CN106555212A - A kind of preparation method of the controllable ultra-thin palladium film of thickness - Google Patents
A kind of preparation method of the controllable ultra-thin palladium film of thickness Download PDFInfo
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- CN106555212A CN106555212A CN201510621786.3A CN201510621786A CN106555212A CN 106555212 A CN106555212 A CN 106555212A CN 201510621786 A CN201510621786 A CN 201510621786A CN 106555212 A CN106555212 A CN 106555212A
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Abstract
The present invention relates to a kind of preparation method of the controllable ultra-thin palladium film of thickness.Using carrier to be plated as working electrode, platinum electrode is that, to electrode, saturated calomel electrode is reference electrode to the present invention, three-electrode system is built, with chlorimide palladium as the main salt of electrolyte, is aided with ammonia for chelating agent, potassium chloride is additional conductive agent, by palladium electro-deposition on carrier, forms fine and close palladium film.In electrochemical plating film system, the compactness extent of film forming can be controlled, regulates and controls total reaction quantity of electric charge, control the quality of palladium film, so as to control the thickness of film forming by regulating and controlling to arrange electric current density.The present invention breaks through the restriction of traditional chemical depositing process, can accurately prepare ultra-thin palladium film, has the advantages that process is simple, reproducible, the preparation of the ultra-thin palladium film of suitable scale.
Description
Technical field：
The present invention relates to a kind of technology of preparing of the controllable ultra-thin palladium film of thickness, specially adopts
Electrochemical method prepares ultra-thin palladium membrane technology.The method is former based on electrochemical cathode reduction reaction
Reason, realizes reduction deposition of the palladium ion on porous stainless steel carrier and cellular ceramic substrate, leads to
The total quantity of electric charge of control electric current density and electrochemical reaction is crossed, is realized to palladium film surface compact degree
With the control of film thickness, and then the ultra-thin palladium film of ideal thickness can be prepared.
Background technology：
21 century is the epoch that membrane science is developed rapidly, and film is used as a kind of cleaning, efficient material
Material, is widely used in the fields such as food, weaving, medicine, chemical industry.Membrane separation technique is used as one
Plant low-carbon (LC), the technology of energy-saving and environmental protection, product in the purification, production process in domestic water
The every aspects such as the separation of harmful gass in enrichment and purification, environmental conservation, play which not
It is alternative to act on.It is by taking the separation of hydrogen and purification as an example, flat based on thermodynamical equilibrium and absorption
The tradition separating and purifying technology such as pressure-variable adsorption and temp.-changing adsorption of weighing apparatus, in traditional Hydrogen Separation and
Purification field is extensively applied, but as equipment investment is big, high energy consumption, technological process are complicated, point
Affected by many factors from efficiency, therefore in terms of purifying and preparing ultra-pure hydrogen, also
Very big weak point.
The research of load type metal palladium film, for people provide it is a kind of efficiently, cleaning, energy-conservation
High-purity hydrogen isolation technics.Compared to non-loading type palladium film prepared by mechanical press method, with many
Hole ceramics or porous stainless Steel material are the load type palladium film of carrier, not only reduce precious metal palladium
Consumption, reduce production cost, the carrier structure of porous reduces hydrogen in Metal Palladium in addition
Resistance to mass tranfer in film so that hydrogen process is changed into external diffusion control from bulk diffusion rate-determining steps thoroughly,
Hydrogen penetration is improve, while remain higher hydrogen selective.
When load type palladium film is prepared, the thickness and mechanical strength of film are to ensure Hydrogen Separation process
In key factor, on the premise of the higher mechanical strength of palladium film is ensured, reduce the thickness of palladium film
Degree, can largely improve load type palladium membrane separation efficiency.With self-catalysis film formation reaction
Based on chemical palladium-plating method, the pattern strong adaptability of carrier simple with its equipment operation,
Reaction is gentle and the field such as be widely used in testing, produce, but be intended to the palladium of acquisition exact thickness
Film, but has certain difficulty.This is also a difficult problem of load type palladium film research field.
The present invention is directed to traditional chemical plated film, and the thickness for existing is difficult to the problem of accurate control, root
According to principle of electrochemical reaction, with reference to the practical situation of coating process, three-electrode system is built, led to
Electric current density size is overregulated, the surface topography and compactness extent of palladium film forming process is controlled；
The total quantity of electric charge of electrochemical reaction is adjusted, palladium atomic deposition total amount is controlled.And then reach control palladium
The purpose of the mechanical strength and film thickness of film.
The content of the invention：
It is an object of the invention to provide a kind of method of the controllable load type palladium film of thickness, solves real
In border experiment production process, Hydrogen Separation and purification process, to the ultra-thin palladium film of high-performance supported type
Needs.For achieving the above object, inventor is by the comparison to traditional chemical film-forming method,
Method using palladium plating film is determined finally, by electric current density in electrochemical reaction process
With the control of total amount of electric charge, fine and close so as to obtain membrane superficial tissue, high mechanical strength, thickness can
Control, the good ultra-thin palladium film of hydrogen selective.
To achieve these goals, this patent provides a kind of controllable load type palladium film of thickness
Preparation method.Concrete technology flow process is as follows：
1. the selection and surface preparation of carrier, based on the electric conductivity of carrier, can be divided into porous not
Rust steel carrier and cellular ceramic substrate.
Porous stainless steel carrier aperture defect is 0.2 μm -0.5 μm, first in dehydrated alcohol
(99.7%) NaCO3Solution (NaCO3Concentration is 0.05mol/L) middle immersion supersound process
20min-40min, removes carrier surface greasy dirt, afterwards the supersound process in the hydrochloric acid of 5-10%
5min-10min, removes the sull of carrier surface, finally in deionized water at ultrasound
Reason 20min-40min, removes acid, alkali and the ethanol solution of residual.Cellular ceramic substrate aperture
Defect is 0.1 μm -0.2 μm, the NaCO of dehydrated alcohol (99.7%)3Solution (NaCO3Concentration is
Immersion supersound process 20min-40min in 0.05mol/L), removes carrier surface greasy dirt, afterwards
Immersion in deionized water washes 10min-20min, removes the alcoholic solution of residual.Due to porous
Ceramic monolith main component is γ-Al2O3And ZrO2There is no electric conductivity, so will carry in advance
One layer of palladium core of body surface face kind, increases its electric conductivity.Concrete operations are as follows：Patent [Xu is can refer to (
Permanent swimming, Tang Chunhua, Li Chunlin, Ge Qingjie, a kind of high hydrogen permeation selectivity metal palladium-based composite membrane
Preparation method, 101670245 A of CN]) be first carrier sensitization, cellular ceramic substrate is soaked
Enter in the dimethylamino monoborane of 0.02mol/L-0.05mol/L, reduce 3～5min, Zhi Houyong
Distilled water flushing is clean, immerses the Borax mixing of the palladium sulfate and 0.02mol/L of 0.05mol/L
In liquid, activation kind palladium core.Repeat aforesaid operations 3～5 times, until carrier film surface, color by
Till white is changed into black gray expandable.So far, palladium kernel covering is uniform, and cellular ceramic substrate pretreatment is complete
Into.
2. three-electrode electro Chemical work system (as shown in Figure 1) is built, Metal Palladium electrolyte, choosing is prepared
Select suitable parameter.
In three-electrode system, working electrode connects porous stainless steel carrier or pretreated porous
Ceramic monolith, is connected by electrode holder, and metallic rod is vertically fixed on iron stand, immersion electrolysis
In liquid.Reference electrode is connected as saturated calomel electrode, and model (217) is perpendicular by iron stand
It is straight fixed, electrolyte is immersed, against working electrode, reduction concentration polarization as little as possible and Europe
The error that nurse drop (IR drops) is produced.For cellular ceramic substrate, electrode connection gauze platinum electrode (is had
Imitate long 60mm, diameter 40mm), electrode holder connection inserts carrier in gauze platinum electrode, with
Keeping parallelism, ensure electroplating process in uniform current density.For porous stainless steel carrier,
Connect platinum electrode to electrode, model (Pt005) is connected by electrode holder, is vertically fixed on
In electrolyte, with working electrode keeping parallelism.In order to ensure in electroplating process, electric current density
Uniformly, by rotation electrode relative position (as shown in Fig. 1 (a), 3), or change electrode
Geometrical morphology, such as prepares tubulose to electrode, working electrode is inserted in parallel into wherein (such as Fig. 1 (b)
It is shown), realize the uniformity of electrochemical filming.Electrochemical parameter is adjusted, suitable work is selected
Make interval.Three-electrode system connection is finished, and starts electrochemical workstation, first to reaction system
Open-circuit voltage be scanned, determine that the balanced voltage of electrochemical reaction is interval, concrete operations are：
Setup—Techniques—Open Circuit Potential-Time.Parameter is set to：Run Time (400s～800s),
Sample Interval (0.1s～0.05s), High E Limit (1V～4V), Low E Limit (- 4V～-1V).Start scanning,
Till treating voltage stabilization.Open-circuit voltage E nowOAs in electrochemical filming course of reaction,
Upper voltage limit to be controlled.Secondly cyclic voltammetry (CV) is selected to carry out electrochemical plating film reaction.
Concrete operations are：Setup—Techniques—Cyclic Voltammetry.Parameter is set to：Init
E (- 0.45V～-0.85V), High E (- 0.45V～-0.85V), Low E (- 0.85V～-1.25V), Final
E (- 0.45V～-0.85V), Initial Scan Polarity (negative or positive), Scan Rate (0.01V/s～0.001V/s),
Sweep Segments (200～2000),
SampleInterval (0.05V～0.001V), Sensitivity (0.001A/V～0.0001A/V).By Control-Run
Status-About Experiment at Level Charge (C) come control electrochemical plating palladium reaction, required electricity
Lotus total amount.According to required palladium film thickness (d), it is determined that the quality (m) of required Metal Palladium, thing
The amount (n) of matter, according to Faraday laws：Q=zFn, (wherein Q is total quantity of electric charge, and z is
The stoichiometric coefficient of electron transfer in electrochemical reaction, the z=2 when palladium participates in reacting；F is Faraday
Constant, about 96500C/mol；N is the amount of the material of the metal for participating in electrode reaction) determine
Total quantity of electric charge needed for electrode reaction.
3. electrochemical filming, according to the pattern volume of the thickness and carrier of required film, is converted to
The corresponding quantity of electric charge.Operation program CHI600E Electrochemical Analyzer, Control-Run
Experiment.Electric current density general control is in 0.2A/dm3-0.3A/dm3, electroplating time is according to plating
Thickness degree it is different and different.
Compared to the method for traditional plated film, advantage of the invention is that：1. by control
The total amount of electric charge of electrode reaction, realizes and palladium film thickness is more accurately controlled.2. by right
The control of electric current density, realizes the further optimization to palladium film mechanical strength.3. electrochemical plating
In membrane process, the introducing of electric current instead of the effect of reducing agent, accelerate the migration of palladium ion
Speed, promotes reduction reaction rate of the palladium ion in carrier surface, and then when shortening reaction
Between, simplify technological process.
Description of the drawings：
Fig. 1 is three-electrode electro Chemical work system.A () is column-to electrode front view and top view；
B () is tubulose-to electrode front view and top view.Wherein 1 is that, to electrode, 2 is working electrode,
3 is reference electrode.
Cross Section Morphology structures of the Fig. 2 for palladium film.A it is 0.8 that () palladium film thickness is 0.4 μm of (b) palladium film thickness
μm。
Fig. 3 is column-rotate schematic diagram around working electrode to electrode.Wherein, W is working electrode,
C is that, to electrode, R is reference electrode.
Specific embodiment：
It should be noted that during cellular ceramic substrate seed nucleus pretreatment, the carrier for imitating traditional chemical plating is quick
Change and plant kernel mode, referring in particular to patent [Xu Hengyong, Tang Chunhua, Li Chunlin, Ge Qingjie,
A kind of preparation method of high hydrogen permeation selectivity metal palladium-based composite membrane, 101670245 A of CN], it is real
Test principle and detailed protocol is not being repeated.
By the detailed description in addition of following embodiments, illustrated embodiment its effect is the technology of the present invention details
The technical characteristic of the present invention is further illustrated, rather than limits the present invention.
Embodiment 1
The preparation of the palladium membrane sample with porous stainless steel as carrier of 0.5 μ m-thick
1. the preparation of palladium electrolyte
1.665g palladium chloride (PdCl are weighed accurately with HFA2004 analytical balances2), it is dissolved in
7.5mL, in 5% hydrochloric acid (HCl), generates dark red solution chloric acid palladium (H by 55 DEG C2PdCl4)。
Reaction equation is:
PdCl2After being completely dissolved, 2.5mL relative densities are slowly added under stirring for 0.89g/cm3Ammonia
Water (NH3H2O), pink gelatinous precipitate is generated with dark red solution reaction, add excess
Ammonia, until the red precipitate for generating is completely dissolved, and generate graminaceous dichloride ammonium palladium
([Pd(NH3)4]Cl2) till solution.Reaction equation is：
Undesired impurities are filtered off, the hydrochloric acid of 40mL10% is slowly added to toward clear liquid, until complete in solution
It is complete to separate out glassy yellow dichloride ammonium Asia palladium ([Pd (NH3)2]Cl2) till precipitation.Subtracted with buchner funnel
Pressure sucking filtration precipitation, and with distilled water to precipitation cleaning, until being formed, glassy yellow is thick to be precipitated as
Only.Clean [Pd (NH will be washed3)2]Cl250mL relative densities are dissolved in for 0.89g/cm3's
NH3H2In O, the ammonium chloride (NH of the 1mol/L for preparing in advance is added4Cl) solution regulation system
PH to 7.0, that is, obtain micro- green transparent dichloride ammonium Asia palladium electrolyte.
2. Vehicle element
The long 20mm of porous stainless steel carrier, wide 20mm, thick 2mm.First in dehydrated alcohol
(99.7%) NaCO3Solution (NaCO3Concentration is 0.05mol/L) in supersound process 30min,
Carrier surface greasy dirt is removed, the black mark on stainless steel carrier surface disappears.Then 5% hydrochloric acid
Middle supersound process 5min, removes the sull of carrier surface, and stainless steel carrier becomes more
Added with metallic luster.Supersound process 30min in deionized water afterwards, remove residual acid,
Alkali and ethanol solution.Last 150 DEG C of dry for standby in an oven, program are set to：
3. three-electrode system and parameter setting are built
Electrochemical workstation is CHI600E, working electrode (green) connection porous stainless steel carrier,
Connected by electrode holder, vertically in immersion electrolyte.It is sweet that reference electrode (white) is connected as saturation
Mercury electrode, model (217), vertically immerses electrolyte, against working electrode, distance controlling
In 0.4cm, to reduce the error that concentration polarization and ohmmic drop (IR drops) are produced.To electrode (redness)
Connection platinum electrode, model (Pt005) are connected by electrode holder, are vertically immersed in electrolyte
In, with working electrode keeping parallelism.Three-electrode system connection is finished, and starts electrochemical workstation,
The open-circuit voltage of reaction system is scanned first, determines that the balanced voltage of electrochemical reaction is interval, tool
Gymnastics conduct：Setup—Techniques—Open Circuit Potential-Time.Parameter is set to：Run
Time (400s), Sample Interval (0.1s), High E Limit (2V), Low E Limit (- 2V).Start scanning,
Till treating voltage stabilization.Open-circuit voltage E nowO=-0.535V.Cyclic voltammetry (CV) is entered
Row electroplating reaction.Concrete operations are：Setup—Techniques—Cyclic Voltammetry.Parameter setting
For：Init E (- 0.45V), High E (- 0.45V), Low E (- 0.55V), Final E (- 0.45V), Initial Scan
Polarity (negative), Scan Rate (0.01V/s), Sweep Segments (1000), SampleInterval (0.001V),
Sensitivity(0.0001A/V).As the total surface area of carrier is 960mm2, and thickness of coating is required
It it is 0.5 μm, the density of palladium is 12.023g/cm3, according to Faraday laws, this is anti-
In answering, total quantity of electric charge is 10.466C.By Control-Run Status-About Experiment at
Level Charge(C)>10.466C come control electrochemical plating palladium reaction, required total amount of electric charge.
4. electrochemistry palladium plated film
Operation program CHI600E Electrochemical Analyzer, Control-Run Experiment.Electric current
Density domination is 0.12A/dm3, in course of reaction by rotary work electrode, to electrode and ginseng
Than electrode, and change its relative position, realize being uniformly distributed for electric current density, and then reach
The purpose (as shown in Figure 3) of phase film forming.Scanning 8min, that is, complete the preparation of palladium film, and reaction is total
Electricity is 10.466C, and carrier surface deposited one layer of uniform silvery white palladium film.
Embodiment 2
The preparation of the palladium membrane sample with porous ceramic pipe as carrier of 0.4 μ m-thick
1. the preparation of palladium electrolyte
6.660g palladium chloride (PdCl are weighed accurately with HFA2004 analytical balances2), it is dissolved in
30mL, in 5% hydrochloric acid (HCl), generates dark red solution chloric acid palladium (H by 55 DEG C2PdCl4)。
Reaction equation is:
PdCl2After being completely dissolved, 17mL relative densities are slowly added under stirring for 0.89g/cm3
Ammonia (NH3H2O), pink gelatinous precipitate is generated with dark red solution reaction, add
Excess of ammonia water, until the red precipitate for generating is completely dissolved, and generates graminaceous dichloride
Ammonium palladium ([Pd (NH3)4]Cl2) till solution.Reaction equation is：
Undesired impurities are filtered off, the hydrochloric acid of 160mL-200mL10% is slowly added to toward clear liquid, until
Separate out glassy yellow dichloride ammonium Asia palladium ([Pd (NH in solution completely3)2]Cl2) till precipitation.Use cloth
Family name's funnel decompression sucking filtration precipitation, and with distilled water to precipitation cleaning, until it is sticky to form glassy yellow
Till shape is precipitated.Clean [Pd (NH will be washed3)2]Cl2Being dissolved in 200mL relative densities is
0.89g/cm3NH3H2In O, the ammonium chloride (NH of the 1mol/L for preparing in advance is added4Cl)
Solution regulation system pH obtains micro- green transparent dichloride ammonium Asia palladium electrolyte to 8.1.
2. Vehicle element
Cellular ceramic substrate pipe range 50mm, external diameter 14.05mm.First at dehydrated alcohol (99.7%)
NaCO3Solution (NaCO3Concentration is 0.05mol/L) middle immersion 30min, remove surface
Greasy dirt, carrier pipe surface ash point are removed.Immersion washes 15min in deionized water afterwards, removes
Remove the alcoholic solution for remaining, the pure white light of support tube.Last 150 DEG C of dry for standby in an oven,
Program is set to：
The how empty earthenware carrier of drying and processing is sensitized, by porous stainless steel carrier, immersion is also
In former agent (dimethylamino monoborane), 5min is reduced, support tube is rinsed well with distilled water,
Then immerse in the Borax mixed liquor of palladium sulfate and 0.02mol/L of 0.05mol/L, activation kind
Palladium core.Iterative cycles 3 times, until carrier film surface, till color is changed into black gray expandable from white.
So far, palladium kernel covering is uniform, and cellular ceramic substrate pretreatment is completed.
3. three-electrode system and parameter setting are built
Electrochemical workstation is CHI600E, working electrode (green) connection porous stainless steel carrier,
Connected by electrode holder, vertically in immersion electrolyte.It is sweet that reference electrode (white) is connected as saturation
Mercury electrode, model (217), vertically immerses electrolyte, against working electrode, distance controlling
In 0.5cm reducing the error that concentration polarization and ohmmic drop (IR drops) are produced.To electrode (redness)
Carrier is inserted by connection gauze platinum electrode (effectively long 60mm, diameter 40mm), electrode holder connection
Enter in gauze platinum electrode, therewith keeping parallelism, ensure uniform current density in electroplating process.Three is electric
The connection of polar body system is finished, and is started electrochemical workstation, is scanned the open-circuit voltage of reaction system first,
Determine that the balanced voltage of electrochemical reaction is interval, concrete operations are：Setup—Techniques—Open
Circuit Potential-Time.Parameter is set to：Run Time (400s), Sample Interval (0.1s), High E
Limit (2V), Low E Limit (- 2V).Start scanning, till treating voltage stabilization.Open circuit electricity now
Pressure EO=-0.571V.Cyclic voltammetry (CV) carries out electroplating reaction.Concrete operations are：
Setup—Techniques—Cyclic Voltammetry.Parameter is set to：Init E (- 0.5V), High E (- 0.5V),
Low E (- 0.6V), Final E (- 0.5V), Initial Scan Polarity (negative), Scan Rate (0.01V/s), Sweep
Segments (1000), SampleInterval (0.001V), Sensitivity (0.0001A/V).Due to the summary table of carrier
Area is 2215mm2, and thickness of coating requires it is 0.4 μm, the density of palladium is 12.023g/cm3,
According to Faraday laws, in this reaction, total quantity of electric charge is 19.319C.Pass through
Control—Run Status—About Experiment at Level Charge(C)>19.319C to control electrochemistry
Plating palladium reaction, required total amount of electric charge.
4. electrochemistry palladium plated film
Operation program CHI600E Electrochemical Analyzer, Control-Run Experiment.Electric current
Density domination is in 0.12A/dm3In interval, as cellular ceramic substrate is column structure, design
It is cylindrical mesh structure (as shown in Figure 1) to electrode, realizes being uniformly distributed for electric current density,
And then reach the purpose of homogeneous film forming.Scanning about 5min, that is, complete the preparation of palladium film, reacts
Total electricity is 19.319C, and carrier surface deposited the palladium of one layer of uniform silvery white metallic luster
Film.
Embodiment 3
The preparation of the palladium membrane sample with porous stainless steel as carrier of 1 μ m-thick
1. the preparation of palladium electrolyte
3.330g palladium chloride (PdCl are weighed accurately with HFA2004 analytical balances2), it is dissolved in
15mL, in 5% hydrochloric acid (HCl), generates dark red solution chloric acid palladium (H by 55 DEG C2PdCl4)。
Reaction equation is:
PdCl2After being completely dissolved, 7mL relative densities are slowly added under stirring for 0.89g/cm3
Ammonia (NH3H2O), pink gelatinous precipitate is generated with dark red solution reaction, add
Excess of ammonia water, until the red precipitate for generating is completely dissolved, and generates graminaceous dichloride
Ammonium palladium ([Pd (NH3)4]Cl2) till solution.Reaction equation is：
Undesired impurities are filtered off, the hydrochloric acid of 93mL10% is slowly added to toward clear liquid, until solution
In separate out glassy yellow dichloride ammonium Asia palladium ([Pd (NH completely3)2]Cl2) till precipitation.Leaked with Bu Shi
Bucket decompression sucking filtration precipitation, and with distilled water to precipitation cleaning, until it is thick heavy to form glassy yellow
Till shallow lake.Clean [Pd (NH will be washed3)2]Cl2Being dissolved in 100mL relative densities is
0.89g/cm3NH3H2In O, the ammonium chloride (NH of the 1mol/L for preparing in advance is added4Cl)
Solution regulation system pH obtains micro- green transparent dichloride ammonium Asia palladium electrolyte to 8.0.
2. Vehicle element
The long 20mm of porous stainless steel carrier, wide 20mm, thick 2mm.First in dehydrated alcohol
(99.7%) NaCO3Solution (NaCO3Concentration is 0.05mol/L) in supersound process 30min,
Carrier surface greasy dirt is removed, the black mark on stainless steel carrier surface disappears.Then 5% hydrochloric acid
Middle supersound process 5min, removes the sull of carrier surface, and stainless steel carrier becomes more
Added with metallic luster.Supersound process 30min in deionized water afterwards, remove residual acid,
Alkali and ethanol solution.Last 150 DEG C of dry for standby in an oven, program are set to：
3. three-electrode system and parameter setting are built
Electrochemical workstation is CHI600E, working electrode (green) connection porous stainless steel carrier,
Connected by electrode holder, vertically in immersion electrolyte.It is sweet that reference electrode (white) is connected as saturation
Mercury electrode, model (217), vertically immerses electrolyte, against working electrode, distance controlling
The error that concentration polarization and ohmmic drop (IR drops) are produced is reduced in 0.5cm.To electrode (redness) even
Platinum electrode is connect, model (Pt005) is connected by electrode holder, is vertically immersed in electrolyte,
With working electrode keeping parallelism.Three-electrode system connection is finished, and starts electrochemical workstation, first
The open-circuit voltage of reaction system is first scanned, determines that the balanced voltage of electrochemical reaction is interval, specifically
Operate and be：Setup—Techniques—Open Circuit Potential-Time.Parameter is set to：Run
Time (400s), Sample Interval (0.1s), High E Limit (2V), Low E Limit (- 2V).Start scanning,
Till treating voltage stabilization.Open-circuit voltage E nowO=-0.555V.Cyclic voltammetry (CV) is entered
Row electroplating reaction.Concrete operations are：Setup—Techniques—Cyclic Voltammetry.Parameter setting
For：Init E (- 0.45V), High E (- 0.45V), Low E (- 0.50V), Final E (- 0.45V), Initial Scan
Polarity (negative), Scan Rate (0.01V/s), Sweep Segments (1000), SampleInterval (0.001V),
Sensitivity(0.0001A/V).As the total surface area of carrier is 960mm2, and thickness of coating is required
It it is 1 μm, the density of palladium is 12.023g/cm3, according to Faraday laws, this reaction
In the total quantity of electric charge be 20.932C.By Control-Run Status-About Experiment at Level
Charge(C)>20.932C come control electrochemical plating palladium reaction, required total amount of electric charge.
4. electrochemistry palladium plated film
Operation program CHI600E Electrochemical Analyzer, Control-Run Experiment.Electric current
Density domination is in 0.09A/dm3In interval, in course of reaction by rotary work electrode, to electricity
Pole and reference electrode, and change its relative position, being uniformly distributed for electric current density is realized, and then
Reach the purpose (as shown in Figure 3) of homogeneous film forming.Scanning about 15min, that is, complete the system of palladium film
Standby, reaction total electricity is 20.932C, and carrier surface deposited one layer of uniform silvery white palladium film.
Embodiment 4
The preparation of the palladium membrane sample with porous ceramic pipe as carrier of 0.8 μ m-thick
1. the preparation of palladium electrolyte
6.660g palladium chloride (PdCl are weighed accurately with HFA2004 analytical balances2), it is dissolved in
30mL, in 5% hydrochloric acid (HCl), generates dark red solution chloric acid palladium (H by 55 DEG C2PdCl4)。
Reaction equation is:
PdCl2After being completely dissolved, 16mL relative densities are slowly added under stirring for 0.89g/cm3
Ammonia (NH3H2O), pink gelatinous precipitate is generated with dark red solution reaction, add
Excess of ammonia water, until the red precipitate for generating is completely dissolved, and generates graminaceous dichloride
Ammonium palladium ([Pd (NH3)4]Cl2) till solution.Reaction equation is：
Undesired impurities are filtered off, the hydrochloric acid of 160mL-200mL10% is often slowly added in clear liquid, directly
Separate out glassy yellow dichloride ammonium Asia palladium ([Pd (NH into solution completely3)2]Cl2) till precipitation.With
Buchner funnel decompression sucking filtration precipitation, and with distilled water to precipitation cleaning, until form glassy yellow gluing
Till thick shape is precipitated.Clean [Pd (NH will be washed3)2]Cl2Being dissolved in 200mL relative densities is
0.89g/cm3NH3H2In O, the ammonium chloride (NH of the 1mol/L for preparing in advance is added4Cl)
Solution regulation system pH obtains micro- green transparent dichloride ammonium Asia palladium electrolyte to 7.7.
2. Vehicle element
Cellular ceramic substrate pipe range 100mm, external diameter 14.05mm.First in dehydrated alcohol
(99.7%) NaCO3Solution (NaCO3Concentration is 0.05mol/L) middle immersion 30min, remove
The greasy dirt on surface, carrier pipe surface ash point are removed.Immersion is washed in deionized water afterwards
15min, removes the alcoholic solution of residual, the pure white light of support tube.It is last 150 DEG C in an oven
Dry for standby, program are set to：
The how empty earthenware carrier of drying and processing is sensitized, by porous stainless steel carrier, immersion is also
In the Borax mixed liquor of the palladium sulfate and 0.02mol/L of former agent 0.05mol/L, 4min is reduced,
Support tube is rinsed well with distilled water, then immersed in the mixed liquor of palladium sulfate and Borax, it is living
Change kind of a palladium core.Iterative cycles 5 times, up to carrier film surface, color is changed into black gray expandable from white
Till.So far, palladium kernel covering is uniform, and cellular ceramic substrate pretreatment is completed.
3. three-electrode system and parameter setting are built
Electrochemical workstation is CHI600E, working electrode (green) connection porous stainless steel carrier,
Connected by electrode holder, vertically in immersion electrolyte.It is sweet that reference electrode (white) is connected as saturation
Mercury electrode, model (217), vertically immerses electrolyte, against working electrode, distance controlling
The error that concentration polarization and ohmmic drop (IR drops) are produced is reduced in 0.5cm.To electrode (redness) even
Gauze platinum electrode (effectively long 60mm, diameter 40mm) is connect, carrier is inserted by electrode holder connection
In gauze platinum electrode, keeping parallelism, ensures uniform current density in electroplating process therewith.Three electrodes
System connection is finished, and is started electrochemical workstation, is scanned the open-circuit voltage of reaction system first,
Determine that the balanced voltage of electrochemical reaction is interval, concrete operations are：Setup—Techniques—Open
Circuit Potential-Time.Parameter is set to：Run Time (400s), Sample Interval (0.1s), High E
Limit (2V), Low E Limit (- 2V).Start scanning, till treating voltage stabilization.Open circuit electricity now
Pressure EO=-0.596V.Cyclic voltammetry (CV) carries out electroplating reaction.Concrete operations are：
Setup—Techniques—Cyclic Voltammetry.Parameter is set to：Init E (- 0.4V), High E (- 0.4V),
Low E (- 0.5V), Final E (- 0.4V), Initial Scan Polarity (negative), Scan Rate (0.01V/s), Sweep
Segments (1000), SampleInterval (0.001V), Sensitivity (0.0001A/V).Due to the summary table of carrier
Area is 4430mm2, and thickness of coating requires it is 0.8 μm, the density of palladium is 12.023g/cm3,
According to Faraday laws, in this reaction, total quantity of electric charge is 77.275C.Pass through
Control—Run Status—About Experiment at Level Charge(C)>77.275C to control electrochemistry
Plating palladium reaction, required total amount of electric charge.
4. electrochemistry palladium plated film
Operation program CHI600E Electrochemical Analyzer, Control-Run Experiment.Electric current
Density domination is in 0.11A/dm3In interval, as cellular ceramic substrate is column structure, design
It is cylindrical mesh structure (as shown in Figure 1) to electrode, realizes being uniformly distributed for electric current density,
And then reach the purpose of homogeneous film forming.Scanning about 20min, that is, complete the preparation of palladium film, reacts
Total electricity is 77.275C, and carrier surface deposited the palladium of one layer of uniform silvery white metallic luster
Film.
Claims (10)
1. the preparation method of the controllable ultra-thin palladium film of a kind of thickness, it is characterised in that：Carrier construction
Working electrode, platinum filament to electrode, saturated calomel reference electrode three-electrode system, using palladium
Ion obtains the principle of electron reduction on the working electrode (s, and the palladium ion in electrolyte is in work
On electrode electron reduction be the electro-deposition of palladium simple substance on carrier, by regulate and control electric current density
With reaction total charge dosage, make palladium film layer by layer deposition, obtain different-thickness densification it is ultra-thin
Palladium film.
2. the method according to claim as described in right 1, it is characterised in that：The work electricity
Pole material is porous stainless steel carrier material or cellular ceramic substrate material.
3. the method according to claim as described in right 1 or 2, it is characterised in that：The work
Make electrode material for tubulose or tabular.
4. the method according to claim as described in right 1, it is characterised in that：The electrolyte
Composition be：Chlorimide palladium, concentration are 2g/L-15g/L；Ammonium chloride concentration is
4g/L-20g/L；Potassium chloride concentration 0.1g/L-1.5g/L；Ammonium hydroxide concentration is
0.37mol/L-1.85mol/L；Free ammonia (NH3) concentration be 1g/L-10g/L.
5. the method according to claim as described in right 1, it is characterised in that：The electrolyte
PH be 6.1-9.9.
6. the method according to claim as described in right 1, it is characterised in that：Electrolyte makes
With temperature be depositing temperature be 20 DEG C -80 DEG C.
7. the method according to claim as described in right 1, it is characterised in that：Electric current density is
In 0.04A/dm3-0.6A/dm3, according to required film thickness degree, controlling sedimentation time is
5min-30min, so as to the total electricity for adjusting reaction is 10C-50C.
8. the method according to claim as described in right 1 or 2, it is characterised in that：When described
When working electrode material is cellular ceramic substrate material, first have in cellular ceramic substrate table
One layer of palladium film of face self-catalyzed deposition, as the conductor of next step plating；Cellular ceramic substrate
On carrier aperture defect be 0.1 μm -0.2 μm；The aperture defects of porous stainless steel carrier
For 0.2 μm -0.5 μm.
9. the method according to claim as described in right 1 or 2, it is characterised in that：When described
When working electrode material is porous stainless steel carrier material, the ultra-thin palladium film of preparation is in porous
On stainless steel carrier, thickness is 300nm-3 μm；When the working electrode material is porous
During ceramic carrier material, on cellular ceramic substrate, thickness is the ultra-thin palladium film of preparation
1μm-5μm。
10. the method according to claim as described in right 1, it is characterised in that：Prepare
Palladium film, finally will be in N2Under atmosphere, 350 DEG C of -550 DEG C of activation 1000min-3000min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108441845A (en) * | 2018-04-13 | 2018-08-24 | 河南科技学院 | A kind of preparation method for the method and abrasion-proof screen accurately controlling chemical plating coating thickness |
| CN108624923A (en) * | 2018-06-21 | 2018-10-09 | 深圳市西凡谨顿科技有限公司 | Electroforming thickness of coating automatic control device and system |
| CN109837562A (en) * | 2017-11-24 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of method that chemical plating/plating prepares palladium tube |
| CN110903265A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院大连化学物理研究所 | Method for carrying out gas phase propylene epoxidation reaction in palladium membrane reactor |
| CN111778416A (en) * | 2020-07-13 | 2020-10-16 | 西北有色金属研究院 | Preparation method of palladium alloy thin-diameter thin-wall capillary tube |
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| CN108441845B (en) * | 2018-04-13 | 2020-03-31 | 河南科技学院 | Method for accurately controlling thickness of chemical plating layer and preparation method of wear-resistant screen |
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| CN110903265A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院大连化学物理研究所 | Method for carrying out gas phase propylene epoxidation reaction in palladium membrane reactor |
| CN111778416A (en) * | 2020-07-13 | 2020-10-16 | 西北有色金属研究院 | Preparation method of palladium alloy thin-diameter thin-wall capillary tube |
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