CN117721489A - Catalyst for synthesizing amino acid and preparation method and application thereof - Google Patents
Catalyst for synthesizing amino acid and preparation method and application thereof Download PDFInfo
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- CN117721489A CN117721489A CN202311800194.9A CN202311800194A CN117721489A CN 117721489 A CN117721489 A CN 117721489A CN 202311800194 A CN202311800194 A CN 202311800194A CN 117721489 A CN117721489 A CN 117721489A
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- catalyst
- acid
- amino acid
- electrolyte
- salt
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- 239000011135 tin Substances 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 239000010955 niobium Substances 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims description 37
- 239000011133 lead Substances 0.000 claims description 34
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000002608 ionic liquid Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
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- 238000004070 electrodeposition Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052751 metal Inorganic materials 0.000 claims description 9
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- 239000008139 complexing agent Substances 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 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 description 8
- AFSJUFFXOPXIOH-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound CC[NH+]1CN(C)C=C1.[O-]S(=O)(=O)C(F)(F)F AFSJUFFXOPXIOH-UHFFFAOYSA-N 0.000 claims description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
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- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 claims description 6
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- 238000004769 chrono-potentiometry Methods 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 229940107700 pyruvic acid Drugs 0.000 claims description 4
- 239000001903 2-oxo-3-phenylpropanoic acid Substances 0.000 claims description 3
- QHKABHOOEWYVLI-UHFFFAOYSA-N 3-methyl-2-oxobutanoic acid Chemical compound CC(C)C(=O)C(O)=O QHKABHOOEWYVLI-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004716 alpha keto acids Chemical class 0.000 claims description 3
- DEDGUGJNLNLJSR-UHFFFAOYSA-N alpha-hydroxycinnamic acid Natural products OC(=O)C(O)=CC1=CC=CC=C1 DEDGUGJNLNLJSR-UHFFFAOYSA-N 0.000 claims description 3
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- -1 halide salt Chemical class 0.000 claims description 3
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000004718 beta keto acids Chemical class 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims description 2
- 150000004721 gamma keto acids Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000007858 starting material Substances 0.000 claims 1
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- 239000001257 hydrogen Substances 0.000 abstract description 9
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- 230000009467 reduction Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 235000001014 amino acid Nutrition 0.000 description 80
- 229940024606 amino acid Drugs 0.000 description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
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- 210000004027 cell Anatomy 0.000 description 13
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 10
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- 235000011150 stannous chloride Nutrition 0.000 description 10
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- 238000005406 washing Methods 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 239000004471 Glycine Substances 0.000 description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
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- XOYUVEPYBYHIFZ-UHFFFAOYSA-L diperchloryloxylead Chemical compound [Pb+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O XOYUVEPYBYHIFZ-UHFFFAOYSA-L 0.000 description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
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- 230000001105 regulatory effect Effects 0.000 description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
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- 238000001000 micrograph Methods 0.000 description 4
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- 239000004317 sodium nitrate Substances 0.000 description 4
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- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 3
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- 150000001371 alpha-amino acids Chemical class 0.000 description 2
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of electrocatalytic amino acid synthesis, and particularly relates to a catalyst for synthesizing amino acid, and a preparation method and application thereof. The components of the catalyst comprise PbX; x is at least one of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth. The catalyst has high hydrogen evolution potential, can simultaneously realize reduction of oxalic acid and nitrate radical, can be used for preparing amino acid under high current, and has high synthesis efficiency. The catalyst contains lead and X, so that the hydrogen evolution potential can be improved, and the catalyst has the technical effect of double reduction. The catalyst contains at least one metal ion of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth, and can solve the problems of serious hydrogen evolution reaction, poor product selectivity and low current density in the electrocatalytic amino acid synthesis process.
Description
Technical Field
The invention belongs to the field of electrocatalytic amino acid synthesis, and particularly relates to a catalyst for synthesizing amino acid, and a preparation method and application thereof.
Background
The amino acid can form peptide chain, which is the basic component of protein, and can be used as various functional materials such as feed additive, flavoring agent, fiber, medicine, etc. Plays an indispensable role in a plurality of industries such as food health care, biological medicine, agriculture, animal husbandry and the like. At present, the fermentation process for producing amino acids mainly by microbial fermentation culture of sugar raw materials has non-negligible disadvantages, such as high energy consumption and long time for culture, and complicated separation and purification processes of products. Chemical synthesis is a simple and effective method for producing amino acid, and the traditional method for synthesizing amino acid mainly depends on a Strecker synthesis scheme using cyanide as a raw material, and has strong toxicity and is not good for environment.
Electrocatalytic synthesis technology is considered to be one of the new approaches to achieve high value-added chemical synthesis. The waste pollutants or carbon dioxide, nitrate, nitrogen and the like are used as raw materials to become a green strategy for constructing the electrochemical C-N bond. However, these molecules are chemically stable and activation is relatively difficult. Some researchers have successfully performed electrochemical methods for constructing C-N bonds to amino acids using ammonia, hydroxylamine or nitrogen oxides as nitrogen sources and α -keto acids or oxalic acid as carbon sources. Among them, oxalic acid is one of the most common organic acids and is widely available, such as straw, pineapple waste, jute sticks, and the like. Reduction of nitrate ions is widely studied as a widely occurring contaminant in wastewater. The oxalic acid and nitrate are used as raw materials to synthesize amino acid, so that the conversion of high-added-value chemicals can be realized, and the removal of pollutants can be realized.
Since oxalic acid has a very negative reduction potential, acidic conditions are often required to achieve selective reduction. In addition, the electrocatalytic synthesis of amino acids from oxalic acid and nitrate requires a multi-step, multi-electron, multi-proton process. How to effectively inhibit hydrogen evolution under high current and achieve high selectivity has not been an effective solution. Therefore, the development of a catalyst which has high hydrogen evolution overpotential and can simultaneously realize selective reduction of oxalic acid and nitrate is of great significance for improving the synthesis efficiency of amino acid.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to develop a catalyst with high hydrogen evolution potential and capable of realizing selective reduction of oxalic acid and nitrate radical simultaneously so as to improve the synthesis efficiency of amino acid, and provide a catalyst for synthesizing amino acid, a preparation method and application thereof.
For this purpose, the invention provides the following technical scheme.
The invention provides a catalyst for synthesizing amino acid, wherein the components of the catalyst comprise PbX; x is at least one of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth.
The molar ratio of Pb to X in the PbX is (0-1): (0-1), and neither is 0;
preferably, the molar ratio of Pb and X in the PbX is (0.5-1): (0.1-0.65);
preferably, X is at least one of Sn and Bi;
preferably, the molar ratio of Sn to Bi is (0.25-0.75): 0.05-0.5.
The catalyst has a pore structure;
preferably, the pore structure has a pore size of 5-50 μm;
preferably, the pore walls of the pore structure have a multi-stage rod-like dendrite structure.
The invention also provides a preparation method of the catalyst for synthesizing amino acid, which comprises the steps of preparing an electrocatalyst containing PbX by adopting an electrochemical deposition method;
wherein X is at least one of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth.
The preparation method comprises the following steps:
preparing a first electrolyte; wherein the first electrolyte comprises at least lead salt and metal X salt;
and placing a substrate in the first electrolyte for electrochemical deposition.
The first electrolyte further comprises perchloric acid and/or a complexing agent;
preferably, the complexing agent is at least one of sodium citrate and disodium edetate;
preferably, the metal X salt is at least one of perchlorate, nitrate, halide salt and acetate;
preferably, the lead salt is at least one of perchlorate and nitrate;
preferably, the substrate is made of lead, copper or carbon.
The concentration of the perchloric acid in the first electrolyte is not higher than 5mol/L;
preferably, the dosage ratio of the complexing agent, the metal salt X and the lead salt in the first electrolyte is (0-2): 0-1, and the non-uniformity is 0;
preferably, the dosage ratio of the complexing agent, the metal salt X and the lead salt in the first electrolyte is (0.2-2): 0.25-0.75): 0.5-1;
performing the electrochemical deposition with constant current;
preferably, the current density of the deposition is 0.1-5A cm -2 The time is 10-120s.
Further, in the preparation of the catalyst for synthesizing amino acid, a carbon rod, a lead sheet or a titanium sheet is used as a counter electrode.
The invention also provides a method for synthesizing amino acid, which comprises the following steps: the catalyst for synthesizing amino acid or the catalyst prepared by the preparation method is adopted to perform electrocatalytic synthesis on amino acid.
Further, the raw materials for synthesizing the amino acid comprise a carbon source and a nitrogen source;
preferably, the carbon source is at least one of oxalic acid and a keto acid;
preferably, the keto acid is at least one of an alpha-keto acid, a beta-keto acid and a gamma-keto acid;
preferably, the keto acid comprises at least one of 2-oxo-3-methylbutyric acid, phenylpyruvic acid, glyoxylic acid, pyruvic acid and acetophenone acid;
preferably, the nitrogen source is one of nitrate, nitrite, nitric oxide and hydroxylamine;
preferably, the molar ratio of the carbon source to the nitrogen source is (0-10): (0-10) and neither is 0;
preferably, the molar ratio of the carbon source to the nitrogen source is (0.5-2): (0.5-1.5).
Further, when the nitrogen source is a gas, the nitrogen source gas is always introduced until the carbon source is completely reacted in the process of synthesizing the amino acid, and the nitrogen source gas is not particularly limited.
The method adopts an electrochemical chronoamperometry or chronopotentiometry to prepare the amino acid;
preferably, when the amino acid is prepared by chronopotentiometry, the current density is 20mA.cm -2 ～1.5A·cm -2 ；
Preferably, when the amino acid is prepared by adopting a chronoamperometric method, the potential is open circuit voltage-1.8V vs. SCE;
preferably, in carrying out the electrochemical reaction, the second electrolyte comprises H 2 SO 4 And/or ionic liquids;
preferably, H in the second electrolyte 2 SO 4 The concentration of (2) is 0.1-2.5mol/L;
preferably, the concentration of the ionic liquid in the second electrolyte is 5-100mmol/L;
preferably, the ionic liquid is at least one of pyridine ionic liquid, pyrrole ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid and imidazole ionic liquid;
preferably, the ionic liquid is 1-ethyl-3-methylimidazole triflate salt. When the amino acid is prepared, irTaTi net is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode.
The amino acids of the present invention may be glycine, leucine, isoleucine, alanine, glutamic acid, lysine, etc., and the kind of the synthesized amino acid depends on the choice of the carbon source and the nitrogen source of the raw material. The catalyst of the invention is particularly useful for synthesizing alpha-amino acids, such as glycine.
The technical scheme of the invention has the following advantages:
1. the catalyst for synthesizing amino acid provided by the invention comprises PbX; x is at least one of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth. The catalyst has high hydrogen evolution potential, can simultaneously realize reduction of oxalic acid and nitrate radical, can be used for preparing amino acid under high current, and has high synthesis efficiency. The catalyst contains lead and X, so that the hydrogen evolution potential can be improved, and the catalyst has the technical effect of double reduction. The catalyst contains at least one metal ion of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth, and can solve the problems of serious hydrogen evolution reaction, poor product selectivity and low current density in the electrocatalytic amino acid synthesis process.
The catalyst has rich pore structure and multi-dendrite structure, has larger specific surface area, exposes more active sites, is favorable for enrichment of reaction products and diffusion of substrates, and further improves catalytic activity.
2. The preparation method of the catalyst for synthesizing amino acid provided by the invention adopts an electrochemical deposition method to prepare the PbX catalyst, the morphology and structure of the catalyst are adjustable and controllable, and when the catalyst is used for synthesizing amino acid, the current density and Faraday efficiency in the electrocatalytic amino acid synthesizing process can be obviously improved.
Further, the method is favorable for preparing the catalyst with rich pore structures and multi-dendrite structures, the specific surface area of the catalyst is larger, more active sites can be exposed, the enrichment of reactants and the diffusion of substrates are facilitated, and the catalytic activity is further improved.
3. The preparation method of the catalyst for synthesizing amino acid is simple and easy, can realize the synthesis of the catalyst only by short-time electrodeposition, and has application value in amino acid synthesis.
4. The method for synthesizing amino acid provided by the invention can realize high-selectivity synthesis of amino acid under industrial current density by using the catalyst disclosed by the invention for synthesizing amino acid, and expands the design thought of the amino acid synthesizing catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the catalyst of example 1 of the present invention at different resolutions;
FIG. 2 is a transmission electron microscope image and a plain distribution mapping image of the catalyst of example 1 of the present invention; wherein 2a-b are transmission electron microscope pictures, and 2c-f are element distribution mapping pictures;
FIG. 3 is an X-ray powder diffraction pattern of the catalyst of example 1 of the present invention;
FIG. 4 shows the Faraday efficiency of the catalyst of example 1 of the invention for the electrocatalytic synthesis of amino acids at different potentials in an H-cell;
FIG. 5 is an i-t curve for electrocatalytically synthesizing amino acids in an H-cell using the catalyst of example 1 of the present invention;
FIG. 6 is a stability test of the catalyst of example 1 of the present invention in the electrocatalytic synthesis of amino acids in an H-cell.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a catalyst for synthesizing amino acid, which comprises the following steps:
(1) And mixing perchloric acid, sodium citrate, lead perchlorate, stannous chloride and bismuth nitrate to obtain a clear and transparent solution serving as electrolyte. Wherein the concentration of perchloric acid in the electrolyte is 1mol/L, the concentration of sodium citrate is 0.2mol/L, the concentration of lead perchlorate is 0.1mol/L, the concentration of stannous chloride is 0.05mol/L, and the concentration of bismuth nitrate is 0.0125mol/L.
(2) Washing the lead sheet with concentrated nitric acid, and taking the lead sheet as a working electrode substrate after drying; using a carbon rod as a counter electrode, performing electrochemical deposition by using a constant-current regulated power supply, and depositing on a lead sheet to form PbSnBi with current density of 5A cm -2 And (3) carrying out electrochemical deposition for 30s, washing for a plurality of times by using ethanol and deionized water after the deposition is finished, and drying to obtain the catalyst for synthesizing the amino acid.
The embodiment also provides a method for synthesizing glycine, which adopts a three-electrode system to electrochemically synthesize amino acid, and comprises the following steps:
synthesizing amino acid in an H pool by adopting a three-electrode system; the catalyst prepared by the above method was used as a working electrode (1 cm 2 ) The IrTaTi net is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the Nafion117 type proton exchange membrane is used as a diaphragm, and the electrolyte comprises H 2 SO 4 And 1-ethyl-3-methylimidazole triflate, H 2 SO 4 The concentration of (2) was 1.5mol/L, and the concentration of the ionic liquid was 10mmol/L. 12.5mmol of oxalic acid and 12.5mmol of sodium nitrate are added into a cathode cell, an H-type electrolytic cell is assembled, glycine is synthesized by adopting a chronoamperometry, and the potential of the chronoamperometry is-1.5V vs. Wherein the electrochemical workstation is the Shanghai Chenhua CHI1140 model.
Example 2
The embodiment provides a preparation method of a catalyst for synthesizing amino acid, which comprises the following steps:
(1) Perchloric acid, sodium citrate, lead perchlorate and stannous chloride are mixed to obtain clear and transparent solution which is used as electrolyte. Wherein the concentration of perchloric acid in the electrolyte is 1mol/L, the concentration of sodium citrate is 0.2mol/L, the concentration of lead perchlorate is 0.1mol/L, and the concentration of stannous chloride is 0.1mol/L.
(2) Washing the lead sheet with concentrated nitric acid, and taking the lead sheet as a working electrode substrate after drying; using a carbon rod as a counter electrode to enableElectrochemical deposition is carried out by using a constant-current regulated power supply, pbSn is formed on a lead sheet by deposition, and the current density is 2.5A cm -2 And (3) carrying out electrochemical deposition for 60 seconds, washing for a plurality of times by using ethanol and deionized water after the deposition is finished, and drying to obtain the catalyst for synthesizing the amino acid.
The embodiment also provides a method for synthesizing alanine, which adopts a three-electrode system to electrochemically synthesize amino acid, and comprises the following steps:
synthesizing amino acid in an H pool by adopting a three-electrode system; the catalyst prepared by the above method was used as a working electrode (1 cm 2 ) The IrTaTi net is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the Nafion117 type proton exchange membrane is used as a diaphragm, and the electrolyte comprises H 2 SO 4 And 1-ethyl-3-methylimidazole triflate, H 2 SO 4 The concentration of (2) was 1.5mol/L, and the concentration of the ionic liquid was 10mmol/L. Adding 12.5mmol of pyruvic acid and 12.5mmol of sodium nitrate into a cathode cell, assembling an H-type electrolytic cell, synthesizing amino acid by adopting a chronopotentiometric method, wherein the current density of the chronopotentiometric method is 500mA cm -2 . Wherein the electrochemical workstation is the Shanghai Chenhua CHI1140 model.
Example 3
The embodiment provides a preparation method of a catalyst for synthesizing amino acid, which comprises the following steps:
(1) Perchloric acid, sodium citrate, lead perchlorate, stannous chloride and indium nitrate are mixed to obtain clear and transparent solution which is used as electrolyte. Wherein the concentration of perchloric acid in the electrolyte is 1mol/L, the concentration of sodium citrate is 0.2mol/L, the concentration of lead perchlorate is 0.1mol/L, the concentration of stannous chloride is 0.05mol/L, and the concentration of indium nitrate is 0.0125mol/L.
(2) Washing the lead sheet with concentrated nitric acid, and taking the lead sheet as a working electrode substrate after drying; using a carbon rod as a counter electrode, performing electrochemical deposition by using a constant-current regulated power supply, and depositing PbSnIn on a lead sheet to form a current density of 1A cm -2 And (3) carrying out electrochemical deposition for 60 seconds, washing for a plurality of times by using ethanol and deionized water after the deposition is finished, and drying to obtain the catalyst for synthesizing the amino acid.
The embodiment also provides a method for synthesizing valine, which adopts a three-electrode system to electrochemically synthesize amino acid, and comprises the following steps:
synthesizing amino acid in an H pool by adopting a three-electrode system; the catalyst prepared by the above method was used as a working electrode (1 cm 2 ) The IrTaTi net is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the Nafion117 type proton exchange membrane is used as a diaphragm, and the electrolyte comprises H 2 SO 4 And 1-ethyl-3-methylimidazole triflate, H 2 SO 4 The concentration of (2) was 0.2mol/L, and the concentration of the ionic liquid was 5.0mmol/L. 15mmol of 2-oxo-3-methylbutyric acid and 12.5mmol of sodium nitrite are added into a cathode cell, an H-type electrolytic cell is assembled, amino acid is synthesized by adopting a chronopotentiometric method, and the current density of the chronopotentiometric method is 250mA cm -2 . Wherein the electrochemical workstation is the Shanghai Chenhua CHI1140 model.
Example 4
The embodiment provides a preparation method of a catalyst for synthesizing amino acid, which comprises the following steps:
(1) And mixing perchloric acid, disodium ethylenediamine tetraacetate, lead nitrate, stannous chloride and copper acetate to obtain a clear and transparent solution serving as electrolyte. Wherein the concentration of perchloric acid in the electrolyte is 1mol/L, the concentration of disodium ethylenediamine tetraacetate is 0.2mol/L, the concentration of lead nitrate is 0.1mol/L, the concentration of stannous chloride is 0.05mol/L, and the concentration of cupric acetate is 0.0125mol/L.
(2) Washing the lead sheet with concentrated nitric acid, and taking the lead sheet as a working electrode substrate after drying; using a carbon rod as a counter electrode, performing electrochemical deposition by using a constant-current regulated power supply, and depositing on a lead sheet to form PbSnCu with a current density of 1A cm -2 And (3) carrying out electrochemical deposition for 120s, washing for a plurality of times by using ethanol and deionized water after the deposition is finished, and drying to obtain the catalyst for synthesizing the amino acid.
The embodiment also provides a method for synthesizing phenylalanine, which adopts a three-electrode system to electrochemically synthesize amino acid, and comprises the following steps:
synthesizing amino acid in an H pool by adopting a three-electrode system; is applied toThe catalyst obtained by the method was used as a working electrode (1 cm 2 ) The IrTaTi net is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the Nafion117 type proton exchange membrane is used as a diaphragm, and the electrolyte comprises H 2 SO 4 And 1-ethyl-3-methylimidazole triflate, H 2 SO 4 The concentration of (2) was 1.0mol/L, and the concentration of the ionic liquid was 20mmol/L. 20mmol of phenylpyruvic acid and 15mmol of potassium nitrate are added into a cathode cell, and an H-type electrolytic cell is assembled for synthesizing the amino acid by adopting a chronoamperometry, wherein the current of the chronoamperometry is-1.0V vs. Wherein the electrochemical workstation is the Shanghai Chenhua CHI1140 model.
Example 5
The embodiment provides a preparation method of a catalyst for synthesizing amino acid, which comprises the following steps:
(1) Perchloric acid, disodium ethylenediamine tetraacetate, lead nitrate, stannous chloride and chromium nitrate are mixed to obtain clear and transparent solution which is used as electrolyte. Wherein the concentration of perchloric acid in the electrolyte is 1mol/L, the concentration of disodium ethylenediamine tetraacetate is 0.2mol/L, the concentration of lead nitrate is 0.1mol/L, the concentration of stannous chloride is 0.05mol/L, and the concentration of chromium nitrate is 0.0125mol/L.
(2) Washing the lead sheet with concentrated nitric acid, and taking the lead sheet as a working electrode substrate after drying; using a carbon rod as a counter electrode, performing electrochemical deposition by using a constant-current regulated power supply, and depositing PbSnCr on a lead sheet to form the lead sheet with the current density of 5A cm 2 The electrochemical deposition time is 30s, after the deposition is finished, ethanol and deionized water are used for washing for a plurality of times, and the catalyst for synthesizing amino acid is obtained after drying
The embodiment also provides a method for synthesizing alanine, which adopts a three-electrode system to electrochemically synthesize amino acid, and comprises the following steps:
synthesizing amino acid in an H pool by adopting a three-electrode system; the catalyst prepared by the above method was used as a working electrode (1 cm 2 ) The IrTaTi net is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the Nafion117 type proton exchange membrane is used as a diaphragm, and the electrolyte comprises HClO 4 And 1-ethyl-3-methylimidazole acetate, H 2 SO 4 Is 0.5The concentration of the ionic liquid is 5.0mmol/L. 15mmol of pyruvic acid and 10mL/min of nitric oxide are added into a cathode cell, an H-type electrolytic cell is assembled, the amino acid is synthesized by adopting a chronoamperometry, and the current of the chronoamperometry is-1.5V vs. Wherein the electrochemical workstation is the Shanghai Chenhua CHI1140 model.
Test example 1
This test example characterizes the performance of the catalyst of example 1 for the synthesis of amino acids, with the following results:
(1) FIG. 1 is a scanning electron microscope image of the catalyst of example 1 at different resolutions. It can be seen from fig. 1a that the catalyst has a rich pore structure, the pore diameter is about 20 μm, and the pore wall is a multi-stage rod-like dendrite.
(2) FIG. 2 is a transmission electron microscope image (FIGS. 2 a-b) and an element distribution mapping image (FIGS. 2 c-f) of the catalyst of example 1. From the figure, it can be seen that the catalyst has distinct crystal lattice fringes and the selective diffraction has no distinct diffraction ring. It can be seen from FIGS. 2d, 2e and 2f that Pb, sn and Bi elements are uniformly distributed.
(3) FIG. 3 is an X-ray powder diffraction pattern of the catalyst of example 1. It can be seen from the figure that the catalyst shows distinct diffraction peaks for Pb, sn and Bi metals.
Figures 1-3 illustrate that the catalyst is porous in structure.
Test example 2
This test example characterizes the performance of the amino acid synthesized by the catalyst of example 1, with the following results:
FIG. 4 is the Faraday efficiency of the catalyst of example 1 on glycine at different potentials in the electrocatalytic synthesis of amino acids in an H-cell. The results show that the catalyst has the highest amino acid Faraday efficiency for amino acids at a potential of-1.5V (vs. SCE).
Faraday efficiency fe= (n×f×c×v)/Qx 100%
Wherein F is Faraday constant 96485 C.mol -1 C is the concentration of glycine, V is the volume of electrolyte, and Q is the total charge of the reaction.
FIG. 5 is an i-t curve for the electrocatalytic synthesis of amino acids in an H-cell using the catalyst of example 1. FIG. 6 is a stability test of the catalyst of example 1 in the electrocatalytic synthesis of amino acids in an H-cell. FIGS. 5-6 illustrate that the catalyst of example 1 has good catalytic cycling stability, can maintain high current density and Faraday efficiency of amino acid, and further illustrates that the catalyst of the invention has high activity and great application potential.
The stability shown in fig. 6 is obtained by testing in a cyclic test mode, and specifically includes: synthesizing amino acid in an H pool by adopting a three-electrode system; the catalyst prepared by the above method was used as a working electrode (1 cm 2 ) The IrTaTi net is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the Nafion117 type proton exchange membrane is used as a diaphragm, and the electrolyte comprises H 2 SO 4 And 1-ethyl-3-methylimidazole triflate, H 2 SO 4 The concentration of (2) was 1.5mol/L, and the concentration of the ionic liquid was 10mmol/L. To the cathode cell, 0.25mol of oxalic acid and 0.25mol of sodium nitrate were added, and the H-type cell was assembled for testing. Wherein the electrochemical workstation is the Shanghai Chenhua CHI1140 model. At-1.5 v vs. sce potential, the reaction time was 2 hours, after each reaction was completed, the reaction electrode was rinsed with deionized water, the new electrolyte was replaced, and the same amount of oxalic acid and sodium nitrate as in the first reaction was added, at-1.5 v vs. sce potential, the reaction time was 2 hours, the above-described operations were repeated, and faraday efficiency was tested after each experiment was completed.
Further, as seen from the results of fig. 6, the average current density of the H cell in the synthesis of amino acids according to the present invention: 800mA cm -2 SCE has excellent stability at-1.5V vs. SCE, and can be stably reused for 10 times under the current density, and has the following advantages>The Faraday efficiency of 50% of amino acid is superior to that of the prior art for preparing amino acid, and the CoFe catalyst reported by Electrosynthesis of alpha-Amino Acids from NO and other NOx species over CoFe alloy-decollated Self-standing Carbon Fiber Membranes only shows<20mA·cm -2 The HgCu catalyst reported by Electrochemical Synthesis of Glycine from Oxalic Acid and Nitrate only showed 90 mA.cm with a current density of-0.7V vs. RHE and an amino acid Faraday efficiency of 41.2% -2 Current density at-1.4V vs. Ag/AgCl and amino acid Faraday efficiency of 43.1%The catalyst of the invention is obviously superior to the catalyst provided by the prior art.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A catalyst for synthesizing amino acids, wherein the catalyst comprises PbX as a component; x is at least one of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth.
2. The catalyst of claim 1 wherein the molar ratio of Pb to X in PbX is (0-1): (0-1) and neither is 0;
preferably, the molar ratio of Pb and X in the PbX is (0.5-1): (0.1-0.65);
preferably, X is at least one of Sn and Bi;
preferably, the molar ratio of Sn to Bi is (0.25-0.75): 0.05-0.5.
3. The catalyst according to claim 1 or 2, characterized in that the catalyst has a pore structure;
preferably, the pore structure has a pore size of 5-50 μm;
preferably, the pore walls of the pore structure have a multi-stage rod-like dendrite structure.
4. A method for preparing a catalyst for synthesizing amino acids, which is characterized by comprising the steps of preparing an electrocatalyst containing PbX by adopting an electrochemical deposition method;
wherein X is at least one of tin, chromium, copper, antimony, cadmium, niobium, gallium, indium and bismuth.
5. The method according to claim 4, comprising:
preparing a first electrolyte; wherein the first electrolyte comprises at least lead salt and metal X salt;
and placing a substrate in the first electrolyte for electrochemical deposition.
6. The method of claim 4 or 5, wherein the first electrolyte further comprises perchloric acid and/or a complexing agent;
preferably, the complexing agent is at least one of sodium citrate and disodium edetate;
preferably, the metal X salt is at least one of perchlorate, nitrate, halide salt and acetate;
preferably, the lead salt is at least one of perchlorate and nitrate;
preferably, the substrate is made of lead, copper or carbon.
7. The production method according to claim 5 or 6, wherein the concentration of perchloric acid in the first electrolytic solution is not higher than 5mol/L;
preferably, the dosage ratio of the complexing agent, the metal salt X and the lead salt in the first electrolyte is (0-2): 0-1, and the non-uniformity is 0;
preferably, the dosage ratio of the complexing agent, the metal salt X and the lead salt in the first electrolyte is (0.2-2): 0.25-0.75): 0.5-1;
performing the electrochemical deposition with constant current;
preferably, the current density of the deposition is 0.1-5A cm -2 The time is 10-120s.
8. A method of synthesizing an amino acid comprising the steps of: electrocatalytic synthesis of amino acids using a catalyst according to any one of claims 1 to 3 or a catalyst prepared by a process according to any one of claims 4 to 7.
9. The method of claim 8, wherein the starting material for synthesizing the amino acid comprises a carbon source and a nitrogen source;
preferably, the carbon source is at least one of oxalic acid and a keto acid;
preferably, the keto acid is at least one of an alpha-keto acid, a beta-keto acid and a gamma-keto acid;
preferably, the keto acid comprises at least one of 2-oxo-3-methylbutyric acid, phenylpyruvic acid, glyoxylic acid, pyruvic acid and acetophenone acid;
preferably, the nitrogen source is one of nitrate, nitrite, nitric oxide and hydroxylamine;
preferably, the molar ratio of the carbon source to the nitrogen source is (0-10): (0-10) and neither is 0;
preferably, the molar ratio of the carbon source to the nitrogen source is (0.5-2): (0.5-1.5).
10. The method according to claim 8 or 9, wherein the amino acid is prepared using an electrochemical chronoamperometry or chronopotentiometry;
preferably, when the amino acid is prepared by chronopotentiometry, the current density is 20mA.cm -2 ～1.5A·cm -2 ；
Preferably, when the amino acid is prepared by adopting a chronoamperometric method, the potential is open circuit voltage-1.8V vs. SCE;
preferably, in carrying out the electrochemical reaction, the second electrolyte comprises H 2 SO 4 And/or ionic liquids;
preferably, H in the second electrolyte 2 SO 4 The concentration of (2) is 0.1-2.5mol/L;
preferably, the concentration of the ionic liquid in the second electrolyte is 5-100mmol/L;
preferably, the ionic liquid is at least one of pyridine ionic liquid, pyrrole ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid and imidazole ionic liquid;
preferably, the ionic liquid is 1-ethyl-3-methylimidazole triflate salt.
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