CN115845904A - Preparation method of catalyst and application of catalyst in preparation of hydrogen by catalyzing formic acid - Google Patents
Preparation method of catalyst and application of catalyst in preparation of hydrogen by catalyzing formic acid Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 56
- 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 54
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
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- 239000003575 carbonaceous material Substances 0.000 claims abstract description 80
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000012696 Pd precursors Substances 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 229910052796 boron Inorganic materials 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 20
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- COIQUVGFTILYGA-UHFFFAOYSA-N (4-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=C(O)C=C1 COIQUVGFTILYGA-UHFFFAOYSA-N 0.000 claims description 2
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 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
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 229960001484 edetic acid Drugs 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
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- TWJZAIVFYJWAJC-UHFFFAOYSA-L 2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate;cobalt(2+) Chemical compound [Co+2].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O TWJZAIVFYJWAJC-UHFFFAOYSA-L 0.000 description 1
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- 239000004280 Sodium formate Substances 0.000 description 1
- ONATYSLUCORNRQ-UHFFFAOYSA-N [K].[K].[K].[K].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O Chemical compound [K].[K].[K].[K].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O ONATYSLUCORNRQ-UHFFFAOYSA-N 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GHTWQCXOBQMUHR-UHFFFAOYSA-M potassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [K+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O GHTWQCXOBQMUHR-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention discloses a preparation method of a catalyst and application of the catalyst in preparation of hydrogen by catalyzing formic acid, relates to the technical field of catalyst synthesis, and aims to overcome the defects of low catalytic efficiency and poor stability of the catalyst in the process of catalyzing formic acid to prepare hydrogen. The catalyst is a boron-nitrogen co-doped carbon-loaded palladium-based catalyst, and comprises the following components: grinding and mixing a nitrogen-containing organic substance and a boron-containing compound precursor, and carbonizing by a high-temperature pyrolysis method to obtain a boron-nitrogen co-doped carbon material; loading a palladium precursor on a boron-nitrogen co-doped carbon material to obtain the palladium precursor-loaded boron-nitrogen co-doped carbon material; reducing the boron-nitrogen co-doped carbon material loaded with the palladium precursor by using hydrogen to obtain the target catalyst, wherein the loading capacity of palladium particles is 1-20%, and the size of palladium particles is 0.1-2nm. The preparation method of the catalyst and the application of the catalyst in preparing hydrogen by catalyzing formic acid are used for preparing the catalyst which has higher catalytic efficiency and catalytic stability in the process of preparing hydrogen by catalyzing formic acid.
Description
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to a preparation method of a catalyst and application of the catalyst in preparation of hydrogen by catalyzing formic acid.
Background
Formic acid is considered to be a promising hydrogen storage material because of its high hydrogen content, low toxicity, wide source, and low cost. Formic acid can be decomposed not only into carbon dioxide and hydrogen but also into carbon monoxide and water in the presence of a catalyst. At present, the homogeneous catalyst is difficult to recycle, and the cost is high due to the use of noble metals, so that the homogeneous catalyst is not suitable for large-scale production and utilization. The heterogeneous catalyst can be recycled, has high atom utilization rate, and is widely applied to hydrogen production by formic acid decomposition. A large number of researches show that the palladium-based catalyst has excellent catalytic performance on hydrogen production by formic acid. Xi Zhao et al uses sodium borohydride as reducing agent, and adopts wet reduction method to synthesize a novel palladium catalyst, said catalyst uses superfine metal nano-particles to anchor NH 2 Functionalized reduced graphene oxide (NH) 2 -rGO) gave a Pd particulate catalyst with an average particle size of 2.3nm, which at 25 ℃ had a turnover frequency TOF (calculated as the total moles of palladium) for the catalytic dehydrogenation of formic acid without additive of 767h -1 (ii) a The catalyst retained 91.3% of the initial activity after 3 cycles (ZHao X, dai P, xu D, et al. International Journal of Hydrogen Energy,2020,45 (55)). At present, the defects of low catalytic efficiency and poor stability still exist. Since the metal particles have high surface energy and small volume, and are easily aggregated in synthesis and catalytic reactions, resulting in a decrease in activity, various methods have been developed for preparing highly dispersed metal particles. This includes the use of interactions between the active metal particles and the support, the use of mild reduction, and the use of organic reagents as stabilizers, etc.; wherein enhancing the interaction between the active metal particles and the support is the most effective method.
The boron-nitrogen co-doped carbon material is widely applied to the field of heterogeneous catalysis due to the fact that the boron-nitrogen co-doped carbon material contains abundant B and N species. Xiong wei et al are threeThe preparation method comprises the steps of preparing a nitrogen atom-rich two-dimensional covalent organic framework material, namely 2D-COFs, by using dicyandiamide and terephthalaldehyde as monomers through a solvothermal method, loading a boron atom-containing precursor compound through an impregnation method to obtain a composite COFs material, and finally performing high-temperature carbonization to obtain the heteroatom nitrogen and boron co-doped carbon nanosheet nonmetal hydrogenation catalyst. The obtained nitrogen-shed co-doped carbon nanosheet has high hydrogen dissociation capability, shows excellent catalytic performance in the catalytic liquid-phase hydrogenation reduction reaction of aromatic nitro compounds, and avoids the problems that the traditional metal hydrogenation catalyst is poisoned and dissolved out to cause catalyst deactivation and heavy metals flow into the environment to cause pollution and the like (bear-weih, king eupatorium, liuping, and the like, CN 202010665775.6). Wei Cheng et al prepared B, N, F-codoped porous carbon (BNF-C) by direct and simple one-step calcination method, successfully supported a catalyst with a palladium particle size of about 3.3nm, and catalyzed the dehydrogenation of formic acid at 40 ℃ and with sodium formate as an additive for a TOF value of 3828h -1 (Cheng W, zhao X, hu H, et al. Applied Surface science.2022, 597.). At present, the reported preparation process of the boron-nitrogen co-doped carbon material is complicated, the research on the high-efficiency boron-nitrogen co-doped carbon material loaded palladium catalyst for formic acid dehydrogenation reaction is less, the content of B and N species contained in the prepared B and N co-doped carbon material is less, and the dispersibility of palladium is still poor, so that the catalytic formic acid dehydrogenation performance is poor.
Disclosure of Invention
The invention aims to provide a preparation method and application of a catalyst, so that the prepared catalyst has higher catalytic efficiency and catalytic stability in the process of catalyzing formic acid to prepare hydrogen.
In order to achieve the above object, the present invention provides a preparation method of a catalyst, wherein the catalyst is a boron-nitrogen co-doped carbon material supported palladium-based catalyst, and the preparation method comprises:
mixing a nitrogen-containing organic substance and a boron-containing compound precursor, and then carbonizing to obtain a boron-nitrogen co-doped carbon material; the nitrogen-containing organic matter comprises one or more of ethylenediamine tetraacetic acid alkali metal salt, ethylenediamine tetraacetic acid alkaline earth metal salt and ethylenediamine tetraacetic acid transition metal salt; loading a palladium precursor on the boron-nitrogen co-doped carbon material to obtain a palladium precursor-loaded boron-nitrogen co-doped carbon material;
and reducing the boron-nitrogen co-doped carbon material loaded with the palladium precursor by using hydrogen to obtain the boron-nitrogen co-doped carbon material loaded palladium catalyst, wherein the loading capacity of palladium particles is 1-20%, and the size of palladium particles is 0.1-2nm.
Compared with the prior art, in the preparation method of the catalyst provided by the invention, the nitrogen-containing organic matter and the boron-containing compound precursor are mixed and then carbonized, and heteroatom nitrogen and boron are introduced in the process of generating the carbon material, so that a large amount of B-O and pyridine-N species which can form strong interaction with palladium particles are formed, the dispersibility of the palladium nanoparticles is improved in the preparation process, and the particle size of the palladium nanoparticles is reduced. So that the size of palladium particles in the prepared catalyst is controlled in the range of 0.1-2nm. The nitrogen-containing organic matter comprises one or more of ethylenediamine tetraacetic acid alkali metal salt, ethylenediamine tetraacetic acid alkaline earth metal salt and ethylenediamine tetraacetic acid transition metal salt, the prepared boron-nitrogen co-doped carbon material has higher boron and nitrogen doping amount by taking the nitrogen-containing organic matter as a precursor, and the metal salt can create more pore structures at high temperature, so that more adsorption sites can be provided for palladium nanoparticles, the particle size of the palladium nanoparticles is reduced, and the catalytic activity and stability of the catalyst are improved. In addition, the precursor for preparing the carbon material has wide source, and the preparation process of the catalyst is not complex, so the reproducibility is good, and the method can be applied to industrial large-scale production.
In a second aspect, the invention provides an application of a preparation method utilizing a catalyst in preparation of hydrogen by catalyzing formic acid.
Compared with the prior art, the beneficial effect of the application of the preparation method of the catalyst in preparing hydrogen by catalyzing formic acid provided by the invention is the same as that of the preparation method of the catalyst provided by the first aspect, and details are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a flow chart of a method for preparing a catalyst provided by an embodiment of the invention;
FIG. 2 shows the gas phase product results of the catalyst prepared in the first example when catalyzing formic acid to prepare hydrogen;
fig. 3 shows the evaluation results of the catalysts prepared in the first and second examples and the first and second comparative examples when catalyzing formic acid to produce hydrogen.
Fig. 4 shows the stability results of the catalyst prepared in the first example for catalyzing hydrogen production from formic acid through five cycles.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. The meaning of "a number" is one or more unless specifically limited otherwise.
At present, the homogeneous catalyst is difficult to recycle, and the cost is high due to the use of noble metals, so the homogeneous catalyst is not suitable for large-scale production and utilization. The heterogeneous catalyst can be recycled, has high atom utilization rate, and is widely applied to hydrogen production by formic acid decomposition. And a large number of researches show that the palladium-based catalyst has excellent catalytic performance for hydrogen production by formic acid. However, the defects of low catalytic efficiency and poor stability still exist at present.
In order to solve the above problems, the preparation method of the catalyst provided by the embodiment of the invention enables the prepared catalyst to have higher catalytic efficiency and catalytic stability in the process of catalyzing formic acid to prepare hydrogen. Fig. 1 shows a flow chart of a preparation method of a catalyst provided by an embodiment of the invention. As shown in fig. 1, the preparation method comprises:
step 101: and mixing the nitrogen-containing organic matter and the boron-containing compound precursor, and carbonizing to obtain the boron-nitrogen co-doped carbon material.
The precursor of the boron-nitrogen co-doped carbon material is nitrogen-containing organic matter and comprises one or more of ethylenediamine tetraacetic acid alkali metal salt, ethylenediamine tetraacetic acid alkaline earth metal salt and ethylenediamine tetraacetic acid transition metal salt. The prepared boron-nitrogen co-doped carbon material has higher boron and nitrogen doping amount by taking the nitrogen-containing organic matter as the precursor, and the metal salt can create more pore structures at high temperature, so that more adsorption sites can be provided for the palladium nano particles, the particle size of the palladium nano particles is reduced, and the catalytic activity and the stability of the catalyst are improved. Experiments prove that when the catalyst prepared by the preparation method is used for catalyzing formic acid to prepare hydrogen at 50 ℃ without additives, the TOF value of the initial conversion frequency can reach 2760h as high as possible -1 . And no carbon monoxide is generated, and the hydrogen selectivity reaches 100 percent. The catalytic efficiency is not reduced after the catalyst is circulated for 5 times. It is worth to be noted that, when the mass ratio of the nitrogen-containing organic substance to the boron-containing precursor is 2:1, the prepared catalyst shows excellent catalytic performance and excellent stability. Wherein the nitrogen-containing organic matter comprises one or more of ethylenediamine tetraacetic acid alkali metal salt, ethylenediamine tetraacetic acid alkaline earth metal salt and ethylenediamine tetraacetic acid transition metal salt. Specifically, the nitrogen-containing organic substance may be one or more of a nitrogen-containing organic substance including lithium salt of ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, potassium salt of ethylenediaminetetraacetic acid, magnesium salt of ethylenediaminetetraacetic acid, calcium salt of ethylenediaminetetraacetic acid, chromium salt of ethylenediaminetetraacetic acid, manganese salt of ethylenediaminetetraacetic acid, iron salt of ethylenediaminetetraacetic acid, cobalt salt of ethylenediaminetetraacetic acid, zinc salt of ethylenediaminetetraacetic acid, and cobalt salt of ethylenediaminetetraacetic acid. Wherein the boron compound precursor comprisesOne or more of an inorganic boron compound and an organic boron compound.
For example, in order to obtain the boron-nitrogen co-doped carbon material, a nitrogen-containing organic substance may be mixed with a boron-containing compound precursor to obtain an organic mixture of the boron-nitrogen material. In order to prevent the boron-nitrogen material organic mixture from being oxidized by air at high temperature, the organic mixture can be carbonized under the protection of inert gas, and a boron-nitrogen co-doped carbon material semi-finished product is obtained. And finally, washing and drying impurities in the boron-nitrogen co-doped carbon material semi-finished product by using 1mol/L acid solution to obtain the boron-nitrogen co-doped carbon material.
Wherein, the boron-containing compound precursor comprises one or more of boric acid, trimethyl borate, triethyl borate, phenylboronic acid, p-hydroxyphenylboronic acid, p-methylphenylboronic acid and boron oxide. In addition, the mixing method is physical grinding mixing or aqueous solution stirring mixing. The carbonization temperature is 500-900 ℃, and the reaction time is 1-3 h.
It is worth mentioning that when the boric acid and the disodium ethylene diamine tetraacetate are selected to be physically mixed by grinding, then reacted at 800 ℃ for 2h and inert gas (such as N) 2 ) The organic mixture of the boron-nitrogen material is carbonized under the protection of the carbon solution, so that after impurities in the organic mixture are washed and dried by using 1mol/L acid solution, the obtained boron-nitrogen co-doped carbon material has less impurities, and the doping effect of the boron-nitrogen co-doped carbon material prepared in the subsequent steps is the best.
Illustratively, in the process of washing and drying the impurities in the solution by using 1mol/L of acid solution, the stirring time is 1-24 h and the stirring temperature is 0-100 ℃ in the washing process. The drying temperature is 60-110 ℃, and the drying time is 1-24 h. It is worth noting that after the boron-nitrogen co-doped carbon material semi-finished product is stirred and washed for 6 hours at 30 ℃ by using 1mol/L acid solution, the boron-nitrogen co-doped carbon material semi-finished product is dried for 12 hours at 100 ℃, and the drying effect and the washing effect on the boron-nitrogen co-doped carbon material semi-finished product are the best.
Step 102: and loading a palladium precursor on the boron-nitrogen co-doped carbon material to obtain the palladium precursor-loaded boron-nitrogen co-doped carbon material.
Illustratively, the palladium precursor is one or more of chloropalladate, sodium tetrachloropalladate, palladium nitrate, palladium acetate, and tetraamminepalladium dichloride. The method for loading the palladium precursor on the boron-nitrogen co-doped carbon material may be a deposition precipitation method, and it should be understood that the method for loading the palladium precursor on the boron-nitrogen co-doped carbon material may be adjusted according to actual situations, and is not limited herein. When a deposition precipitation method is adopted to load the palladium precursor on the boron-nitrogen co-doped carbon material, the stirring time is 1-12 h, and the stirring temperature is 0-100 ℃. It is worth noting that the loading effect is best when palladium chloride acid is stirred in an aqueous solution for 4 hours at 30 ℃ to be deposited and loaded on the boron-nitrogen co-doped carbon material.
Step 103: and reducing the boron-nitrogen co-doped carbon material loaded with the palladium precursor by using hydrogen to obtain the boron-nitrogen co-doped carbon material loaded palladium catalyst.
Illustratively, the target catalyst is obtained by a deposition precipitation method and a hydrogen reduction method, wherein the loading of palladium nano particles in the catalyst is 1-20%, and the size of palladium particles is 0.1-2nm. Because the palladium nano particles have higher surface free energy and are easy to spontaneously agglomerate, the loading capacity of the palladium nano particles is 5 percent, and the mass ratio of the nitrogen-containing organic matter to the boron-containing precursor is 2: at 1, boron and nitrogen provide more adsorption sites for adsorption of palladium nanoparticles, and the catalyst at this ratio shows the highest catalytic activity.
In addition, the precursor for preparing the carbon material has wide source and low price, the preparation method of the catalyst is simple, and the target catalyst can be obtained only by mixing the nitrogen-containing organic matter and the boron-containing compound precursor and then carbonizing the mixture, so the reproducibility is good, and the method can be applied to industrial large-scale production.
The embodiment of the invention also provides application of the preparation method of the catalyst in preparing hydrogen by catalyzing formic acid, so that the prepared catalyst has higher catalytic efficiency and catalytic stability in the process of preparing hydrogen by catalyzing formic acid. In the process of catalyzing formic acid to prepare hydrogen, the concentration of formic acid is 0.5-10 mol/L, and the volume of the catalyst is 1-50 mL; the reaction temperature is 10-100 ℃. Finally, according to the experimental results, the temperature is 50 ℃ without addingUnder the condition of the agent, the TOF value of the initial conversion frequency is up to 2760h -1 . And no carbon monoxide is generated, and the hydrogen selectivity reaches 100 percent. The catalytic efficiency is not reduced after the catalyst is circulated for 5 times.
In order to verify the effect of the preparation method of the catalyst provided by the embodiment of the invention, the embodiment of the invention is proved by comparing the embodiment with the comparative example.
Example one
The preparation method of the catalyst provided by the embodiment of the invention comprises the following steps:
step one, preparing a boron-nitrogen co-doped carbon material: accurately weighing 2g of disodium ethylene diamine tetraacetate and 4g of boric acid, and putting the disodium ethylene diamine tetraacetate and the boric acid into a mortar for grinding and uniformly mixing to obtain the organic mixture of the boron-nitrogen material. And then under the protection of nitrogen in a tube furnace, putting the boron-nitrogen material organic mixture into a quartz boat, and roasting for 2 hours at 800 ℃ to obtain a boron-nitrogen co-doped carbon material semi-finished product. Finally dispersing the boron-nitrogen co-doped carbon material in 1mol/L hydrochloric acid solution, stirring for 6h, filtering, washing, and drying at 100 ℃ for 12h to obtain a boron-nitrogen co-doped carbon material;
step two, preparing a boron-nitrogen co-doped carbon material loading a palladium precursor: weighing 100mg of boron-nitrogen co-doped carbon material, dispersing the boron-nitrogen co-doped carbon material in 30mL of water, dripping 1.05mL of chloropalladate solution (5 mgPd/mL), stirring for 2h, dripping sodium hydroxide solution to adjust the pH value to 10, continuously stirring for 2h, performing suction filtration and washing, and performing vacuum drying at 100 ℃ for 12h to obtain the palladium precursor loaded boron-nitrogen co-doped carbon material.
Step three, preparing the boron-nitrogen co-doped carbon supported palladium-based catalyst: and reducing the boron-nitrogen co-doped carbon material loaded with the palladium precursor for 2h at 250 ℃ under the protection of nitrogen in a tubular furnace to obtain the catalyst.
53mg of the catalyst prepared in the first embodiment is weighed, and is added into a formic acid hydrogen production reaction device to evaluate the effect of catalyzing the formic acid hydrogen production, and the change of the gas generation volume along with time is recorded. The amount of the formic acid aqueous solution is 5mL, the concentration is 1mol/L, and the reaction temperature is 50 ℃. After each reaction is finished, the catalyst is subjected to suction filtration washing and vacuum drying, and then the effect is continuously evaluated, so that the repeated stability of the catalyst is inspected. Fig. 2 shows the gas phase product results of the catalyst prepared in the first example when catalyzing formic acid to produce hydrogen. Referring to the results of the standard gas below, the catalyst prepared in the first embodiment of the present invention does not produce carbon monoxide and methane when catalyzing formic acid to produce hydrogen, and the selectivity of hydrogen is 100%, as shown in fig. 2.
Example two
The preparation method of the catalyst provided by the embodiment of the invention comprises the following steps:
step one, preparing a boron-nitrogen co-doped carbon material: accurately weighing 2g of ethylene diamine tetraacetic acid tetrapotassium and 4g of boric acid, putting the materials into a mortar, grinding and uniformly mixing to obtain the boron-nitrogen material organic mixture. And then under the protection of nitrogen in a tube furnace, putting the boron-nitrogen material organic mixture into a quartz boat, and roasting for 2 hours at 800 ℃ to obtain a boron-nitrogen co-doped carbon material semi-finished product. Finally dispersing the boron-nitrogen co-doped carbon material in 1mol/L hydrochloric acid solution, stirring for 6h, filtering, washing, and drying at 100 ℃ for 12h to obtain a boron-nitrogen co-doped carbon material;
step two, preparing a boron-nitrogen co-doped carbon material loading a palladium precursor: weighing 100mg of boron-nitrogen co-doped carbon material, dispersing the boron-nitrogen co-doped carbon material in 30mL of water, dripping 1.05mL of chloropalladate solution (5 mgPd/mL), stirring for 2h, dripping sodium hydroxide solution to adjust the pH value to 10, continuously stirring for 2h, performing suction filtration and washing, and performing vacuum drying at 100 ℃ for 12h to obtain the palladium precursor loaded boron-nitrogen co-doped carbon material.
Step three, catalyst preparation: and reducing the boron-nitrogen co-doped carbon material loaded with the palladium precursor for 2h at 250 ℃ under the protection of nitrogen in a tubular furnace to obtain the catalyst.
53mg of the catalyst prepared in the second embodiment is weighed and added into a formic acid hydrogen production reaction device to evaluate the effect of catalyzing the formic acid to produce hydrogen, and the change of the gas generation volume along with time is recorded. The amount of the formic acid aqueous solution is 5mL, the concentration is 1mol/L, and the reaction temperature is 50 ℃. After each reaction is finished, the catalyst is subjected to suction filtration washing and vacuum drying, and then the effect is continuously evaluated, so that the repeated stability of the catalyst is inspected.
Comparative example 1
The preparation method of the catalyst provided by the comparative example comprises the following steps:
firstly, preparing a nitrogen-doped carbon material: accurately weighing 2g of tetrasodium ethylene diamine tetraacetate, putting the tetrasodium ethylene diamine tetraacetate into a mortar, uniformly grinding the tetrasodium ethylene diamine tetraacetate, putting the boron-nitrogen material organic mixture into a quartz boat, roasting the mixture for 2 hours at 800 ℃ under the protection of nitrogen in a tube furnace, dispersing the mixture into 1mol/L hydrochloric acid solution, stirring the mixture for 6 hours, performing suction filtration and washing, and drying the mixture for 12 hours at 100 ℃ to obtain the nitrogen-doped carbon material.
Step two, preparing a nitrogen-doped carbon material loaded with a palladium precursor: weighing 100mg of nitrogen-doped carbon material, dispersing the nitrogen-doped carbon material in 30mL of water, dripping 1.05mL of chloropalladate solution (5 mgPd/mL), stirring for 2h, dripping sodium hydroxide solution to adjust the pH value to 10, continuously stirring for 2h, carrying out suction filtration washing, and carrying out vacuum drying at 100 ℃ for 12h to obtain the palladium precursor-loaded nitrogen-doped carbon material.
Step three, catalyst preparation: and reducing the nitrogen-doped carbon material loaded with the palladium precursor for 2 hours at 250 ℃ under the protection of nitrogen in a tubular furnace to obtain the catalyst.
53mg of the catalyst prepared in the comparative example I is weighed, added into a formic acid hydrogen production reaction device to evaluate the effect of catalyzing the formic acid hydrogen production, and the change of the gas generation volume along with time is recorded. The amount of the formic acid aqueous solution is 5mL, the concentration is 1mol/L, and the reaction temperature is 50 ℃. After each reaction is finished, the catalyst is subjected to suction filtration washing and vacuum drying, and then the effect is continuously evaluated, so that the repeated stability of the catalyst is inspected.
Comparative example No. two
The preparation method of the catalyst provided by the comparative example comprises the following steps:
step one, preparing a boron-nitrogen doped carbon material: accurately weighing 2g of polyvinylpyrrolidone and 4g of boric acid, putting the polyvinylpyrrolidone and the boric acid into a mortar, uniformly grinding, putting the organic mixture of boron-nitrogen materials into a quartz boat, roasting for 2h at 800 ℃ under the protection of nitrogen in a tube furnace, dispersing the organic mixture of boron-nitrogen materials into 1mol/L hydrochloric acid solution, stirring for 6h, performing suction filtration and washing, and drying for 12h at 100 ℃ to obtain the boron-nitrogen co-doped carbon material.
Secondly, loading a boron-nitrogen doped carbon material of a palladium precursor: weighing 100mg of boron-nitrogen co-doped carbon material, dispersing the boron-nitrogen co-doped carbon material in 30mL of water, dripping 1.05mL of chloropalladate solution (5 mgPd/mL), stirring for 2h, dripping sodium hydroxide solution to adjust the pH value to 10, continuously stirring for 2h, performing suction filtration and washing, and performing vacuum drying at 100 ℃ for 12h to obtain the palladium precursor loaded boron-nitrogen co-doped carbon material.
Step three, catalyst preparation: and reducing the boron-nitrogen co-doped carbon material loaded with the palladium precursor for 2h at 250 ℃ under the protection of nitrogen in a tubular furnace to obtain the catalyst.
53mg of the catalyst prepared in the comparative example I is weighed, added into a formic acid hydrogen production reaction device to evaluate the effect of catalyzing the formic acid hydrogen production, and the change of the gas generation volume along with time is recorded. The amount of the formic acid aqueous solution is 5mL, the concentration is 1mol/L, and the reaction temperature is 50 ℃. After each reaction is finished, the catalyst is subjected to suction filtration washing and vacuum drying, and then the effect is continuously evaluated, so that the repeated stability of the catalyst is inspected.
Fig. 3 shows the evaluation results of the catalysts prepared in the first and second examples and the first and second comparative examples when catalyzing formic acid to produce hydrogen. As shown in fig. 3, the curves from left to right show the evaluation results of the catalysts prepared in the first example, the second example, the first comparative example and the second comparative example when catalyzing hydrogen production from formic acid. Under the conditions that the reaction temperature is 50 ℃ and no additive exists, 248mL of gas can be generated in 8 minutes when the catalyst prepared in the first embodiment catalyzes formic acid to prepare hydrogen, and the initial TOF value of the reaction is 2760h -1 (TOF = pV/(2 nPd/RTt), where P represents standard atmospheric pressure (101.325 KPa), V represents the total volume of gas produced at 20% FA conversion, nPd represents the total molar amount of Pd in the catalyst, and R is the gas constant (8.314J. Mol. Multidot. -1 ·K -1 ) T is 298K and T represents the reaction time at which FA conversion reaches 20%. ). 248mL of gas can be generated in 10 minutes when the catalyst prepared in the second embodiment catalyzes formic acid to prepare hydrogen, and the initial TOF value of the reaction is 2600h -1 (TOF = pV/(2 nPd/RTt)). And under the condition of 50 ℃ and no additive, the catalyst prepared in the comparative example produces only 154mL of gas in 20 minutes when catalyzing formic acid to produce hydrogen, and the initial TOF value of the reaction is only 1051h < -1 >. Catalyst prepared in comparative example IIWhen formic acid is used for preparing hydrogen, only 134mL of gas is generated in 20 minutes, and the initial TOF value of the reaction is only 591h-1.
Fig. 4 shows the stability results of the catalyst prepared in the first example for five cycles when catalyzing hydrogen production from formic acid. As shown in fig. 4, the curves from left to right are the stability results of the first cycle, the second cycle, the third cycle, the fourth cycle and the fifth cycle of the catalyst prepared in the first example when catalyzing hydrogen production from formic acid. Under the condition that the reaction temperature is 50 ℃ and no additive is added, the catalytic efficiency is not obviously reduced after 5 times of circulation, which shows that the prepared boron-nitrogen co-doped carbon supported palladium catalyst has excellent circulation stability.
While the foregoing is directed to embodiments of the present invention, it will be apparent that various modifications and combinations can be made without departing from the spirit and scope of the invention. Accordingly, the specification and figures are merely exemplary of the invention as defined in the appended claims and are intended to cover any and all modifications, variations, combinations, or equivalents within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present disclosure, and all such changes or substitutions are included in the scope of the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The preparation method of the catalyst is characterized in that the catalyst is a boron-nitrogen co-doped carbon supported palladium-based catalyst, and comprises the following steps:
mixing a nitrogen-containing organic substance and a boron-containing compound precursor, and then carbonizing to obtain a boron-nitrogen co-doped carbon material; the nitrogen-containing organic matter comprises one or more of ethylenediamine tetraacetic acid alkali metal salt, ethylenediamine tetraacetic acid alkaline earth metal salt and ethylenediamine tetraacetic acid transition metal salt;
loading a palladium precursor on the boron-nitrogen co-doped carbon material to obtain a palladium precursor-loaded boron-nitrogen co-doped carbon material;
and reducing the boron-nitrogen co-doped carbon material loaded with the palladium precursor by using hydrogen to obtain the boron-nitrogen co-doped carbon material loaded palladium catalyst, wherein the loading capacity of palladium nano particles is 1-20%, and the size of palladium particles is 0.1-2nm.
2. The method for preparing the catalyst according to claim 1, wherein the step of mixing a nitrogen-containing organic substance with a boron-containing compound precursor and then carbonizing the mixture to obtain the boron-nitrogen co-doped carbon material comprises the following steps:
mixing nitrogen-containing organic matter with boron-containing compound precursor to obtain boron-nitrogen material organic mixture;
carbonizing the boron-nitrogen material organic mixture under the protection of inert gas to obtain a boron-nitrogen co-doped carbon material semi-finished product;
and washing and drying the boron-nitrogen co-doped carbon material semi-finished product by using an acid solution to obtain the boron-nitrogen co-doped carbon material.
3. The method for preparing the catalyst according to claim 1, wherein the temperature of the carbonization is 500 ℃ to 900 ℃ and the time of the carbonization is 1h to 3h.
4. The method for preparing the catalyst according to claim 1, wherein the mixing is physical grinding mixing or aqueous solution stirring mixing.
5. The method for preparing the catalyst according to claim 2, wherein the drying temperature is 60 ℃ to 110 ℃, the drying time is 1h to 24h, and the concentration of the acid solution is 1mol/L.
6. The method for preparing a catalyst according to claim 1, wherein the boron-containing compound precursor comprises one or more of an inorganic boron compound and an organic boron compound, and the boron-containing compound precursor comprises one or more of boric acid, trimethyl borate, triethyl borate, phenylboronic acid, p-hydroxyphenylboronic acid, p-methylphenylboronic acid and boron oxide.
7. The method of claim 1, wherein the palladium precursor is one or more selected from the group consisting of chloropalladic acid, sodium tetrachloropalladate, palladium nitrate, palladium acetate, and tetraamminepalladium dichloride.
8. The method for preparing the catalyst according to claim 1, wherein the hydrogen reduction temperature is 50 ℃ to 350 ℃.
9. Use of a process for the preparation of a catalyst according to any one of claims 1 to 8 in the catalysis of formic acid to hydrogen.
10. The use of the method of claim 9 for the preparation of a catalyst for the catalytic production of hydrogen from formic acid, wherein the formic acid has a concentration of 0.5-10 mol/L and a volume of 1-50 mL; the reaction temperature is 10-100 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112285A (en) * | 1997-06-19 | 1999-01-19 | Agency Of Ind Science & Technol | 2-silylalkenylborane compound and its production |
| CN104689857A (en) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | Preparing method for nitrogen-doped porous carbon material, catalyst comprising material and application of material |
| CN108199055A (en) * | 2018-01-02 | 2018-06-22 | 珠海光宇电池有限公司 | Nitrogen co-doped carbon supported platinum catalyst of a kind of boron and preparation method thereof |
| CN113457705A (en) * | 2021-06-08 | 2021-10-01 | 广州大学 | Catalyst for hydrogen production from formic acid, preparation method and application thereof |
| CN114100653A (en) * | 2020-08-31 | 2022-03-01 | 台州学院 | Nitride supported palladium catalyst and preparation method and application thereof |
| CN114956268A (en) * | 2022-05-16 | 2022-08-30 | 河南师范大学 | Preparation method and application of nitrogen-boron double-doped porous carbon-based electrode material |
-
2023
- 2023-02-09 CN CN202310109174.0A patent/CN115845904A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112285A (en) * | 1997-06-19 | 1999-01-19 | Agency Of Ind Science & Technol | 2-silylalkenylborane compound and its production |
| CN104689857A (en) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | Preparing method for nitrogen-doped porous carbon material, catalyst comprising material and application of material |
| CN108199055A (en) * | 2018-01-02 | 2018-06-22 | 珠海光宇电池有限公司 | Nitrogen co-doped carbon supported platinum catalyst of a kind of boron and preparation method thereof |
| CN114100653A (en) * | 2020-08-31 | 2022-03-01 | 台州学院 | Nitride supported palladium catalyst and preparation method and application thereof |
| CN113457705A (en) * | 2021-06-08 | 2021-10-01 | 广州大学 | Catalyst for hydrogen production from formic acid, preparation method and application thereof |
| CN114956268A (en) * | 2022-05-16 | 2022-08-30 | 河南师范大学 | Preparation method and application of nitrogen-boron double-doped porous carbon-based electrode material |
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