CN103386319A - Preparation method of amorphous C-N thin film electrocatalyst - Google Patents
Preparation method of amorphous C-N thin film electrocatalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of an amorphous C-N thin film electrocatalyst. The method comprises the following steps of: applying bias voltage on a substrate, depositing an amorphous C-N thin film on a titanium base, wherein the corresponding flow ratio of carbon source air, argon and nitrogen in the reaction process is 25 to 20 to15, and the unit refers to milliliter/per minute at a standard state; performing heat treatment at 700 DEG C on the deposited thin film by using a high-vacuum heat treatment furnace, thus realizing the preparation of the C-N thin film catalyst. The method is simple in preparation, has low cost and can not introduce metal impurities. For the prepared C-N catalyst, the starting potential is -0.02V, the limit current density is 5.46mA/cm<-2>, the specific current can keep 98% in a chronoamperometry test lasting for 18000 seconds, and the methanol poisoning can not be caused. The catalytic activity of the catalyst prepared by the method disclosed by the invention is comparable with that of a Pt/C catalyst, while the stability and the selectivity are better than those of the Pt/C catalyst, the catalyst is a non-noble metal catalyst with an excellent property.
Description
Technical field
The present invention relates to a kind of preparation method of amorphous C-N thin-film electro catalyst material.Be specifically related to use the biased radio frequency magnetron sputtering method of substrate to prepare amorphous C-N film in the titanium substrate, and film is carried out 700 ℃ of heat treatments acquisition C-N thin-film electro catalyst, replace expensive Pt catalyst based with it, be used for accelerating the oxygen reduction reaction of fuel battery negative pole.
Background technology
The energy is the basis of economic development, does not have the development of energy industry just there is no modern civilization.Through revolutionary industrial change several times, how people find more effectively and the mode of utilizing the energy of environmental protection more in the energy industry development, so fuel cell technology has been arranged.Fuel cell is a kind of generating battery that obtains electric energy by the chemical energy in convert fuel.Invent the first briquette fuel battery in the world from British Grove in 1893, constantly studied and innovate, made the fuel cell that has the potential such as high efficiency, pollution-free, easy-maintaining start 21 century new forms of energy and the green revolution of environmental protection.But what make us hanging back is that the cost of fuel cell is high at present, is difficult to commercialization and promotes widely.Main cause wherein is that the catalyst that fuel cell uses is noble metal.Therefore, how to utilize non-precious metal catalyst to replace noble metal catalyst to become the important topic that fuel cell is promoted.
At present a large amount of research shows, carbon-based material such as Graphene, CNT can be used as non-precious metal catalyst and replace platinum based catalyst, and nitrating is the important step that improves catalytic activity.The method of the carbon-based material preparation of these nitratings is mainly concentrated as high temperature pyrolytic cracking (HTP) and chemical vapour deposition technique, these preparation method's operating process more complicated, and cost is higher, the more important thing is in the process of preparation and need to generate Graphene and CNT with metal as catalyst, and then with acid solution, dissolving metal is removed.The problem of this material is to be difficult to 1. judge that last catalytic activity derives from the carbon-based material of nitrating or residual metal impurities; 2. probably active sites pyridine nitrogen proton is changed in the process of dissolution of metals and there is no active pyridine nitrogen-hydrogen.So find a kind of simple to operately, cost is lower, and the carbon-based material that does not need the preparation method of metal to synthesize nitrating becomes research emphasis.At present not about utilizing the biased radio-frequency magnetron sputter method of substrate to prepare the report of amorphous C-N thin-film electro catalyst, this method is simple to operate, cost is lower, and do not introduce any metal impurities in whole preparation process, Electrochemical results shows its catalytic activity, stability and selectively can match in excellence or beauty with the Pt/C eelctro-catalyst.
Summary of the invention
The object of the invention is to,, from above background, propose not introduce any metal impurities in a kind of preparation method, particularly whole process of amorphous C-N thin-film electro catalyst.At first, by the biased radiofrequency magnetron sputtering technology of substrate, use carbon-source gas and nitrogen as reacting gas, argon gas deposits the C-N film in the titanium substrate as sputter gas.Then by the high vacuum heat-treatment furnace, film is carried out the C-N thin-film electro catalyst of the heat treatment acquisition amorphous of 700 ℃.The oxygen reduction catalyst production cost of this method preparation is low, catalytic activity is high, selective and good stability.
Basic technical scheme of the present invention is summarized as follows:
Select the polycrystalline titanium as substrate, use methane as carbon-source gas, nitrogen, as nitrogen source gas, passes into argon gas simultaneously as sputter gas, and the substrate biasing carries out the deposition of film.Then use argon gas as protective gas, film is carried out the heat treatment acquisition C-N thin-film electro catalyst of 700 ℃ in the high vacuum heat-treatment furnace.
Concrete technical parameter of the present invention and optimum Choice are described below:
A kind of method for preparing amorphous C-N thin-film electro catalyst material, deposit metal-free C-N film on polycrystalline titanium base material by the biased radiofrequency magnetron sputtering technology of substrate, and the C-N film is heat-treated and obtained C-N thin-film electro catalyst, concrete steps comprise:
Steps A: base material is placed in vacuum plant, and system vacuumizes, and certain vacuum degree to be reached, pass into sputter gas and reacting gas, waits for a period of time, and gas is mixed;
Step B: utilize the r. f. magnetron sputtering method, adjust reaction pressure, set radio-frequency power, substrate bias and sputtering time, make carbon-source gas, nitrogen source gas, argon gas ionization under the effect of radio-frequency power supply, decomposition, finally the C-N film of deposited amorphous in substrate;
Step C: the high vacuum heat-treatment furnace is put in the substrate that will deposit the C-N film, passes into protective gas, while being warming up to predetermined reaction temperature, insulation a period of time, the C-N film is heat-treated;
Step D: after heat treatment finishes, continue logical protective gas, be cooled to room temperature; Can obtain the C-N film catalyst of amorphous.
In steps A, described base material selects the titanium sheet of polycrystalline backing material commonly used; Described sputter gas is argon gas, its flow velocity 10～40sccm; Described reacting gas is carbon-source gas and nitrogen source gas.
Described carbon-source gas selects methane; Described nitrogen source gas selects nitrogen.
In steps A, the background pressure in described vacuum plant is 1 * 10
-4Below Pa.
In step B, described substrate bias be from floating voltage～-250V.
In step B, described reacting gas pressure is 0.5Pa, and radio-frequency power is 150～250W, sputtering time is 20～40min, carbon-source gas and nitrogen source gas and sputter gas flowrate proportioning are 25:5:20～25:25:20, and unit is sccm, the standard state ml/min.
In step B, described radio-frequency power is 150W, and sputtering time is 40min, and carbon-source gas and nitrogen source gas and sputter gas flowrate proportioning are 25:15:20.
In step C, described protective gas selects argon gas, and the heating-up time is selected between 1-3h, and temperature retention time is selected between 5min-2h, and reaction temperature is selected 300-1000 ℃.
The present invention has following obvious advantage:
1) at first, in the present invention, the preparation method of amorphous C-N catalyst is the biased radio-frequency magnetron sputter method of substrate, preparation method with the catalyst material of traditional C-N base such as Graphene, CNT, compare with chemical vapour deposition technique as high temperature pyrolytic cracking (HTP), has cost low, advantage simple to operate.
2) secondly, need not use any metal material as catalyst in the present invention in the preparation process of amorphous C-N catalyst, compare with the preparation method of Graphene and CNT, can get rid of the effect of metal pair catalytic activity, for the ownership of catalytic active site determine easier.
3) again, the C-N catalyst for preparing by the method has higher nitrogen content, can reach 12at.%, catalytic activity is higher, can match in excellence or beauty with the Pt/C catalyst of commercialization, stability is better, and anti-methyl alcohol ability is stronger, even surpass commercial Pt/C catalyst, so can replace the Pt/C catalyst to be used as the catalyst of methyl alcohol alkalescence fuel battery negative pole oxygen reduction reaction.
Description of drawings
Fig. 1 (a, b, c, d) is respectively X-ray diffractogram, Raman spectrogram, scanning electron microscope diagram and the transmission electron microscope figure of the C-N catalyst of amorphous in the present invention.
Fig. 2 (a, b) is respectively that the C-N catalyst of amorphous is to the linear sweep voltammetry figure (different electrode rotary speed) of the reduction reaction of oxygen and the K-L curve of being described by Fig. 2 (a) according to the utechy-Levich theory.The C-N catalyst of amorphous to the unlatching current potential of the reduction of oxygen is-0.02V, the reduction reaction of 4 electronics oxygen that can catalytic one-stage, and catalytic activity can match in excellence or beauty with the Pt/C catalyst of commercialization.
Fig. 3 (a, b) is respectively chronoamperogram and the test of anti-methyl alcohol of the C-N catalyst of amorphous.The current density of C-N catalyst has kept 98% in the timing testing current of 18000s, and does not observe the methanol poisoning phenomenon, illustrates that the Pt/C catalyst of stability and selectivity ratios commercialization is good.
The specific embodiment
Further illustrate particular content of the present invention and embodiment below in conjunction with instantiation.
The preparation of C-N film in the present invention, adopt the r. f. magnetron sputtering technology, take the polycrystalline titanium as substrate.Mainly be divided into following steps:
1) system vacuumizes, and passes into sputter gas and reacting gas, waits for a period of time, and gas is mixed.
2) carbon-source gas, nitrogen source gas, sputter gas rational proportion, i.e. CH
4/ N
2/ Ar=25/15/20, unit are sccm, adjust back end pressure, set radio-frequency power, sputtering time and substrate bias, and the abundant ionization of reaction raw materials, decomposition, be transformed into active group, final deposition C-N film in the substrate of polycrystalline titanium.
3) logical protective gas is cooled to below 100 ℃.
Utilize the high vacuum heat-treatment furnace to heat-treat and obtain final C-N catalyst film in the present invention, key step comprises:
1) system vacuumizes, and passes into protective gas, is warming up to predetermined temperature (reaction temperature), when temperature reaches reaction temperature, and insulation a period of time.
2) continuing logical protective gas is cooled to below 100 ℃.
In the present invention, in the preparation process of C-N film, the preferred argon gas of protective gas and sputter gas, put into reaction vessel with the substrate of polycrystalline titanium, vacuumizes processing, makes the back end pressure of system 1 * 10
-4Below Pa.
In the present invention, in the preparation process of C-N film, step 2) the preferred 0.5Pa of back end pressure in, substrate bias is preferred-100V.
In the present invention, in the preparation process of C-N film, step 2) the preferred 150W of radio-frequency power, the preferred 40min of sputtering time.
In the present invention, in the heat treated preparation process of C-N film, the preferred argon gas of protective gas, in the C-N film high vacuum heat-treatment furnace of deposition, vacuumize processing, makes the back end pressure of system 1 * 10
-4Below Pa.
In the present invention, in the heat treated preparation process of C-N film, preferred 2h of step 1) heating-up time, the preferred 5min of temperature retention time, preferred 700 ℃ of reaction temperature.
In the present invention, in the heat treated preparation process of C-N film, step 2) temperature-fall period is to lower the temperature with stove.
In sum, in the present invention, the basic comprising of optimization technique parameter is: substrate polycrystalline titanium is under the condition that methane (preferred gas), nitrogen, argon gas coexist, pass through radiofrequency magnetron sputtering technology, prepare the C-N film, then the C-N film that obtains is heat-treated the C-N catalyst that makes amorphous.The cost of raw material of using in the method is lower, and operating process is simple, and does not contain in preparation process and introduce any metal impurities, through electro-chemical test show system C-N catalyst activity higher, selective and excellent in stability.
Embodiment 1:
1) utilize rf magnetron sputtering equipment, deposition C-N film, use highly purified carbon target, when background pressure reaches 1 * 10 on polycrystalline titanium sheet
-4During Pa, pass into successively CH
4, N
2With Ar gas, and adjusting gas flow is respectively 25,15,20sccm, waits for a period of time, and gas is mixed.
2) conditioned reaction air pressure is 0.5Pa, and after stable gas pressure, the adjusting substrate bias is-150V.
3) open radio-frequency power supply, radio-frequency power is 150W, starts sputter, and sputtering time is 40min.
4) after sputter finishes, sample is taken out and treats that next step is standby.
5) sample is put into the high vacuum heat-treatment furnace, when background pressure reaches 1 * 10
-4During Pa, pass into protective gas Ar, the heating-up time is 2h, and heat treatment temperature is 700 ℃, and temperature retention time is 5min.
6) after heat treatment finishes, continue logical protective gas Ar, be cooled to room temperature; Can obtain the C-N film catalyst of amorphous.
7) (Pt is to electrode to adopt three-electrode system, the Ag/AgCl electrode is reference electrode, the electrode of applicant preparation is working electrode) carry out electrochemical property test, comprise linear sweep voltammetry test and timing testing current, adopting electrolyte is the KOH solution of 0.1mol/L, sweep speed is 5mV/s, and when electrode rotary speed was 900rpm, current density can reach 2.56mA cm
-2
Embodiment 2:
With embodiment 1 step 2) the substrate bias value changed into-50V by floating voltage, and all the other steps are identical with embodiment 1, and current density can reach 3.22mA cm
-2
Embodiment 3:
With embodiment 1 step 2) the substrate bias value changed into-100V by floating voltage, and all the other steps are identical with embodiment 1, and current density can reach 5.46mA cm
-2
Embodiment 4:
With embodiment 1 step 2) the substrate bias value changed into-150V by floating voltage, and all the other steps are identical with embodiment 1, and current density can reach 4.57mA cm
-2
Embodiment 5:
With embodiment 1 step 2) the substrate bias value changed into-200V by floating voltage, and all the other steps are identical with embodiment 1, and current density can reach 4.83mA cm
-2
Embodiment 6:
With embodiment 1 step 2) the substrate bias value changed into-250V by floating voltage, and all the other steps are identical with embodiment 1, and current density can reach 3.65mA cm
-2
According to the exemplary method of foregoing invention, can prepare the C-N thin-film electro catalyst material of amorphous, this film catalyst material has following feature:
1), to by the prepared C-N film of said method, carrying out the observation of X-ray diffractogram, ESEM and transmission electron microscope, can find that prepared C-N film is amorphous state.
2) the C-N film sample that obtains by said method being carried out X-ray photoelectron spectroscopic analysis obtains: the N1s power spectrum can fit to two parts, correspond respectively to pyridine nitrogen and pyrroles's nitrogen, and in film, the content of nitrogen is up to arriving 12at.%, and wherein pyridine nitrogen has catalytic activity to the reduction reaction of oxygen.
4) the catalyst material activity that obtains under example 4 conditions is higher, the reduction reaction of 4 electronics oxygen that can catalytic one-stage, the current density of C-N catalyst has kept 98% in the timing testing current of 18000s, and do not observe the methanol poisoning phenomenon, illustrate that the catalytic performance of this C-N catalyst is better than the Pt/C catalyst of commercialization.
Claims (8)
1. method for preparing amorphous C-N thin-film electro catalyst material is characterized in that:
Deposit metal-free C-N film by the biased radio-frequency magnetron sputter method of substrate on polycrystalline titanium base material, and the C-N film is heat-treated and obtained C-N thin-film electro catalyst, concrete steps comprise:
Steps A: base material is placed in vacuum plant, and system vacuumizes, and certain vacuum degree to be reached, pass into sputter gas and reacting gas, waits for a period of time, and gas is mixed;
Step B: utilize the r. f. magnetron sputtering method, adjust reaction pressure, set radio-frequency power, substrate bias and sputtering time, make carbon-source gas, nitrogen source gas, argon gas ionization under the effect of radio-frequency power supply, decomposition, finally the C-N film of deposited amorphous in substrate;
Step C: the high vacuum heat-treatment furnace is put in the substrate that will deposit the C-N film, passes into protective gas, while being warming up to predetermined reaction temperature, insulation a period of time, the C-N film is heat-treated;
Step D: after heat treatment finishes, continue logical protective gas, be cooled to room temperature; Can obtain the C-N film catalyst of amorphous.
2. a kind of method for preparing amorphous C-N thin-film electro catalyst material as claimed in claim 1 is characterized in that:
In steps A, described base material selects the titanium sheet of polycrystalline backing material commonly used; Described sputter gas is argon gas, its flow velocity 10～40sccm; Described reacting gas is carbon-source gas and nitrogen source gas.
3. a kind of method for preparing amorphous C-N thin-film electro catalyst material as claimed in claim 2 is characterized in that:
Described carbon-source gas selects methane; Described nitrogen source gas selects nitrogen.
4. a kind of method for preparing amorphous C-N thin-film electro catalyst material as claimed in claim 1 is characterized in that:
In steps A, the background pressure in described vacuum plant is 1 * 10
-4Below Pa.
5. a kind of method for preparing amorphous C-N thin-film electro catalyst material as claimed in claim 1 is characterized in that:
In step B, described substrate bias be from floating voltage～-250V.
6. a kind of method for preparing amorphous C-N thin-film electro catalyst material as claimed in claim 1 is characterized in that:
In step B, described reacting gas pressure is 0.5Pa, and radio-frequency power is 150～250W, sputtering time is 20～40min, carbon-source gas and nitrogen source gas and sputter gas flowrate proportioning are 25:5:20～25:25:20, and unit is sccm, the standard state ml/min.
7. a kind of method for preparing amorphous C-N thin-film electro catalyst material as claimed in claim 1 is characterized in that:
In step B, described radio-frequency power is 150W, and sputtering time is 40min, and carbon-source gas and nitrogen source gas and sputter gas flowrate proportioning are 25:15:20.
8. a kind of method for preparing amorphous C-N thin-film electro catalyst material as claimed in claim 1 is characterized in that:
In step C, described protective gas selects argon gas, and the heating-up time is selected between 1-3h, and temperature retention time is selected between 5min-2h, and reaction temperature is selected 300-1000 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126834A (en) * | 2018-08-30 | 2019-01-04 | 合肥工业大学 | A kind of FeSe base noncrystal membrane catalyst and the preparation method and application thereof |
Citations (2)
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| JPH08158040A (en) * | 1994-11-29 | 1996-06-18 | Denki Kagaku Kogyo Kk | Thin carbon nitride film and its formation |
| CN102409305A (en) * | 2011-10-11 | 2012-04-11 | 宁波市瑞通新材料科技有限公司 | Preparation method B-C-N optical thin film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08158040A (en) * | 1994-11-29 | 1996-06-18 | Denki Kagaku Kogyo Kk | Thin carbon nitride film and its formation |
| CN102409305A (en) * | 2011-10-11 | 2012-04-11 | 宁波市瑞通新材料科技有限公司 | Preparation method B-C-N optical thin film |
Non-Patent Citations (3)
| Title |
|---|
| D. LI ET AL.: "Ionized magnetron sputter deposition of amorphous carbon nitride thin films", 《J. VAC. SCI. TECHNOL. A》, vol. 13, no. 3, 30 June 1995 (1995-06-30), pages 1063 - 1066 * |
| E.BROITMAN ET AL.: "Mechanical and tribological properties of CNx films deposited by reactive magnetron sputtering", 《WEAR》, vol. 248, 31 December 2001 (2001-12-31), pages 55 - 64 * |
| 李俊杰: "非晶碳氮薄膜的制备表征及其场发射特性研究", 《吉林大学博士学位论文》, 31 December 2003 (2003-12-31), pages 1 - 136 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126834A (en) * | 2018-08-30 | 2019-01-04 | 合肥工业大学 | A kind of FeSe base noncrystal membrane catalyst and the preparation method and application thereof |
| CN109126834B (en) * | 2018-08-30 | 2021-06-29 | 合肥工业大学 | FeSe-based amorphous thin film catalyst and preparation method and application thereof |
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