of formate. Wherein the Au atom pair is CO and H 2 Weak adsorption of molecules is not only beneficial to H 2 And the stable complex is difficult to form on the surface of Au due to the difficulty of CO, which is beneficial to alleviating the poisoning phenomenon of Pd/C, thereby improving the stability of the catalyst.
TABLE 1 TOF values for hydrogen production by carbon supported palladium gold nano heterogeneous catalyst catalyzed formic acid decomposition
Table 2 catalyst catalyzed formic acid decomposition to hydrogen production recyclability test
It can be seen from the above examples and comparative examples that the present invention can be used as a simple catalyst preparation method, and can be applied to different carriers, metal precursors, and palladium-gold molar ratios to prepare a series of carbon-supported palladium-gold nano heterogeneous catalysts, and the prepared catalysts are applied to formic acid decomposition hydrogen production reaction, and have very good catalytic activity and stability, so that a new approach is provided for developing cheap, safe and efficient heterogeneous catalysts, and further the application of formic acid as a hydrogen storage material in actual production and life is promoted.
Claims (10)
1. The carbon supported palladium-gold nano heterogeneous catalyst is characterized by comprising a carbon carrier and active component palladium-gold nano particles supported on the carbon carrier, wherein the total metal loading amount is 3.0-15.0 wt.%, and the catalyst comprises the following components: the palladium content is 0.46 to 9.28wt.% and the gold content is 1.14 to 12.71wt.%.
2. A method for preparing a carbon supported palladium gold nano heterogeneous catalyst according to claim 1, comprising the steps of:
step 1, preparation of a carrier suspension A: dispersing a carbon carrier in deionized water, and performing ultrasonic dispersion and stirring to form a carrier suspension A;
step 2, preparing gold nanoparticle suspension B: dissolving sodium citrate in water, and then adding chloroauric acid solution to form gold nanoparticle suspension B;
step 3, preparing a palladium precursor solution C: sodium citrate is dissolved in water, and then palladium precursor solution is added to form palladium precursor solution C;
step 4, mixing the suspension D: adding gold nanoparticle suspension B and palladium precursor solution C into carrier suspension A in a stirring state, and stirring at room temperature to form mixed solution D;
step 5, ultrasonic mixing: ultrasonic mixing the mixed suspension D;
step 6, stirring and dipping: transferring the mixed suspension D into a low-temperature constant-temperature reaction bath, stirring at the temperature of 0-50 ℃ and soaking for 1-4 h;
step 7, reduction: dropwise adding sodium carbonate aqueous solution containing sodium borohydride, and continuously reducing and stirring at 0-50 ℃;
step 8, suction filtration and drying: suction filtering, washing the filter cake with a large amount of water, drying the filter cake in a vacuum oven, and grinding to obtain Pd x Au 1-x catalyst/C.
3. The preparation method according to claim 2, characterized in that:
in the step 1, the carbon carrier comprises conductive carbon black XC-72, superconducting carbon black ECP600JD and high-purity coconut shell carbon powder SAC-02;
in step 3, the palladium precursor includes palladium chloride acid, sodium chloride, potassium chloride, palladium nitrate and palladium acetate.
4. The method of claim 2, wherein in step 2:
the ratio of the molar quantity of gold contained in chloroauric acid to the molar quantity of sodium citrate is 1:8;
the mixed solution of chloroauric acid and sodium citrate is stood for reduction time of 10-30 min at room temperature.
5. The preparation method according to claim 2, characterized in that:
in step 3, the ratio of the molar amount of palladium contained in the palladium precursor to the molar amount of sodium citrate was 1:8.
6. The preparation method according to claim 2, characterized in that:
in the step 4, the ratio of the molar amount of gold contained in the gold nanoparticle suspension B to the molar amount of palladium contained in the palladium precursor solution C is 1:0.333-3, and the total mass of palladium and gold in the catalyst is 3.0-15.0 wt.% of the catalyst.
7. The method of any one of claims 2-6, wherein:
in step 7, the ratio of the total molar amount of palladium to gold in the mixed suspension D to the molar amount of sodium borohydride in the sodium carbonate solution is 1:8 to 1:20; the reduction time is 2-16 h, and the reduction temperature is 0-50 ℃.
8. The method of any one of claims 2-6, wherein:
in the step 7, the molar concentration of sodium borohydride in the aqueous solution of sodium carbonate of 0.05mol/L is 0.1mol/L; the dropping speed of the mixed suspension D was 0.5mL/min.
9. Use of the palladium-on-carbon gold nano heterogeneous catalyst according to claim 1 for catalyzing hydrogen production from aqueous formic acid-sodium formate solution.
10. The use of the carbon-supported palladium gold nano heterogeneous catalyst according to claim 9 for catalyzing hydrogen production from aqueous formic acid-sodium formate solution, characterized in that: the carbon-supported palladium-gold nano heterogeneous catalyst is dispersed in water, formic acid-sodium formate aqueous solution is injected, and the reaction temperature is 303-333K for hydrogen production; wherein the molar concentration of formic acid and sodium formate in the reaction system is 1.1mol/L and 2.4mol/L respectively.
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