CN103386319B - A kind of preparation method of amorphous C-N thin-film electro catalyst - Google Patents
A kind of preparation method of amorphous C-N thin-film electro catalyst Download PDFInfo
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- CN103386319B CN103386319B CN201310336434.4A CN201310336434A CN103386319B CN 103386319 B CN103386319 B CN 103386319B CN 201310336434 A CN201310336434 A CN 201310336434A CN 103386319 B CN103386319 B CN 103386319B
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Abstract
The present invention relates to a kind of preparation method of amorphous C-N thin-film electro catalyst, pass through radio-frequency magnetron sputter method, utilize substrate biasing, the C-N film of deposited amorphous in titanium substrate, in course of reaction, the corresponding discharge of carbon-source gas, argon gas and nitrogen is than being 25:20:15, and unit is standard state milliliter per minute; Then the film of hypertonic solutions stove to deposition is utilized to carry out 700 DEG C of heat treatments to realize the preparation of C-N film catalyst.The method is simple to operate, and cost is lower, can not introduce metal impurities.Current potential opened by the C-N catalyst of preparation is-0.02V, and limiting current density is 5.46mAcm
-2, in the chrono-amperometric test of 18000s, still can keep 98% than electric current; Methanol poisoning can not be there is.Its catalytic activity can match in excellence or beauty with Pt/C catalyst, and stability and the selective Pt/C catalyst that is better than, be a kind of non-precious metal catalyst of function admirable.
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 in titanium substrate, prepare amorphous C-N film, and 700 DEG C of heat treatments acquisition C-N thin-film electro catalyst are carried out to film, replace expensive Pt catalyst based, for accelerating the oxygen reduction reaction of fuel battery negative pole with it.
Background technology
The energy is the basis of economic development, does not have the development of energy industry just not have modern civilization.Through revolutionary industrial change several times, how people find more effectively and the mode utilizing the energy of environmental protection more while energy industry development, so there has been fuel cell technology.Fuel cell is a kind of generating battery being obtained electric energy by the chemical energy in convert fuel.Invented the first briquette fuel battery in the world from British Grove in 1893, constantly research and innovation, the fuel cell making to have the potential such as high efficiency, pollution-free, easy-maintaining has started 21 century new forms of energy and the green revolution of environmental protection.But make us hanging back, the cost of current fuel cell is high, is difficult to commercialization and promotes widely.Main cause is wherein the catalyst that fuel cell uses is noble metal.Therefore, the important topic that non-precious metal catalyst is promoted to replace noble metal catalyst to become fuel cell how is utilized.
Large quantifier elimination shows at present, and carbon-based material such as Graphene, CNT can replace platinum based catalyst as non-precious metal catalyst, and nitrating is the important step improving catalytic activity.Method prepared by the carbon-based material 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 needs to generate Graphene and CNT with metal as catalyst in the process of preparation, and then is removed by dissolving metal with acid solution.The problem of this material is 1. to be difficult to 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 operate, cost is lower, does not need the preparation method of metal to become research emphasis to the carbon-based material synthesizing nitrating.At present not about the report utilizing the biased radio-frequency magnetron sputter method of substrate to prepare 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 to match in excellence or beauty with 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.First by the biased radiofrequency magnetron sputtering technology of substrate, using carbon-source gas and nitrogen as reacting gas, argon gas deposits C-N film as sputter gas in titanium substrate.Then by hypertonic solutions stove, film is carried out to the C-N thin-film electro catalyst of the heat treatment acquisition amorphous of 700 DEG C.Oxygen reduction catalyst production cost prepared by this method is low, catalytic activity is high, selective and good stability.
Basic technical scheme of the present invention is summarized as follows:
Select polycrystalline titanium as substrate, use methane as carbon-source gas, nitrogen, as nitrogen source gas, passes into argon gas as sputter gas, substrate biasing simultaneously, carries out the deposition of film.Then use argon gas as protective gas, film is carried out to the heat treatment acquisition C-N thin-film electro catalyst of 700 DEG C in hypertonic solutions stove.
Concrete technical parameter of the present invention and optimum Choice are described below:
A kind of method preparing amorphous C-N thin-film electro catalyst material, on polycrystalline titanium base material, metal-free C-N film is deposited by the biased radiofrequency magnetron sputtering technology of substrate, and acquisition C-N thin-film electro catalyst is heat-treated to C-N film, concrete steps comprise:
Steps A: base material is placed in vacuum plant, system vacuumizes, and certain vacuum degree to be achieved, passes into sputter gas and reacting gas, wait for a period of time, and makes gas and vapor permeation even;
Step B: utilize r. f. magnetron sputtering method, adjustment reaction pressure, setting radio-frequency power, substrate bias and sputtering time, make the ionization under the effect of radio-frequency power supply of carbon-source gas, nitrogen source gas, argon gas, decomposition, finally the C-N film of deposited amorphous in substrate;
Step C: hypertonic solutions stove is put in the substrate of deposition C-N film, passes into protective gas, when being warming up to predetermined reaction temperature, insulation a period of time, C-N film is heat-treated;
Step D: after heat treatment terminates, continues logical protective gas, is cooled to room temperature; The C-N film catalyst of amorphous can be obtained.
In steps A, described base material selects the titanium sheet of polycrystalline to commonly use backing material; 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 is 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, 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 selects 300-1000 DEG C.
The present invention has following obvious advantage:
1) first, in the present invention, the preparation method of amorphous C-N catalyst is the biased radio-frequency magnetron sputter method of substrate, with the catalyst material of traditional C-N base as the preparation method of Graphene, CNT, as high temperature pyrolytic cracking (HTP) is compared with chemical vapour deposition technique, there is cost low, advantage simple to operate.
2) secondly, in the present invention amorphous C-N catalyst preparation process in any metal material need not be used as catalyst, compare with the preparation method of CNT with Graphene, can get rid of the effect of metal pair catalytic activity, the determination for the ownership of catalytic active site is easier.
3) again, the C-N catalyst prepared by the method has higher nitrogen content, 12at.% can be reached, catalytic activity is higher, can match in excellence or beauty with the Pt/C catalyst of commercialization, stability is better, and methanol tolerant ability is stronger, Pt/C catalyst even surpasses commercial Pt/C catalyst, so can be replaced to be used as the catalyst of methyl alcohol alkaline fuel cell cathode oxygen reduction reaction.
Accompanying drawing explanation
Fig. 1 (a, b, c, d) is the X-ray diffractogram of C-N catalyst of amorphous in the present invention, Raman spectrogram, scanning electron microscope diagram and transmission electron microscope figure respectively.
Fig. 2 (a, b) is that the C-N catalyst of amorphous is to the linear sweep voltammetry figure (different electrode rotary speed) of the reduction reaction of oxygen with according to the K-L curve described by Fig. 2 (a) of utechy-Levich theory respectively.The unlatching current potential of C-N catalyst to the reduction of oxygen of amorphous is-0.02V, can the reduction reaction of 4 electronics oxygen of catalytic one-stage, and catalytic activity can match in excellence or beauty with the Pt/C catalyst of commercialization.
Fig. 3 (a, b) is the chronoamperogram of C-N catalyst and the methanol tolerant test of amorphous respectively.In the chrono-amperometric test of 18000s, the current density of C-N catalyst remains 98%, and does not observe methanol poisoning phenomenon, illustrates that the Pt/C catalyst of stability and selectivity ratios commercialization is good.
Detailed description of the invention
Particular content of the present invention and embodiment is further illustrated below in conjunction with instantiation.
The preparation of C-N film in the present invention, adopts r. f. magnetron sputtering technology, with polycrystalline titanium for 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 makes gas and vapor permeation even.
2) carbon-source gas, nitrogen source gas, sputter gas rational proportion, i.e. CH
4/ N
2/ Ar=25/15/20, unit is sccm, adjustment back end pressure, setting 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 less than 100 DEG C.
Utilize hypertonic solutions stove to heat-treat film in the present invention and obtain final C-N catalyst, 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) continue logical protective gas and be cooled to less than 100 DEG C.
In the present invention, in the preparation process of C-N film, protective gas and the preferred argon gas of sputter gas, put into reaction vessel by the substrate of polycrystalline titanium, carries out vacuumizing process, 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 middle preferred 0.5Pa of back end pressure, substrate bias is-100V preferably.
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, by the C-N film hypertonic solutions stove of deposition, carries out vacuumizing process, 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, step 1) heating-up time preferred 2h, the preferred 5min of temperature retention time, reaction temperature preferably 700 DEG C.
In the present invention, in the heat treated preparation process of C-N film, step 2) temperature-fall period be lower the temperature with stove.
In sum, in the present invention, the basic comprising of optimization technique parameter is: under the condition that substrate polycrystalline titanium coexists at methane (preferred gas), nitrogen, argon gas, pass through radiofrequency magnetron sputtering technology, prepare C-N film, then the C-N film obtained is heat-treated to the C-N catalyst of obtained amorphous.The cost of raw material used in the method is lower, and operating process is simple, and in preparation process containing introduce any metal impurities, through electro-chemical test show make C-N catalyst activity higher, selective and excellent in stability.
Embodiment 1:
1) utilize rf magnetron sputtering equipment, polycrystalline titanium sheet deposits C-N film, use highly purified carbon target, when background pressure reaches 1 × 10
-4during Pa, pass into CH successively
4, N
2with Ar gas, and adjusting gas flow is respectively 25,15,20sccm, wait for a period of time, make gas and vapor permeation even.
2) regulate reaction pressure to be 0.5Pa, after stable gas pressure, regulate substrate bias to be-150V.
3) open radio-frequency power supply, radio-frequency power is 150W, and start sputtering, sputtering time is 40min.
4), after sputtering terminates, sample is taken out and treats that next step is for subsequent use.
5) sample is put into hypertonic solutions stove, 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 DEG C, and temperature retention time is 5min.
6), after heat treatment terminates, continue logical protective gas Ar, be cooled to room temperature; The C-N film catalyst of amorphous can be obtained.
7) (Pt is to electrode to adopt three-electrode system, Ag/AgCl electrode is reference electrode, electrode prepared by applicant is working electrode) carry out electrochemical property test, comprise linear sweep voltammetry test and chrono-amperometric test, electrolyte is adopted to be the KOH solution of 0.1mol/L, sweep speed is 5mV/s, and when electrode rotary speed is 900rpm, current density can reach 2.56mA cm
-2.
Embodiment 2:
By embodiment 1 step 2) substrate bias value changes 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:
By embodiment 1 step 2) substrate bias value changes 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:
By embodiment 1 step 2) substrate bias value changes 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:
By embodiment 1 step 2) substrate bias value changes 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:
By embodiment 1 step 2) substrate bias value changes 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 agent material has following feature:
1) to the observation being carried out X-ray diffractogram, ESEM and transmission electron microscope by the C-N film prepared by said method, can find that prepared C-N film is amorphous state.
2) carry out X-ray photoelectron spectroscopic analysis to the C-N film sample obtained by said method to obtain: 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 the reduction reaction of pyridine nitrogen to oxygen has catalytic activity.
4) the catalyst material activity obtained under example 4 condition is higher, can the reduction reaction of 4 electronics oxygen of catalytic one-stage, in the chrono-amperometric test of 18000s, the current density of C-N catalyst remains 98%, and do not observe methanol poisoning phenomenon, illustrate that the catalytic performance of this C-N catalyst is better than the Pt/C catalyst of commercialization.
Claims (2)
1. prepare a method for amorphous C-N thin-film electro catalyst material, it is characterized in that:
On polycrystalline titanium base material, deposit metal-free C-N film by the biased radio-frequency magnetron sputter method of substrate, and heat-treat acquisition C-N thin-film electro catalyst to C-N film, concrete steps comprise:
Steps A: base material is placed in vacuum plant, system vacuumizes, and certain vacuum degree to be achieved, passes into sputter gas and reacting gas, wait for a period of time, and make gas and vapor permeation even, described sputter gas is argon gas, its flow velocity 10 ~ 40sccm; Described reacting gas is carbon-source gas and nitrogen source gas, and wherein carbon-source gas selects methane, and described nitrogen source gas selects nitrogen;
Background pressure in described vacuum plant is 1 × 10
-4below Pa;
Step B: utilize r. f. magnetron sputtering method, adjustment reaction pressure, setting radio-frequency power, substrate bias and sputtering time, make the ionization under the effect of radio-frequency power supply of carbon-source gas, nitrogen source gas, argon gas, decomposition, finally the C-N film of deposited amorphous in substrate;
Described substrate bias is from floating voltage ~-250V, described reacting gas pressure is 0.5Pa, 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, unit is sccm, standard state ml/min;
Step C: hypertonic solutions stove is put in the substrate of deposition C-N film, passes into protective gas, when being warming up to predetermined reaction temperature, insulation a period of time, C-N film is heat-treated;
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 selects 300-1000 DEG C;
Step D: after heat treatment terminates, continues logical protective gas, is cooled to room temperature; The C-N film catalyst of amorphous can be obtained.
2. a kind of method 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.
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| 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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| 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 |
|---|
| Ionized magnetron sputter deposition of amorphous carbon nitride thin films;D. Li et al.;《J. Vac. Sci. Technol. A》;19950630;第13卷(第3期);第1063-1066页 * |
| Mechanical and tribological properties of CNx films deposited by reactive magnetron sputtering;E.Broitman et al.;《Wear》;20011231;第248卷;第55-64页 * |
| 非晶碳氮薄膜的制备表征及其场发射特性研究;李俊杰;《吉林大学博士学位论文》;20031231;第14页（4）化学气相沉积方法部分，第20页2.1节，图2.1，图2.2，第24页2.3节，第25页表2.1，第63页第4.2节，图4.1 * |
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