CN100432297C - Electrode for removing nitrate from water and preparation method thereof - Google Patents
Electrode for removing nitrate from water and preparation method thereof Download PDFInfo
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- CN100432297C CN100432297C CNB200410098589XA CN200410098589A CN100432297C CN 100432297 C CN100432297 C CN 100432297C CN B200410098589X A CNB200410098589X A CN B200410098589XA CN 200410098589 A CN200410098589 A CN 200410098589A CN 100432297 C CN100432297 C CN 100432297C
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Abstract
The present invention discloses an electrode for removing nitrate from water and a preparation method thereof. The electrode uses a copper plate as a carrier; the copper plate is ground with sand paper and is cleaned with acetone supersound; after acid corrosion, one kind of palladium precious metal, platinic precious metal, auriferous precious metal, rhodium precious metal and ruthenic precious metal, and tin are respectively deposited on the copper plate, and accordingly, an electrode which can reduce the nitrate in water can be obtained. The electrode of the present invention has the advantages of low cost, high activity, simple preparation method of the electrode, and easy operation.
Description
Invention field
The present invention relates to a kind of electrode of removing nitrate in the water and preparation method thereof, specifically is a kind of metal-modified copper electrode, with the nitrate reduction in the water, belongs to the Application Areas of water technology under the situation of energising.
Background of invention
Owing to being extensive use of and the reasons such as a large amount of dischargings of municipal effluent and trade effluent of agrochemical, causing global pollution of nitrate nitrogen in underground water, and be the trend that goes from bad to worse.Increase 0.8mg/L every year on average as nitrate in the many regional water of the U.S., Germany has the concentration of 50% agricultural well water nitrate to surpass 60mg/L.The situation of China also allows of no optimist.At present, the most of areas of China are subjected to azotate pollution to some extent as the underground water of drinking water source, and the trend that increases the weight of is year by year arranged, and its concentration of indivedual areas has surpassed 100mg-N/L.
The nitrate of Excessive Intake has a lot of harm to HUMAN HEALTH, can cause methemoglobinemia, can cause hypoxia death when serious.And effect such as that the inferior ammonium nitrate that forms in the nitrate conversion process etc. also have is carcinogenic, teratogenesis and mutagenesis.Therefore the pollution of nitrate nitrogen in the purifying drinking water becomes crucial environmental problem.
The method of removing nitrate in the water at present mainly contains physics method, biological denitrification method and chemical reduction method.The required expense of nitrate that the physics method is removed in the underground water is too high, does not have selectivity, and the transfer of nitrate pollutants has just taken place or concentrates, and in fact it is not removed up hill and dale, so be subjected to certain restriction in application; Though the biological denitrificaion method can thoroughly be reduced into nitrogen with nitrate, but still the shortcoming that exists some to be difficult to overcome is low as capacity of resisting impact load, has secondary pollution, complex process is not suitable on a small scale and disperses to water treatment etc.Chemical reduction method comprises metal simple-substance reduction method, hydrogen catalysis reduction method and electrochemical reducing.The metal simple-substance reduction method is to be that reductive agent is a nitrogen with nitrate reduction with metal simple-substances such as iron, aluminium, zinc, and its reaction conditions is difficult to control, easily produces by product and causes secondary pollution.The hydrogen catalysis reduction method is to be reductive agent with hydrogen, under the effect of catalyzer nitrate is reduced, and its speed of response is fast, can avoid the secondary pollution to water.But the solubleness of hydrogen in water is low, and inflammable and explosive, and the transportation difficulty has inconvenience when using.Electrochemical reducing is a kind of method of denitration that just develops out in recent years, and it is reductive agent with the electronics, need not add any medicament, can avoid going out the water generates secondary pollution, and technology is simple, and easy handling still is in theoretical research stage at present.
Summary of the invention
The objective of the invention is: provide that a kind of cost is low, high reactivity, in order to remove the electrode and the preparation method of nitrate in the water.
The said electrode of the present invention is to utilize electric plating method that a kind of (A) in the precious metal of palladium, platinum, gold, rhodium, ruthenium and tin successively are deposited on the copper coin copper electrode of the surface modification that makes respectively.
A kind of electrode method of removing nitrate in the water for preparing, it is that first corresponding solubility lead compound with precious metal (A) is dissolved in the hydrochloric acid soln, be added drop-wise to it in ammonium chloride solution lentamente then, and powerful the stirring, be prepared into the ammonium complex compound of this kind precious metal, with this complex compound is electroplate liquid, Electrodeposition of Noble Metal on copper coin (A); Then with the copper electrode of precious metal (A) modification as negative electrode, place the hydrochloric acid soln galvanic deposit Sn of tin protochloride, distilled water promptly gets the electrode of removing nitrate in the water after cleaning.
The electroplate liquid of described Electrodeposition of Noble Metal (A) is formed: precious metal (A) content: 0.5-10mmol/L, NH
4Cl:0.01-1mol/L, pH=0.3-2; Galvanic deposit tin electroplating liquid is formed: SnCl
2: 0.025mmol/L, hydrochloric acid: 0.1mol/L;
The preparation method of described Electrodeposition of Noble Metal (A): (1) Constant Electric Current deposition: current density 4mA/cm
2, depositing time 5-60min; (2) constant voltage galvanic deposit: sedimentation potential-0.1V-0.9V, depositing time 0.5-60min.In the power on preparation method of deposit tin of the copper electrode of precious metal (A) modification: constant voltage galvanic deposit: sedimentation potential-0.1V--0.8V, depositing time 1-20min.
The present invention can be used for removing the nitrate pollutants in underground water or the surface water, and electrical catalyze reduction nitrate is had very high activity.
Outstanding advantage of the present invention is: the electrode activity height, electrode preparation method is simple, cost is low.
Embodiment
Example 1
At first with standby after copper coin sand papering, acetone ultrasonic cleaning, the phosphoric acid cleaning.
The 0.08866g Palladous chloride is dissolved in the appropriate hydrochloric acid solution, then it is added drop-wise in the ammonium chloride solution lentamente, and powerful the stirring, be settled to 500mL, make wherein that Pd content is 1mmol/L, NH
4Cl is 0.01mol/L, and utilizing dilute hydrochloric acid or sodium hydroxide solution to regulate pH is 1, and this solution is the electroplate liquid of depositing noble metal Pd.With the copper coin after cleaning is negative electrode, and platinized platinum is an anode, Constant Electric Current deposition Pd in this solution.Current density 4mA/cm
2, depositing time 20min utilizes distilled water to clean subsequently and promptly gets the copper electrode of Pd modification.Then with this electrode as negative electrode, platinized platinum is an anode, at 0.025mmol/L SnCl
2Constant voltage galvanic deposit Sn in the+0.1mol/L hydrochloric acid soln, sedimentation potential-0.8V, depositing time 5min, distilled water promptly gets the electrode of removing nitrate in the water after cleaning.
Adopt this electrode as the nitrate in the cathodic reduction water, the nitrate radical starting point concentration is 100mg/L, and initial pH is 7.6, and after 120min was carried out in reaction, the nitrate radical clearance can reach more than 90%.
Example 2
Copper coin pre-treatment and electrode preparation method such as example 1, that different is constant voltage galvanic deposit Pd, sedimentation potential-0.3V, depositing time 35min.Utilize distilled water to clean subsequently and promptly get the copper electrode of Pd modification.Then with this electrode as negative electrode, platinized platinum is an anode, at 0.025mmol/LSnCl
2Constant voltage galvanic deposit Sn in the+0.1mol/L hydrochloric acid soln, sedimentation potential-0.8V, depositing time 1min, distilled water promptly gets the electrode of removing nitrate in the water after cleaning.
Adopt this electrode as the nitrate in the cathodic reduction water, the nitrate radical starting point concentration is 100mg/L, and initial pH is 7.6, and after 120min was carried out in reaction, the nitrate radical clearance can reach more than 90%.
Claims (6)
1. an electrode of removing nitrate in the water is characterized in that, is carrier with the copper coin, utilizes electric plating method that a kind of and tin in precious metal (A) palladium, platinum, gold, rhodium, the ruthenium successively is deposited on respectively on the copper coin, promptly gets the electrode of nitrate in the reducible water.
2. the preparation method of the described electrode of claim 1, it is characterized in that, corresponding solubility lead compound with precious metal (A) is dissolved in the hydrochloric acid soln earlier, be added drop-wise to it in ammonium chloride solution lentamente then, and powerful the stirring, being prepared into the ammonium complex compound of this kind precious metal, is electroplate liquid with this complex compound, Electrodeposition of Noble Metal on copper coin (A); Then with the copper electrode of precious metal (A) modification as negative electrode, place the hydrochloric acid soln galvanic deposit Sn of tin protochloride, distilled water promptly gets the electrode of removing nitrate in the water after cleaning.
3. according to the described preparation method of claim 2, it is characterized in that nitrate, acetate, chlorate that the corresponding solubility lead compound of described precious metal (A) is precious metal (A); The electroplate liquid of Electrodeposition of Noble Metal (A) is formed: precious metal (A) content: 0.5-10mmol/L, NH
4Cl:0.01-1mol/L, pH=0.3-2.
4. according to the described preparation method of claim 2, it is characterized in that the preparation method of described Electrodeposition of Noble Metal (A): (1) Constant Electric Current deposition: current density 4mA/cm
2, depositing time 5-60min; (2) constant voltage galvanic deposit: sedimentation potential-0.1V-0.9V, depositing time 0.5-60min.
5. according to the described preparation method of claim 2, it is characterized in that the power on electroplate liquid of deposit tin of described copper electrode in precious metal (A) modification is formed: SnCl
2: 0.025mmol/L, hydrochloric acid: 0.1mol/L.
6. according to the described preparation method of claim 2, it is characterized in that the power on preparation method of deposit tin of described copper electrode: constant voltage galvanic deposit, sedimentation potential-0.1V--0.8V, depositing time 1-20min in precious metal (A) modification.
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| CNB200410098589XA CN100432297C (en) | 2004-12-15 | 2004-12-15 | Electrode for removing nitrate from water and preparation method thereof |
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| CNB200410098589XA CN100432297C (en) | 2004-12-15 | 2004-12-15 | Electrode for removing nitrate from water and preparation method thereof |
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| CN1789497A CN1789497A (en) | 2006-06-21 |
| CN100432297C true CN100432297C (en) | 2008-11-12 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101537353B (en) * | 2009-04-29 | 2011-05-11 | 安徽师范大学 | Preparation method of single-dimensional nano composite material |
| CN101700924B (en) * | 2009-11-30 | 2011-06-29 | 重庆大学 | Device for removing nitrate in water |
| CN104671362B (en) * | 2013-11-29 | 2016-08-17 | 中国科学院生态环境研究中心 | Remove electrode of bromate and preparation method thereof in water |
| CN105973955A (en) * | 2016-04-26 | 2016-09-28 | 中国科学院电子学研究所 | Tin-palladium composite electrode and preparation method and application thereof |
| CN106564984B (en) * | 2016-10-19 | 2019-06-25 | 天津中智科技发展有限公司 | A kind of reductive water generation restores the preparation method of piece with quantum |
| CN108862472A (en) * | 2018-07-04 | 2018-11-23 | 南京大学 | A kind of advanced waste treatment method of ion exchange resin and the integrated removing nitrate nitrogen of electrochemistry |
| CN111115768B (en) * | 2019-12-13 | 2021-03-16 | 南京大学 | Electrode for removing nitrate nitrogen and total nitrogen in water and preparation method thereof |
| CN111170416B (en) * | 2020-01-09 | 2021-04-02 | 中国原子能科学研究院 | Method for removing nitric acid in nitric acid-containing solution |
| CN112591856B (en) * | 2020-12-04 | 2021-12-14 | 北京师范大学 | Electrocatalytic activity regulation and control method based on inert ion intercalation |
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| JPH07216579A (en) * | 1994-02-03 | 1995-08-15 | Hitachi Koki Co Ltd | Formation of gold-tin soldered layer and method for joining the same |
| WO2003100135A2 (en) * | 2002-05-24 | 2003-12-04 | De Nora Elettrodi S.P.A. | Electrode for gas evolution and method for its production |
| CN1508074A (en) * | 2002-12-13 | 2004-06-30 | 中国科学院生态环境研究中心 | Method and apparatus for treating water by catalytic reduction of nano metal-memebrane composite electrode |
| JP2004190065A (en) * | 2002-12-09 | 2004-07-08 | Fcm Kk | Connector terminal, and connector having same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07216579A (en) * | 1994-02-03 | 1995-08-15 | Hitachi Koki Co Ltd | Formation of gold-tin soldered layer and method for joining the same |
| WO2003100135A2 (en) * | 2002-05-24 | 2003-12-04 | De Nora Elettrodi S.P.A. | Electrode for gas evolution and method for its production |
| JP2004190065A (en) * | 2002-12-09 | 2004-07-08 | Fcm Kk | Connector terminal, and connector having same |
| CN1508074A (en) * | 2002-12-13 | 2004-06-30 | 中国科学院生态环境研究中心 | Method and apparatus for treating water by catalytic reduction of nano metal-memebrane composite electrode |
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| N03-和NO2-在有机锡修饰电极上的电化学研究. 罗胜联，廖见培，黄杉生.湖南大学学报（自然科学版），第30卷第2期. 2003 * |
| 甲醇在欠电位沉积Sn/Pt电极上催化氧化. 魏子栋，三木敦史，大森唯义，大泽雅俊.物理化学学报，第18卷第12期. 2002 * |
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