CN105274560A - Preparing method of novel Ce-La co-doped high-catalytic-activity Ti/Ce-Lanano-TiO2 modified electrode and method for electrocatalytic reduction of L-cystine through modified electrode - Google Patents
Preparing method of novel Ce-La co-doped high-catalytic-activity Ti/Ce-Lanano-TiO2 modified electrode and method for electrocatalytic reduction of L-cystine through modified electrode Download PDFInfo
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Abstract
The invention discloses a preparing method of a novel Ce-La co-doped high-catalytic-activity Ti/Ce-Lanano-TiO2 modified electrode and a method for electrocatalytic reduction of L-cystine through the modified electrode, and belongs to the technical field of organic electricity synthesis. The method comprises the specific steps that the rare earth Ce-La co-doped Ti/Ce-Lanano-TiO2 modified electrode is prepared; organic electricity synthesis is carried out, electrocatalytic reduction of L-cystine is carried out, L-cysteine is prepared, a self-assembled diaphragm plate frame type electrolytic cell is included, an electrolyte is prepared, and electrolysis operation is carried out; and product extraction is carried out, the electrolyzed electrolyte is extracted and purified, and then the L-cysteine product is obtained. The high-catalytic-activity Ti/Ce-Lanano-TiO2 modified electrode prepared through co-doped modification of rare earth Ce and rare earth La serves as a cathode, electrode crystal particles are fine and even, and the catalytic activity and stability of a TiO2 electrode are improved; and the electro-catalytic property, the corrosion resistance and selectivity of the electrode are greatly improved.
Description
Technical field
The invention belongs to Organic electro-synthesis technical field, more particularly, relate to a kind of high catalytic activity Ti/Ce-Lanano-TiO of novel C e-La codoped
2the method of the preparation of modified electrode and electrical catalyze reduction CYSTINE synthesis Cys thereof.
Background technology
Cys (L-cysteine) is one of 20 seed amino acids of constitutive protein matter, belongs to aliphatic amino acid.In protein, the CYSTINE form of Cys Chang Yiqi oxidized form exists, and the disulphide bridges (disulfidebridge) being oxidized to covalency by the-SH base on two Cys side chains is formed by connecting.Cys is found with the form of Gelucystine from vesical calculus in 1810 the earliest, and its chemical name is L-pantonine-thiohydracrylic acid (C
3h
7nO
2s), molecular mass is 121.12, and Cys is white crystalline powder, foreign odor, taste acid, soluble in water, and be slightly soluble in ethanol, stablize acid, and easy oxidation by air is Gelucystine in neutrality and basic solution, trace iron and heavy metal can impel it to be oxidized.Because the sulfydryl (-SH) polarity on Cys side chain is very strong, except there is chemical reaction that all amino acid can occur, also have some special chemical reactions.
According to the difference of configuration, halfcystine can be divided into L-type, D type and DL type point, and have in vivo physiologically active for L-type halfcystine.Cys is one of composition of constitutive protein matter, exists with the form of alpha amino acid.Its existence can keep the stability of protein, connects between same or different polypeptide chain two Cys residues with disulfide linkage (-S-S-), makes protein have stable space multistory knot.Cys forms the amino acid in protein 20 multiple amino acids with sulfhydryl-group activity, and it has been widely used at industry tools such as medicine, food, feed, makeup.Such as at field of medicaments, L-cysteine hydrochloride has the effect recovering liver function, can be used for radiopharmaceutic poisoning, the treatment of hepatitis, serum sickness, N-acetyl-L-cysteine is mucolysis expectorant in addition, and sputum can be made to be easy to expectoration or sucking-off, thus improve breath state, it is applicable to treatment acute/chronic bronchitis disease, bronchial asthma, the thick sputum that pulmonary tuberculosis etc. cause and airway obstruction etc.Cys also has the effects such as anti-inflammatory, pain relieving, anti-bacteria and growth of cancer cells simultaneously.In food service industry, Cys can as food flavoring agent and chromogenic reagent, bread additives, milk powder and the purposes such as fruit juice oxidation inhibitor and preservation agent, and in makeup, it is found that to produce skin-lightening cosmetic with Cys ideal, during its exploitation and use are in and are developed by leaps and bounds.Nearest photomedicine, photobiologic research show: can produce bottom melanochrome and cause melanin pigmentation in the undermost pigment cell of epidermis, epidermis is made to occur blackspot, and because the sulfydryl (-SH) of Cys has reducing power and chemical reactivity, thus melanic generation in regulating colouring matter cell.In animal-feed, the consumption of CYSTINE is very large, but due to the solubleness of CYSTINE too little, just can add in feed used so need to be prepared into Cys.And in recent years, because amino acid has purposes widely in food, medicine, feed, daily use chemicals etc., especially along with the fast development of cancer therapy drug, amino acid transfusion preparation and small peptide drug manufacture, current domestic and international market increases day by day to the amino acid whose annual requirement of raw material, more than 2000 tons, its price has increased to 7,80,000 yuan/ton by 30,000 yuan/ton (Renminbi).Therefore, the study on the synthesis carrying out Cys has realistic meaning importantly.
The synthesis mode of synthesis Cys mainly contains reduction method, enzymatic clarification method, chemical synthesis and fermentation method etc. after hair-hydrolyzation.China obtains CYSTINE after mainly relying on hair-hydrolyzation to the production of Cys, then CYSTINE is prepared Cys through electrolytic reduction or chemical mode, external mode mainly contains biological enzyme etc., various method is described below now:
1, reduction method after hair-hydrolyzation
The main component of hair (hair, pig hair, feather stem) is Keratin sulfate, it is made up of various a-amino acid, wherein Cys content is 12% ~ 14%, and therefore the industrial hair-hydrolyzation that often utilizes is to produce CYSTINE, then obtains Cys through electrolytic reduction.Keratic hydrolysis generally adopts basic hydrolysis and acid hydrolysis two kinds of methods, because after the hydrolysis of alkali hydrolysis method keratin, amino acid destroys more serious, yield is lower, and basic hydrolysis also can produce amino acid whose racemization in addition, and therefore the general acid-hydrolysis method that adopts is produced at present.The CYSTINE that acid hydrolysis obtains needs just can obtain Cys with electrolytic reduction or glass putty reduction further.This is a kind of method comparatively extensively adopted at present.
2, chemical synthesis
The approach chemically synthesizing Cys is made mainly to utilize alkyl chloride compounds through peroxidation, addition reaction, reduction reaction, the steps such as substitution reaction, finally obtain Cys, chemosynthesis Cys not only needs a lot of step, and produces DL-type racemic modification, only have and just can obtain required Cys through chemical resolution, therefore only for the synthesis of the intermediate of Cys.The extraction yield of the Cys that this method obtains only has 7.5%.
3 biological enzymes
In recent years, receive the attention of more and more people with the technology of enzyme process Preparation of amino acid, enzymatic clarification has self advantage, first its technique is comparatively simple, and there is optical activity, for the fine chemical product of costliness, adopt enzymatic clarification to have incomparable advantage.Current this technology also in fast development, the shortcomings such as it also exists expensive, and productive rate is lower.
4 fermentation methods
The fermentative Production of Cys is also present at present attempts the exploratory stage, large-scale volume production also has a lot of problems demand to solve, this method mainly by synthesizing in microbe, for most plant and microorganism ,-SH radical sources is in SO
4 2-, and SO
4 2-reducible is certain sulfide, this just fermentation method produce the insoluble problem of Cys.More external scholars are still probing into the method by enzyme system and regulatory gene, carry out fermentative production Cys with engineering strain and mutant bacteria.Even if but to today, this kind of mode cost is still very high, and transformation efficiency is still very low, so the scale production that cannot have high input.
Electrolytic reduction is the green synthesis method of generally acknowledging at present, and it is of reduced contamination, simple to operate, and technical process is simple, and quality product is high, and at present, existing research starts trial to be made electrochemically to synthesize Cys.But in the industry of Cys electrosynthesis, widely use pure Pb plate as cathode material, current efficiency is general not high, and this type of technical scheme exists electrode catalyst poor activity more simultaneously, and electrolytic efficiency is not high, electrode easy in inactivation in electrolytic process, electrode corrosion resistance nature is poor, and thus selectivity is bad causes side reaction many, in suitability for industrialized production, cannot realize, economic benefit is not high yet.Through retrieval, " CYSTINE is at Pb/nanoTiO to be published in the 16th volume the 1st phase on electrochemistry magazine in February, 2010
2electrical catalyze reduction on membrane electrode " (Chu Daobao, Wang Feng etc.), because Pb ion is unstable in acid, is certain to be dissolved in acid, easily causes the heavy metal contamination of product, this product is at preparation TiO simultaneously
2after electrode, still need galvanic deposit Pb at electrode surface, comparatively complicated.
Summary of the invention
1. invent the technical problem that will solve
The object of the invention is, in order to overcome above-mentioned shortcoming, to provide a kind of high catalytic activity Ti/Ce-Lanano-TiO of novel C e-La codoped
2the preparation method of modified electrode and employing Ti/Ce-Lanano-TiO
2the method of modified electrode catalytic reduction CYSTINE synthesis Cys, the present invention adopts sol-gel method to prepare the codoping modified high reactivity Ti/Ce-Lanano-TiO of a kind of Rare-Earth Ce, La
2modified electrode, the features such as it is high that this electrode has electro catalytic activity, unsuitable inactivation in electrolytic process, corrosion-resistant, with this Ti/Ce-Lanano-TiO
2modified electrode is negative electrode, and prepare Cys by electrolytic reduction CYSTINE in a cell, productive rate is high, and the selectivity in electrolytic process is good, and electrolysis side reaction is few, and current efficiency is high, ensure that the higher yields of Cys.The electrolytic yield of Cys reaches 98%, and current efficiency reaches 93%, and energy consumption is significantly reduced, energy consumption reduces by 17%, does not have " three wastes " to discharge, environmental protection in whole building-up process, belong to " green syt " technology, preparation process green non-pollution.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
The high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped of the present invention
2the preparation method of modified electrode, the steps include:
1), take pure titanium metal as matrix, polish successively with 800 object sand paper, 2000 object sand paper, deoil with acetone, absolute ethanol washing successively after having polished, and then the mixing solutions Titanium base after oil removing being put into ethylene glycol and HF carries out ultrasonic erosion operation, finally use the supersound washing successively of acetone, ethanol successively, then vacuum drying is stand-by.
2), the composite Nano TiO2 colloidal sol of preparation Rare-Earth Ce, La codoped, process is as follows: solution A is the mixed solution of the composition such as tetrabutyl titanate, dehydrated alcohol, methyl ethyl diketone, distilled water, and B solution is by dehydrated alcohol, distilled water, Ce (NO
3)
36H
20, La (NO
3)
36H
2the mixed solution of O composition, joins B solution in solution A, and under employing ultrasonic echography condition, stir while adding, stirring velocity, at 400 ~ 600r/min, forms colloidal sol after ageing under room temperature, is processed by colloidal sol by ultrasonic wave again, waits until for subsequent use.
3), by step 2) in through the sol coating of ultrasonication in step 1) in process on the Titanium base of the clean surface obtained, infrared drying is placed in retort furnace, carry out alternating temperature roasting, after room temperature cooling, as above operate, coating, roasting 9 times, namely can be made into the nano-TiO2 modification electrode of Ce, La codoped.
As a further improvement on the present invention, step 2) described in solution A in tetrabutyl titanate: dehydrated alcohol: the mol ratio of methyl ethyl diketone is 1:20:1, dehydrated alcohol in B solution: distilled water: La (NO
3)
36H
2o:Ce (NO
3)
36H
2the mol ratio of O is 10:0.15:0.2 ~ 0.7:0.1 ~ 0.5.
As a further improvement on the present invention, step 2) described in colloidal sol carry out ultrasonic echography process, under employing ultrasonic echography condition, stir while adding, under room temperature, ageing formed colloidal sol after 24 hours, and colloidal sol is carried out process 10 ~ 15min by ultrasonic wave again, waited until for subsequent use.
The high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped of the present invention
2the method of modified electrode electrical catalyze reduction CYSTINE, the steps include:
Step one,
The nano-TiO of the Ti/Ce-La codoped that preparation Rare-Earth Ce, La are codoping modified
2modified electrode;
Step 2,
Carry out electrolytic experiment, electrical catalyze reduction CYSTINE synthesis Cys, step is as follows:,
A), assembled belt diaphragm plate frame electrolyzer: the Ti/Ce-Lanano-TiO that the Rare-Earth Ce prepared with step one, La are codoping modified
2modified electrode is negative electrode, and DSA electrode is anode, and barrier film is cationic exchange membrane;
B), electrolytic solution is configured: catholyte is the mixed solution of CYSTINE, HCl solution; Anolyte is HCl solution;
C), electrolysis: the temperature controlling electrolysis is 25 DEG C, adopts constant voltage supply to carry out electrolysis procedure in a cell, and measures the electromotive force of negative electrode with volt ohm-milliammeter, controls the density of electric current at 3 ~ 5mAcm
-2, the time of electrolysis is 6 ~ 10h;
Step 3,
Extract product, take out the electrolytic solution that electrolysis completes in step 2, and carry out extracting, purifying, to obtain Cys product.
As a further improvement on the present invention, the Ti/Ce-Lanano-TiO that the Rare-Earth Ce prepared in step one, La are codoping modified
2the concrete operation step of modified electrode is:
1), take pure titanium metal as matrix, polish successively with 800 object sand paper, 2000 object sand paper, deoil with acetone, absolute ethanol washing successively after having polished, and then the mixing solutions Titanium base after oil removing being put into ethylene glycol and HF carries out ultrasonic erosion operation, finally use the supersound washing successively of acetone, ethanol successively, then vacuum drying is stand-by.
2) the composite Nano TiO of Rare-Earth Ce, La codoped, is prepared
2colloidal sol, process is as follows: solution A is the mixed solution of the compositions such as tetrabutyl titanate, dehydrated alcohol, methyl ethyl diketone, distilled water, and B solution is by dehydrated alcohol, distilled water, Ce (NO
3)
36H
20, La (NO
3)
36H
2the mixed solution of O composition, joins B solution in solution A, and under employing ultrasonic echography condition, stir while adding, stirring velocity, at 400 ~ 600r/min, forms colloidal sol after ageing under room temperature, is processed by colloidal sol by ultrasonic wave again, waits until for subsequent use.
3), by step 2) in through the sol coating of ultrasonication in step 1) in process on the Titanium base of the clean surface obtained, infrared drying is placed in retort furnace, carry out alternating temperature roasting, after room temperature cooling, as above operate, coating, roasting 9 times, namely can be made into the nano-TiO2 modification electrode of Ce, La codoped.
As a further improvement on the present invention, step 2) described in solution A in tetrabutyl titanate: dehydrated alcohol: the mol ratio of methyl ethyl diketone is 1:20:1, dehydrated alcohol in B solution: distilled water: La (NO
3)
36H
2o:Ce (NO
3)
3the mol ratio of 6H2O is 10:0.15:0.2 ~ 0.7:0.1 ~ 0.5.
As a further improvement on the present invention, step 2) described in colloidal sol carry out ultrasonic echography process, under employing ultrasonic echography condition, stir while adding, under room temperature, ageing formed colloidal sol after 24 hours, and colloidal sol is carried out process 10 ~ 15min by ultrasonic wave again, waited until for subsequent use.
As a further improvement on the present invention, step 3) carry out alternating temperature roasting with 100 DEG C ~ 500 DEG C;
As a further improvement on the present invention, steps A) described in electrolyzer be band diaphragm plate frame electrolyzer, described barrier film is Nafion117 type cationic exchange membrane.
As a further improvement on the present invention, step C) in constant voltage supply used be HYL-A type constant voltage supply, volt ohm-milliammeter used is DT9205 type volt ohm-milliammeter.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with prior art, there is following unusual effect:
(1) the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped of the present invention
2the preparation method of modified electrode, adopts sol-gel method to prepare the codoping modified high reactivity Ti/Ce-Lanano-TiO of a kind of Rare-Earth Ce, La
2modified electrode, contriver is concentrated on studies by long-term, and repeatedly repetition test draws to adulterate on original titanium-matrix electrode reasonable particle diameter and appropriate Rare-Earth Ce, La oxide compound, can obtain highly active Ti/Ce-Lanano-TiO
2modified electrode, adding of rare earth element promotes TiO
2electrode crystal grain is more tiny and even, improves and enhances TiO adding of rare earth element simultaneously
2the catalytic activity of electrode and stability, this electrode surface particle is little, and specific surface area is large, and then electrocatalysis position is increased, and specific activity conventional metals lead or zinc electrode strengthen 8 ~ 9 times; Simultaneously by codoped, the concerted catalysis reductive action between Ce, La, compares single doped Ce, La electrode, effectively improves reducing activity, compares common single doped Ce or La electrode enhancing 5 ~ 6 times.
(2) the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped of the present invention
2the method of modified electrode electrical catalyze reduction CYSTINE, reaction conditions is gentle, do not need to add catalyzer, simple to operate, equipment is easy to get, technical process is simple, cost of investment is low, the productive rate of Cys is high, does not have " three wastes " to discharge, environmental protection in whole building-up process, belong to " green syt " technology, preparation process green non-pollution.
(3) the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped of the present invention
2the method of modified electrode electrical catalyze reduction CYSTINE, adopts the high reactivity Ti/Ce-Lanano-TiO that homemade Rare-Earth Ce, La are codoping modified
2modified electrode is as negative electrode, the unsuitable inactivation of electrode in electrolytic process, electrode good corrosion resistance, electrolytic process selectivity is good, electrolysis side reaction greatly reduces, carried out reasonable disposition to some correlation parameters in electrolytic process, electrolytic efficiency improves greatly simultaneously, ensure that the high yield of Cys, the electrolytic yield of Cys reaches 98%, current efficiency reaches 93%, and energy consumption is significantly reduced, and energy consumption reduces by 17%.
Embodiment
For understanding content of the present invention further, below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The method of the high catalytic activity Ti/Ce-Lanano-TiO2 modified electrode electrical catalyze reduction CYSTINE of a kind of novel C e-La codoped of the present embodiment, the steps include:
The high reactivity Ti/Ce-Lanano-TiO that step one, preparation Rare-Earth Ce, La are codoping modified
2modified electrode
1) be, with pure titanium metal matrix, pure titanium metal described herein refers to that purity is the titanium metal of 99.5 ~ 99.7%.
800 orders and 2000 object emery papers are adopted to polish successively this Titanium base, acetone, absolute ethanol washing oil removing is used successively after having polished, Titanium base after oil removing is put into the mixing solutions ultrasonic erosion 20min of HF and ethylene glycol, the volume ratio of hydrofluoric acid and ethylene glycol is 1:4 again.Finally use intermediate water, acetone, dehydrated alcohol supersound washing 20min successively, vacuum-drying is stand-by.
2) the composite Nano TiO of Rare-Earth Ce, La codoped, is prepared
2colloidal sol, process is as follows: solution A by tetrabutyl titanate, methyl ethyl diketone, dehydrated alcohol and distilled water composition mixed solution, wherein tetrabutyl titanate: dehydrated alcohol: the mol ratio of methyl ethyl diketone is 1:20:1.B solution is by dehydrated alcohol, distilled water, Ce (NO
3)
36H
2o and La (NO
3)
36H
2the mixed solution of O composition, dehydrated alcohol in the present embodiment: distilled water: Ce (NO
3)
36H
2o:La (NO
3)
36H
2the mol ratio of O is 10:0.15:0.2:0.1.B solution joined in solution A, under employing ultrasonic echography condition, stir while adding, stirring velocity is 400r/min, and under room temperature, ageing formed colloidal sol after one day, carries out ultrasound procedure 10 minutes to colloidal sol simultaneously.
3), by step 1) in process step 2 in the pure Titanium base surface-coated in the surface that obtains) colloidal sol for preparing of supersound process, infrared drying is placed on alternating temperature roasting in retort furnace, take out after cooling, repeat above operation, 9 coatings, 9 roastings, can prepare the Ti/Ce-Lanano-TiO that Rare-Earth Ce, La are codoping modified
2modified electrode, first in infrared drying oven, 80 DEG C are warming up at a slow speed, and then be placed in retort furnace and carry out alternating temperature calcining, in concrete retort furnace in the present embodiment, 9 heating schedule temperature-rising methods are as follows: a) with 5 DEG C/min temperature programming to 100 DEG C, homogenizing annealing 26min, takes out after naturally cooling in stove; B) with the temperature programming 150 DEG C of 6 DEG C/min, homogenizing annealing 28min, takes out with after stove naturally cooling; C) with 7 DEG C/min temperature programming to 200 DEG C, homogenizing annealing 30min, takes out with after stove naturally cooling; D) with 9 DEG C/min temperature programming to 250 DEG C, homogenizing annealing 32min, takes out with after stove naturally cooling; E) with 11 DEG C/min temperature programming to 300 DEG C, homogenizing annealing 34min, takes out with after stove naturally cooling; F) with 12 DEG C/min temperature programming to 350 DEG C, homogenizing annealing 36min, takes out with after stove naturally cooling; G) with 15 DEG C/min temperature programming to 400 DEG C, homogenizing annealing 38min; H) with 17 DEG C/min temperature programming to 450 DEG C, homogenizing annealing 40min, takes out with after stove naturally cooling; I) with 20 DEG C/min temperature programming to 500 DEG C, homogenizing annealing 42min, takes out with after stove naturally cooling; In above-mentioned 9 heating schedule temperature-rise periods, its temperature rise rate is class stepped form, and its annealing time increases successively, and experiment proves, the Ti/Ce-Lanano-TiO that the Rare-Earth Ce prepared by this kind of heating schedule, La are codoping modified
2modified electrode performance is best, and the codoping modified electrode stability of Rare-Earth Ce, La is best.
Step 2, carry out electrolytic experiment, electrochemical catalysis reduction CYSTINE synthesis Cys, its concrete steps are as follows:
A), assembled belt diaphragm plate frame electrolyzer: with DSA electrode (with titanium for matrix, coating is platiniferous, the precious metal chloride of titanium, palladium, iridium isoreactivity element) be anode, the Rare-Earth Ce prepared with step one, the Ti/Ce-Lanano-TiO of modification of La codoped
2modified electrode is negative electrode, and barrier film is Nafion117 type cationic exchange membrane.
B), electrolytic solution is configured: catholyte is the mixed solution of CYSTINE, HCl solution, and in this example, in catholyte, the concentration of CYSTINE is 1.0molL
-1, the concentration of HCl solution is 1.0molL
-1, anolyte is HCl solution, and wherein the concentration of HCl solution is also 1.0molL
-1.Test proves, the electrolytic solution partition ratio of this exemplary configuration is comparatively suitable, and electrolytic efficiency is high.
C), electrolysis: controlling electrolysis temperature is 25 DEG C, and adopt constant voltage supply to carry out electrolytic experiment in a cell, cathode potential measured by volt ohm-milliammeter, and control current density is 3mAcm
-2, electrolysis time is 10h.Constant voltage supply used in the present embodiment is HYL-A type constant voltage supply, and volt ohm-milliammeter used is DT9205 type volt ohm-milliammeter.
Step 3, extraction product: take out the electrolytic solution that in step 2, electrolysis completes, take out and evaporate part HCl, then crystallisation by cooling, use whizzer to carry out centrifugation, and drying is rear obtains Cys product.The present embodiment adopts Ti/Ce-Lanano-TiO
2the method of modified electrode electrical catalyze reduction CYSTINE synthesis Cys, in electrolytic process, current efficiency is up to 92%, and the productive rate of Cys is up to 98%.
This Ti/Ce-Lanano-TiO adopted in experimental example
2modified electrode electrical catalyze reduction CYSTINE synthesis Cys, adopts the high reactivity Ti/Ce-Lanano-TiO that homemade Rare-Earth Ce, La are codoping modified
2modified electrode is as negative electrode, and this kind of electrode has good corrosion resistance nature, and electrolytic process selectivity is good, and electrolysis side reaction is less.Electrochemical catalysis productive rate is high, and reaction conditions is gentle, does not need to add catalyzer, preparation process green non-pollution.
Embodiment 2
The method of the high catalytic activity Ti/Ce-Lanano-TiO2 modified electrode electrical catalyze reduction CYSTINE of a kind of novel C e-La codoped of the present embodiment, the steps include:
The high reactivity Ti/Ce-Lanano-TiO that step one, preparation Rare-Earth Ce, La are codoping modified
2modified electrode
1) be, with pure titanium metal matrix, pure titanium metal described herein refers to that purity is the titanium metal of 99.5 ~ 99.7%.
800 orders and 2000 object emery papers are adopted to polish successively this Titanium base, acetone, absolute ethanol washing oil removing is used successively after having polished, Titanium base after oil removing is put into the mixing solutions ultrasonic erosion 20min of HF and ethylene glycol, the volume ratio of HF and ethylene glycol is 1:4 again.Finally use intermediate water, acetone, dehydrated alcohol supersound washing 20min successively, vacuum-drying is stand-by.
2) the composite Nano TiO of Rare-Earth Ce, La codoped, is prepared
2colloidal sol, process is as follows: solution A by tetra-n-butyl titanate, methyl ethyl diketone, dehydrated alcohol and distilled water composition mixed solution, wherein tetra-n-butyl titanate: dehydrated alcohol: the mol ratio of methyl ethyl diketone is 1:20:1.B solution is by dehydrated alcohol, distilled water, Ce (NO
3)
36H
2o and La (NO
3)
36H
2the mixed solution of O composition, dehydrated alcohol in the present embodiment: distilled water: Ce (NO
3)
36H
2o:La (NO
3)
36H
2the mol ratio of O is 10:0.25:0.3:0.4.B solution joined in solution A, under employing ultrasonic echography condition, stir while adding, stirring velocity is 500r/min, and under room temperature, ageing formed colloidal sol after one day, carries out ultrasound procedure 15 minutes to colloidal sol simultaneously.
3), by step 1) in process step 2 in the pure Titanium base surface-coated in the surface that obtains) colloidal sol for preparing of supersound process, infrared drying is placed on alternating temperature roasting in retort furnace, take out after cooling, repeat above operation, 9 coatings, 9 roastings, can prepare the Ti/Ce-Lanano-TiO that Rare-Earth Ce, La are codoping modified
2modified electrode, first in infrared drying oven, 80 DEG C are warming up at a slow speed, and then be placed in retort furnace and carry out alternating temperature calcining, in concrete retort furnace in the present embodiment, 9 heating schedule temperature-rising methods are as follows: a) with 5 DEG C/min temperature programming to 100 DEG C, homogenizing annealing 26min, takes out after naturally cooling in stove; B) with the temperature programming 150 DEG C of 6 DEG C/min, homogenizing annealing 28min, takes out with after stove naturally cooling; C) with 7 DEG C/min temperature programming to 200 DEG C, homogenizing annealing 30min, takes out with after stove naturally cooling; D) with 9 DEG C/min temperature programming to 250 DEG C, homogenizing annealing 32min, takes out with after stove naturally cooling; E) with 11 DEG C/min temperature programming to 300 DEG C, homogenizing annealing 34min, takes out with after stove naturally cooling; F) with 12 DEG C/min temperature programming to 350 DEG C, homogenizing annealing 36min, takes out with after stove naturally cooling; G) with 15 DEG C/min temperature programming to 400 DEG C, homogenizing annealing 38min; H) with 17 DEG C/min temperature programming to 450 DEG C, homogenizing annealing 40min, takes out with after stove naturally cooling; I) with 20 DEG C/min temperature programming to 500 DEG C, homogenizing annealing 42min, takes out with after stove naturally cooling; In above-mentioned 9 heating schedule temperature-rise periods, its temperature rise rate is class stepped form, and its annealing time increases successively, and experiment proves, the Ti/Ce-Lanano-TiO that the Rare-Earth Ce prepared by this kind of heating schedule, La are codoping modified
2modified electrode performance is best, and the codoping modified electrode stability of Rare-Earth Ce, La is best.
This example has prepared the codoping modified high reactivity Ti/Ce-Lanano-TiO of a kind of Rare-Earth Ce, La by adopting sol-gel method
2modified electrode, contriver is concentrated on studies by long-term, and repeatedly repetition test draws to adulterate on original titanium-matrix electrode reasonable particle diameter and appropriate rare earth La, Ce oxide compound, can obtain highly active Ti/Ce-Lanano-TiO
2modified electrode, this electrode surface grain diameter can reach about 23nm, and specific surface area is large, and then electrocatalysis position is increased.Meanwhile, the Ti/Ce-Lanano-TiO that contriver is codoping modified to preparation Rare-Earth Ce, La
2the process of modified electrode has carried out repetition test and theoretical deliberation, finally determines the key prepared in electrode process: the composite Nano TiO of preparation Rare-Earth Ce, La codoped
2the component of A, B solution in sol-process, proportioning, supersound process and coating, the temperature rise rate of roasting process, annealing time.
Step 2, carry out electrolytic experiment, electrochemical catalysis reduction CYSTINE synthesis Cys, its concrete steps are as follows:
A), assembled belt diaphragm plate frame electrolyzer: with DSA electrode (with titanium for matrix, coating is platiniferous, the precious metal chloride of titanium, palladium, iridium isoreactivity element) be anode, the Rare-Earth Ce prepared with step one, the Ti/Ce-Lanano-TiO of modification of La codoped
2modified electrode is negative electrode, and barrier film is Nafion117 type cationic exchange membrane.
B), electrolytic solution is configured: catholyte is the mixed solution of CYSTINE, HCl solution, and in this example, in catholyte, the concentration of CYSTINE is 1.0molL
-1, the concentration of HCl solution is 1.0molL
-1, anolyte is HCl solution, and wherein the concentration of HCl solution is also 1.0molL
-1.Test proves, the electrolytic solution partition ratio of this exemplary configuration is comparatively suitable, and electrolytic efficiency is high.
C), electrolysis: controlling electrolysis temperature is 25 DEG C, and adopt constant voltage supply to carry out electrolytic experiment in a cell, cathode potential measured by volt ohm-milliammeter, and control current density is 5mAcm
-2, electrolysis time is 6h.Constant voltage supply used in the present embodiment is HYL-A type constant voltage supply, and volt ohm-milliammeter used is DT9205 type volt ohm-milliammeter.
Step 3, extraction product: take out the electrolytic solution that in step 2, electrolysis completes, take out and evaporate part HCl, then crystallisation by cooling, use whizzer to carry out centrifugation, and drying is rear obtains Cys product.The present embodiment adopts Ti/Ce-Lanano-TiO
2the method of modified electrode electrical catalyze reduction CYSTINE synthesis Cys, in electrolytic process, current efficiency is up to 93%, and the productive rate of Cys is up to 97%.
Embodiment 3
The method of the high catalytic activity Ti/Ce-Lanano-TiO2 modified electrode electrical catalyze reduction CYSTINE of a kind of novel C e-La codoped of the present embodiment, the steps include:
The high reactivity Ti/Ce-Lanano-TiO that step one, preparation Rare-Earth Ce, La are codoping modified
2modified electrode
1) be, with pure titanium metal matrix, pure titanium metal described herein refers to that purity is the titanium metal of 99.5 ~ 99.7%.
800 orders and 2000 object emery papers are adopted to polish successively this Titanium base, acetone, absolute ethanol washing oil removing is used successively after having polished, Titanium base after oil removing is put into the mixing solutions ultrasonic erosion 15min of HF and ethylene glycol, the volume ratio of HF and ethylene glycol is 1:4 again.Finally use intermediate water, acetone, dehydrated alcohol supersound washing 15min successively, vacuum-drying is stand-by.
2) the composite Nano TiO of Rare-Earth Ce, La codoped, is prepared
2colloidal sol, process is as follows: solution A by tetra-n-butyl titanate, methyl ethyl diketone, dehydrated alcohol and distilled water composition mixed solution, wherein tetra-n-butyl titanate: dehydrated alcohol: the mol ratio of methyl ethyl diketone is 1:20:1.B solution is by dehydrated alcohol, distilled water, Ce (NO
3)
36H
2o and La (NO
3)
36H
2the mixed solution of O composition, dehydrated alcohol in the present embodiment: distilled water: Ce (NO
3)
36H
2o:La (NO
3)
36H
2the mol ratio of O is 10:0.25:0.7:0.5.B solution joined in solution A, under employing ultrasonic echography condition, stir while adding, stirring velocity is 600r/min, and under room temperature, ageing formed colloidal sol after one day, carries out ultrasound procedure 13 minutes to colloidal sol simultaneously.
3), by step 1) in process step 2 in the pure Titanium base surface-coated in the surface that obtains) colloidal sol for preparing of supersound process, infrared drying is placed on alternating temperature roasting in retort furnace, take out after cooling, repeat above operation, 9 coatings, 9 roastings, can prepare the Ti/Ce-Lanano-TiO that Rare-Earth Ce, La are codoping modified
2modified electrode, first in infrared drying oven, 80 DEG C are warming up at a slow speed, and then be placed in retort furnace and carry out alternating temperature calcining, in concrete retort furnace in the present embodiment, 9 heating schedule temperature-rising methods are as follows: a) with 5 DEG C/min temperature programming to 100 DEG C, homogenizing annealing 26min, takes out after naturally cooling in stove; B) with the temperature programming 150 DEG C of 6 DEG C/min, homogenizing annealing 28min, takes out with after stove naturally cooling; C) with 7 DEG C/min temperature programming to 200 DEG C, homogenizing annealing 30min, takes out with after stove naturally cooling; D) with 9 DEG C/min temperature programming to 250 DEG C, homogenizing annealing 32min, takes out with after stove naturally cooling; E) with 11 DEG C/min temperature programming to 300 DEG C, homogenizing annealing 34min, takes out with after stove naturally cooling; F) with 12 DEG C/min temperature programming to 350 DEG C, homogenizing annealing 36min, takes out with after stove naturally cooling; G) with 15 DEG C/min temperature programming to 400 DEG C, homogenizing annealing 38min; H) with 17 DEG C/min temperature programming to 450 DEG C, homogenizing annealing 40min, takes out with after stove naturally cooling; I) with 20 DEG C/min temperature programming to 500 DEG C, homogenizing annealing 42min, takes out with after stove naturally cooling; In above-mentioned 9 heating schedule temperature-rise periods, its temperature rise rate is class stepped form, and its annealing time increases successively, and experiment proves, the Ti/Ce-Lanano-TiO that the Rare-Earth Ce prepared by this kind of heating schedule, La are codoping modified
2modified electrode performance is best, and the codoping modified electrode stability of Rare-Earth Ce, La is best.
This example has prepared the codoping modified high reactivity Ti/Ce-Lanano-TiO of a kind of Rare-Earth Ce, La by adopting sol-gel method
2modified electrode, contriver is concentrated on studies by long-term, and repeatedly repetition test draws to adulterate on original titanium-matrix electrode reasonable particle diameter and appropriate rare earth La, Ce oxide compound, can obtain highly active Ti/Ce-Lanano-TiO
2modified electrode, this electrode surface grain diameter can reach about 12nm, and specific surface area is large, and then electrocatalysis position is increased.Meanwhile, the Ti/Ce-Lanano-TiO that contriver is codoping modified to preparation Rare-Earth Ce, La
2the process of modified electrode has carried out repetition test and theoretical deliberation, finally determines the key prepared in electrode process: the composite Nano TiO of preparation Rare-Earth Ce, La codoped
2the component of A, B solution in sol-process, proportioning, supersound process and coating, the temperature rise rate of roasting process, annealing time.Thus, the plumbous or zinc electrode of the modified electrode specific activity conventional metals for preparing of the present embodiment strengthens 8 ~ 9 times.Pass through codoped simultaneously, concerted catalysis reductive action between Ce, La, compares single doped Ce, La electrode, effectively improves reducing activity, compare common single doped Ce or La electrode enhancing 5 ~ 6 times, this synthesizes Cys for follow-up high-level efficiency electrocatalysis and provides guarantee.
Step 2, carry out electrolytic experiment, electrochemical catalysis reduction CYSTINE synthesis Cys, its concrete steps are as follows:
A), assembled belt diaphragm plate frame electrolyzer: with DSA electrode (with titanium for matrix, coating is platiniferous, the precious metal chloride of titanium, palladium, iridium isoreactivity element) be anode, the Rare-Earth Ce prepared with step one, the Ti/Ce-Lanano-TiO of modification of La codoped
2modified electrode is negative electrode, and two interelectrode interpole gaps are 6mm, and barrier film is Nafion117 type cationic exchange membrane.
B), electrolytic solution is configured: catholyte is the mixed solution of CYSTINE, HCl solution, and in this example, in catholyte, the concentration of CYSTINE is 1.0molL
-1, the concentration of HCl solution is 1.0molL
-1, anolyte is HCl solution, and wherein the concentration of HCl solution is also 1.0molL
-1.Test proves, the electrolytic solution partition ratio of this exemplary configuration is comparatively suitable, and electrolytic efficiency is high.
C), electrolysis: controlling electrolysis temperature is 25 DEG C, and adopt constant voltage supply to carry out electrolytic experiment in a cell, cathode potential measured by volt ohm-milliammeter, and control current density is 4mAcm
-2, electrolysis time is 8h.Constant voltage supply used in the present embodiment is HYL-A type constant voltage supply, and volt ohm-milliammeter used is DT9205 type volt ohm-milliammeter.
Step 3, extraction product: take out the electrolytic solution that in step 2, electrolysis completes, take out and evaporate part HCl, then crystallisation by cooling, use whizzer to carry out centrifugation, and drying is rear obtains Cys product.
This Ti/Ce-Lanano-TiO adopted in experimental example 1 ~ 3
2modified electrode electrical catalyze reduction CYSTINE synthesis Cys, adopts the high reactivity Ti/Ce-Lanano-TiO that homemade Rare-Earth Ce, La are codoping modified
2modified electrode is as negative electrode, this kind of electrode has good corrosion resistance nature, electrolytic process selectivity is good, electrochemical catalysis productive rate is high, reaction conditions is gentle, do not need to add catalyzer, the unsuitable inactivation of electrode in electrolytic process, electrolytic process selectivity is good, electrolysis side reaction greatly reduces, carried out reasonable disposition to some correlation parameters in electrolytic process, electrolytic efficiency improves greatly simultaneously, ensure that the high yield of Cys, the electrolytic yield of Cys reaches 98%, current efficiency reaches 93%, and energy consumption is significantly reduced, and energy consumption reduces by 17%.
Schematically above be described the present invention and embodiment thereof, this description does not have restricted, and also just one of the embodiments of the present invention shown in embodiment, actual structure is not limited thereto.So, if those of ordinary skill in the art enlightens by it, when not departing from the invention aim, designing the frame mode similar to this technical scheme and embodiment without creationary, all should protection scope of the present invention be belonged to.
Claims (10)
1. the high catalytic activity Ti/Ce-Lanano-TiO of a novel C e-La codoped
2the preparation method of modified electrode, is characterized in that: the steps include:
1), take pure titanium metal as matrix, polish successively with 800 object sand paper, 2000 object sand paper, deoil with acetone, absolute ethanol washing successively after having polished, and then the mixing solutions Titanium base after oil removing being put into ethylene glycol and HF carries out ultrasonic erosion operation, finally use the supersound washing successively of acetone, ethanol successively, then vacuum drying is stand-by;
2) the composite Nano TiO of Rare-Earth Ce, La codoped, is prepared
2colloidal sol, process is as follows: solution A is the mixed solution of the compositions such as tetrabutyl titanate, dehydrated alcohol, methyl ethyl diketone, distilled water, and B solution is by dehydrated alcohol, distilled water, Ce (NO
3)
36H
20, La (NO
3)
36H
2the mixed solution of O composition, joins B solution in solution A, and under employing ultrasonic echography condition, stir while adding, stirring velocity, at 400 ~ 600r/min, forms colloidal sol after ageing under room temperature, is processed by colloidal sol by ultrasonic wave again, waits until for subsequent use;
3), by step 2) in through the sol coating of ultrasonication in step 1) in process on the Titanium base of the clean surface obtained, infrared drying is placed in retort furnace, carry out alternating temperature roasting, after room temperature cooling, as above operate, coating, roasting 9 times, namely can be made into the nano-TiO of Ce, La codoped
2modification electrode.
2. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 1
2the preparation method of modified electrode, is characterized in that: step 2) described in solution A in tetrabutyl titanate: dehydrated alcohol: the mol ratio of methyl ethyl diketone is 1:20:1, dehydrated alcohol in B solution: distilled water: La (NO
3)
36H
2o:Ce (NO
3)
36H
2the mol ratio of O is 10:0.15:0.2 ~ 0.7:0.1 ~ 0.5.
3. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 1
2the preparation method of modified electrode, it is characterized in that: step 2) described in colloidal sol carry out ultrasonic echography process, under employing ultrasonic echography condition, B solution is joined in solution A, stir while adding, under room temperature, ageing formed colloidal sol after 24 hours, and colloidal sol is carried out process 10 ~ 15min by ultrasonic wave again, waited until for subsequent use.
4. the high catalytic activity Ti/Ce-Lanano-TiO of a novel C e-La codoped
2the method of modified electrode electrical catalyze reduction CYSTINE, is characterized in that, the steps include:
Step one,
The nano-TiO of the Ti/Ce-La codoped that preparation Rare-Earth Ce, La are codoping modified
2modified electrode;
Step 2,
Carry out electrolytic experiment, electrical catalyze reduction CYSTINE synthesis Cys, step is as follows:
A), assembled belt diaphragm plate frame electrolyzer: the Ti/Ce-Lanano-TiO that the Rare-Earth Ce prepared with step one, La are codoping modified
2modified electrode is negative electrode, and DSA electrode is anode, and barrier film is cationic exchange membrane;
B), electrolytic solution is configured: catholyte is the mixed solution of CYSTINE, HCl solution; Anolyte is HCl solution;
C), electrolysis: the temperature controlling electrolysis is 25 DEG C, adopts constant voltage supply to carry out electrolysis procedure in a cell, and measures the electromotive force of negative electrode with volt ohm-milliammeter, controls the density of electric current at 3 ~ 5mAcm
-2, the time of electrolysis is 6 ~ 10h;
Step 3,
Extract product, take out the electrolytic solution that electrolysis completes in step 2, and carry out extracting, purifying, to obtain Cys product.
5. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 4
2the method of modified electrode electrical catalyze reduction CYSTINE, the Ti/Ce-Lanano-TiO that the Rare-Earth Ce of wherein preparation in step one, La are codoping modified
2the concrete operation step of modified electrode is:
1), take pure titanium metal as matrix, polish successively with 800 object sand paper, 2000 object sand paper, deoil with acetone, absolute ethanol washing successively after having polished, and then the mixing solutions Titanium base after oil removing being put into ethylene glycol and HF carries out ultrasonic erosion operation, finally use the supersound washing successively of acetone, ethanol successively, then vacuum drying is stand-by;
2) the composite Nano TiO of Rare-Earth Ce, La codoped, is prepared
2colloidal sol, process is as follows: solution A is the mixed solution of the compositions such as tetrabutyl titanate, dehydrated alcohol, methyl ethyl diketone, distilled water, and B solution is by dehydrated alcohol, distilled water, Ce (NO
3)
36H
20, La (NO
3)
36H
2the mixed solution of O composition, joins B solution in solution A, and under employing ultrasonic echography condition, stir while adding, stirring velocity, at 400 ~ 600r/min, forms colloidal sol after ageing under room temperature, is processed by colloidal sol by ultrasonic wave again, waits until for subsequent use;
3), by step 2) in through the sol coating of ultrasonication in step 1) in process on the Titanium base of the clean surface obtained, infrared drying is placed in retort furnace, carry out alternating temperature roasting, after room temperature cooling, as above operate, coating, roasting 9 times, namely can be made into the nano-TiO of Ce, La codoped
2modification electrode.
6. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 5
2the method of modified electrode electrical catalyze reduction CYSTINE, is characterized in that: step 2) described in solution A in tetrabutyl titanate: dehydrated alcohol: the mol ratio of methyl ethyl diketone is 1:20:1, dehydrated alcohol in B solution: distilled water: La (NO
3)
36H
2o:Ce (NO
3)
36H
2the mol ratio of O is 10:0.15:0.2 ~ 0.7:0.1 ~ 0.5.
7. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 5
2the method of modified electrode electrical catalyze reduction CYSTINE, it is characterized in that: step 2) described in colloidal sol carry out ultrasonic echography process, under employing ultrasonic echography condition, B solution is joined in solution A, stir while adding, under room temperature, ageing formed colloidal sol after 24 hours, and colloidal sol is carried out process 10 ~ 15min by ultrasonic wave again, waited until for subsequent use.
8. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 5
2the method of modified electrode electrical catalyze reduction CYSTINE, is characterized in that: step 3) in carry out alternating temperature roasting with 100 DEG C ~ 500 DEG C.
9. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 5 or 6
2the method of modified electrode electrical catalyze reduction CYSTINE, is characterized in that: steps A) described in electrolyzer be band diaphragm plate frame electrolyzer, described barrier film is Nafion117 type cationic exchange membrane.
10. the high catalytic activity Ti/Ce-Lanano-TiO of a kind of novel C e-La codoped according to claim 7
2the method of modified electrode electrical catalyze reduction CYSTINE, is characterized in that: step C) in constant voltage supply used be HYL-A type constant voltage supply, volt ohm-milliammeter used is DT9205 type volt ohm-milliammeter.
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