CN101240428A - Method for preparing Pd-Ni bimetal modifying titanium catalysis electrode - Google Patents

Method for preparing Pd-Ni bimetal modifying titanium catalysis electrode Download PDF

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Publication number
CN101240428A
CN101240428A CNA2007101779770A CN200710177977A CN101240428A CN 101240428 A CN101240428 A CN 101240428A CN A2007101779770 A CNA2007101779770 A CN A2007101779770A CN 200710177977 A CN200710177977 A CN 200710177977A CN 101240428 A CN101240428 A CN 101240428A
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electrode
solution
pdcl
preparing
preparation
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孙治荣
胡翔
葛慧
李保华
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The invention relates to a preparing method of Pd-Ni bimetallic modified titanium catalytic electrode, belonging to the field of electrochemistry, particularly to a preparing method of a new catalytic electrode for electrochemical reducing to removing chlorinated organic compounds in water. Directed at the high cost of preparing electrochemical catalytic electrode currently, the invention introduces an inexpensive metal nickel to the individual mono-metallic catalyst Pd, in order to lower its preparing cost. NiSO4.7H2O crystal and NH4Cl powder are dissolved in PdCl2 solution, deionized water is added to form 3 to 15mmol/L PdCl2 +7 to 15mmol/L NiSO4.7H2O+0.1 to 0.3mol/L NH4Cl mixed solution, the pH value is adjusted to 6.5 to 8.5 by ammonia. Pd-Ni codeposition is carried out by electrodeposit method with titanium having clean surface as the cathode and the platinum sheet as the anode, the electrodepositing current is 20 to 80mA, the electrodepositing time is 30 minutes. Cleaning and cyclic voltammetry scan are carried out on the prepared Pd-Ni/Ti electrode. The result shows that the Pd-Ni/Ti electrode has higher catalytic activity under the condition of low cost, thus having some application prospect.

Description

The preparation method of Pd-Ni bimetal modifying titanium catalysis electrode
Technical field
The present invention relates to that a kind of what have catalytic capability is the preparation method of the Pd-Ni bimetallic catalytic electrode of carrier with the titanium base, be mainly used in electrochemical reduction and remove chlorinatedorganic in the water, belong to the technical field that electro-chemical water is handled.
Background technology
Chloro organic cpd is a class refractory organics organic compound, has great hazardness, their Stability Analysis of Structures, little, the long half time of volatility, easily in biology and food chain, accumulate, source water is caused severe contamination, human health is caused very big harm, and many chlorinatedorganics are considered to have " carcinogenic, teratogenesis, mutagenesis " effect.Therefore, it is very necessary chlorinatedorganic removal method in the water being studied.For now, the removal method of chlorinatedorganic has biological degradation method, absorption method, Fenton reagent method, wet oxidation process, ozone oxidation method, membrane separation technique, zero-valent metal and bimetallic catalytic reduction system dechlorination technology and electrochemical techniques etc.The electrochemical treatment of chlorinatedorganic is meant when conducting medium exists, and removes the method for pollutent in the decontaminated water by electrochemical reaction.In the research of the electrocatalytic hydrogenation dechlorination electrode preparation of being reported in recent years, palladium is because have excellent active hydrogen storage capability, can guarantee that active hydrogen contacts with the chloro organic molecule that is adsorbed continuously and becomes the emphasis of catalyst research.One of gordian technique of electrochemical reduction dechlorination is electrode, in recent years successively relevant for Pd/ activated carbon fiber (Pd/ACF) electrode, the Pd/GC electrode, the Pd/Ni electrode, monometallics such as Pd/Ti electrode directly are deposited on the research of the electrode on the base material, but because of its current efficiency when handling the lower concentration chlorinatedorganic is low, energy consumption and electrode preparation cost are higher, reasons such as catalytic activity is general are not promoted widely, and the research of efficient modified electrode is still continuing.
Summary of the invention
The present invention aims to provide a kind of preparation method with Pd-Ni bimetal modifying titanium catalysis electrode of catalytic capability, is mainly used in electrochemical reduction and removes chlorinatedorganic in the water.
The preparation method of the said Pd-Ni bimetal modifying titanium catalysis electrode of the present invention, its step is as follows:
1, Palladous chloride (PdCl 2) preparation of solution: with PdCl 2Powder is dissolved in the hydrochloric acid, with deionized water dilute 20～25mmol/L PdCl 2Solution.
2, the preparation of mixed solution: with NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl that step 1 is prepared 2In the solution, add deionized water and be mixed with (3～15) mmol/LPdCl 2+ (7～15) mmol/L NiSO 47H 2O+ (0.1～0.3) mol/L NH 4The mixing solutions of Cl is regulated pH to 6.5～8.5 with ammoniacal liquor.
3, the titanium base successively respectively in sulfuric acid (remove surperficial thing), acetone (oil removing), redistilled water ultrasonic oscillation dried standby to clean up in 10～15 minutes.
4, be negative electrode with the clean Ti of surface cleaning, platinized platinum is an anode, adopts the method for galvanic deposit to carry out Pd-Ni bimetal codeposition in the mixing solutions that step 2 is prepared, and deposition current is 20～80mA, and depositing time is 20～60min.
Pd-Ni/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/L H 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.Quality by the hydrogen adsorption peak value meter impressing electrode performance on the cyclic voltammetry curve.
Selected pH, NiSO 47H 2O concentration, PdCl 2Concentration, deposition current I and depositing time t are influence factor, carry out the optimization of electrode performance.Draw pH=6.5; Ni 2+=10mmol/L; Pd 2+=8.5mmol/L; I=60mA; T=40min is the preparation condition of optimum performance Pd-Ni/Ti electrode in the research range.
Different metal pair evolving hydrogen reactions have different catalytic capabilities, and overpotential of hydrogen evolution is low more, help the carrying out of evolving hydrogen reaction more.Another kind of have medium hydrogen ion adsorption ability and cheap metallic nickel are selected in this invention, the preparation bimetallic catalytic electrode.The adding of nickel has reduced the cost of catalyzer on the one hand, and on the other hand, because the adding of nickel, palladium crystalline defective increases in the catalyzer, thereby increases its surface-area, improves its adsorptive power to hydrogen atom.Adopt the method for electrochemical co-deposition to prepare the Pd-Ni/Ti electrode, not only improved the catalytic performance of electrode, also reduced the preparation cost of electrode, further promoting for it provides possibility.
Description of drawings
Fig. 1 is the cyclic voltammetry curve of embodiment 1,2,3 prepared electrodes.
Fig. 2 is the cyclic voltammetry curve of embodiment 4,5,6 and the prepared electrode of Comparative Examples.
Embodiment
Following embodiment will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1: take by weighing PdCl 2Powder is dissolved in the 3mol/LHCl solution, is mixed with the PdCl of 22.5mmol/L with deionized water 2Solution.
Take by weighing NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl of 22.5mmol/L 2In the solution, be mixed with 7mmol/L Ni with deionized water 2++ 3mmol/L Pd 2++ 0.2mol/L NH 4The mixed solution of Cl is regulated pH value to 7.5 with ammoniacal liquor.
With the Ti that cleans up is negative electrode, and platinized platinum is an anode, is the condition deposit 20min of 80mA in deposition current.
Pd-Ni/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/LH 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.The gained cyclic voltammetry curve is seen curve 1 among Fig. 1, occurs tangible hydrogen adsorption peak about-500mV, and peak value is-17.87mA.
Embodiment 2: take by weighing PdCl 2Powder is dissolved in the HCl solution of 3mol/L, is mixed with the PdCl of 20mmol/L with deionized water 2Solution.
Take by weighing NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl of 20mmol/L 2In the solution, be mixed with 20mmol/L Ni with deionized water 2++ 7mmol/L Pd 2++ 0.1mol/L NH 4The mixed solution of Cl.Regulate pH value to 8.5 with ammoniacal liquor.
With the Ti that cleans up is negative electrode, and platinized platinum is an anode, is the condition deposit 30min of 20mA in deposition current.
Pd-Ni/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/LH 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.The gained cyclic voltammetry curve is seen curve 2 among Fig. 1, occurs tangible hydrogen adsorption peak about-500mV, and peak value is-21.42mA.
Embodiment 3: take by weighing PdCl 2Powder is dissolved in the HCl solution of 3mol/L, is mixed with the PdCl of 25mmol/L with deionized water 2Solution.
Take by weighing NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl of 25mmol/L 2In the solution, be mixed with 10mmol/L Ni with deionized water 2++ 3mmol/L Pd 2++ 0.3mol/L NH 4The mixed solution of Cl.Regulate pH value to 8.0 with ammoniacal liquor.
With the Ti that cleans up is negative electrode, and platinized platinum is an anode, is the condition deposit 60min of 40mA in deposition current.
Pd-Ni/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/LH 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.The gained cyclic voltammetry curve is seen curve 3 among Fig. 1, occurs tangible hydrogen adsorption peak about-500mV, and peak value is-22.89mA.
Embodiment 4: take by weighing PdCl 2Powder is dissolved in the HCl solution of 3mol/L, is mixed with the PdCl of 22.5mmol/L with deionized water 2Solution.
Take by weighing NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl of 22.5mmol/L 2In the solution, be mixed with 10mmol/L Ni with deionized water 2++ 15mmol/L Pd 2++ 0.3mol/L NH 4The mixed solution of Cl.Regulate pH value to 6.3 with ammoniacal liquor.
With the Ti that cleans up is negative electrode, and platinized platinum is an anode, is the condition deposit 40min of 50mA in deposition current.
Pd-Ni/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/LH 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.The gained cyclic voltammetry curve is seen curve 4 among Fig. 2, occurs tangible hydrogen adsorption peak about-500mV, and peak value is-33.66mA.
Embodiment 5: take by weighing PdCl 2Powder is dissolved in the HCl solution of 3mol/L, is mixed with the PdCl of 21mmol/L with deionized water 2Solution.
Take by weighing NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl of 21mmol/L 2In the solution, be mixed with 15mmol/L Ni with deionized water 2++ 8.5mmol/L Pd 2++ 0.2mol/L NH 4The mixed solution of Cl.Regulate pH value to 6.5 with ammoniacal liquor.
With the Ti that cleans up is negative electrode, and platinized platinum is an anode, is the condition deposit 40min of 70mA in deposition current.
Pd-Ni/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/LH 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.The gained cyclic voltammetry curve is seen curve 5 among Fig. 2, occurs tangible hydrogen adsorption peak about-500mV, and peak value is-46.01mA.
Embodiment 6: take by weighing PdCl 2Powder is dissolved in the HCl solution of 3mol/L, is mixed with the PdCl of 22.5mmol/L with deionized water 2Solution.
Take by weighing NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl of 22.5mmol/L 2In the solution, be mixed with 10mmol/L Ni with deionized water 2++ 8.5mmol/L Pd 2++ 0.2mol/L NH 4The mixed solution of Cl.Regulate pH value to 6.5 with ammoniacal liquor.
With the glass carbon plate (GC) that cleans up is negative electrode, and platinized platinum is an anode, is the condition deposit 40min of 60mA in deposition current.
Pd-Ni/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/LH 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.The gained cyclic voltammetry curve tangible hydrogen adsorption peak occurs about-500mV shown in curve among Fig. 26, peak value is-64.40mA.
Comparative Examples: take by weighing PdCl 2Powder is dissolved in the HCl solution of 3mol/L, is mixed with the PdCl of 27mmol/L with deionized water 2Solution.
With the Ti that cleans up is negative electrode, and platinized platinum is an anode, at the PdCl of 27mmol/L 2Carry out the cathode electrodeposition of monometallic Pd in the solution.Deposition current is 20mA, and depositing time is 30min.
Pd/Ti electrode washing after galvanic deposit finished is clean, places 0.5mol/LH 2SO 4In the solution, be counter electrode with the platinized platinum, with Hg/HgSO 4Electrode is that reference electrode carries out cyclic voltammetry scan.The electric potential scanning scope is-700mV～700mV that sweep velocity is 50mV/s.The gained cyclic voltammetry curve tangible hydrogen adsorption peak occurs about-500mV shown in curve among Fig. 27, peak value is-12.19mA.
The result of embodiment and Comparative Examples comparison shows that, Pd in mixed solution 2+Under the lower situation of concentration, the cyclic voltammetry curve of Pd-Ni/Ti electrode can obtain the hydrogen adsorption peak value bigger than Pd/Ti electrode.

Claims (2)

  1. With the preparation method of Pd-Ni bimetal modifying titanium catalysis electrode, it is characterized in that 1, step is as follows:
    1), the preparation of palladium chloride solution: with PdCl 2Powder is dissolved in the hydrochloric acid of 3mol/L, with deionized water dilute 20～25mmol/L PdCl 2Solution;
    2), the preparation of mixed solution: with NiSO 47H 2O crystal and NH 4The Cl powder is dissolved in the PdCl that step 1) is prepared 2In the solution, add deionized water and be mixed with 3～15mmol/L PdCl 2+ 7～15mmol/L NiSO 47H 2O+0.1～0.3mol/LNH 4The mixing solutions of Cl is regulated pH to 6.5～8.5 with ammoniacal liquor;
    3), the titanium base respectively in sulfuric acid, acetone, redistilled water ultrasonic oscillation 10～15 minutes to clean up dry for standby;
    4), be negative electrode with the clean Ti of surface cleaning, platinized platinum is an anode, the method that adopts galvanic deposit is in step 2) carry out Pd-Ni bimetal codeposition in institute's liquid mixture prepared, deposition current is 20～80mA, depositing time is 20～60min.
  2. 2, the preparation method with the Pd-Ni bimetal modifying titanium catalysis electrode as claimed in claim 1 is characterized in that, mixed solution be formulated as 10mmol/L PdCl 2+ 8.5mmol/L NiSO 47H 2O+0.2mol/L NH 4The mixing solutions of Cl, pH value are 6.5, and deposition current is 60mA, and depositing time is 40min.
CNA2007101779770A 2007-11-23 2007-11-23 Method for preparing Pd-Ni bimetal modifying titanium catalysis electrode Pending CN101240428A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838830A (en) * 2010-05-07 2010-09-22 厦门大学 Electrolyte of electroplating palladium-nickel alloy
CN102061493A (en) * 2010-11-05 2011-05-18 北京工业大学 Method for preparing palladium-nickel bimetal catalysis electrode by using hexadecyl trimethylammonium bromide as additive
CN102061483A (en) * 2010-11-05 2011-05-18 北京工业大学 Method for preparing palladium-nickel duplex metal catalytic electrode by using sodium dodecyl benzene sulfonate as aid
CN101811755B (en) * 2009-11-27 2012-07-25 北京工业大学 Method for preparing sodium dodecyl benzene sulfonate doped titanium catalyzed electrode
CN105036259A (en) * 2015-07-01 2015-11-11 湖南大学 Modification method of double-metal-modified activated carbon fiber electrode by electrolytic deposition and application

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101811755B (en) * 2009-11-27 2012-07-25 北京工业大学 Method for preparing sodium dodecyl benzene sulfonate doped titanium catalyzed electrode
CN101838830A (en) * 2010-05-07 2010-09-22 厦门大学 Electrolyte of electroplating palladium-nickel alloy
CN101838830B (en) * 2010-05-07 2012-08-15 厦门大学 Electrolyte of electroplating palladium-nickel alloy
CN102061493A (en) * 2010-11-05 2011-05-18 北京工业大学 Method for preparing palladium-nickel bimetal catalysis electrode by using hexadecyl trimethylammonium bromide as additive
CN102061483A (en) * 2010-11-05 2011-05-18 北京工业大学 Method for preparing palladium-nickel duplex metal catalytic electrode by using sodium dodecyl benzene sulfonate as aid
CN102061483B (en) * 2010-11-05 2012-06-27 北京工业大学 Method for preparing palladium-nickel duplex metal catalytic electrode by using sodium dodecyl benzene sulfonate as aid
CN102061493B (en) * 2010-11-05 2012-07-04 北京工业大学 Method for preparing palladium-nickel bimetal catalysis electrode by using hexadecyl trimethylammonium bromide as additive
CN105036259A (en) * 2015-07-01 2015-11-11 湖南大学 Modification method of double-metal-modified activated carbon fiber electrode by electrolytic deposition and application

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