CN104001521A - Carbon-supported PtCu alloy catalyst with controllable atomic concentration gradient and preparation method thereof - Google Patents
Carbon-supported PtCu alloy catalyst with controllable atomic concentration gradient and preparation method thereof Download PDFInfo
- Publication number
- CN104001521A CN104001521A CN201410183944.7A CN201410183944A CN104001521A CN 104001521 A CN104001521 A CN 104001521A CN 201410183944 A CN201410183944 A CN 201410183944A CN 104001521 A CN104001521 A CN 104001521A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- target
- concentration gradient
- fiber cloth
- graphite fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 197
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 69
- 239000000956 alloy Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 86
- 239000000835 fiber Substances 0.000 claims abstract description 82
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 82
- 239000010439 graphite Substances 0.000 claims abstract description 82
- 229910052802 copper Inorganic materials 0.000 claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000004744 fabric Substances 0.000 claims abstract description 64
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003610 charcoal Substances 0.000 claims description 75
- 230000001276 controlling effect Effects 0.000 claims description 25
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052774 Proactinium Inorganic materials 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 230000002262 irrigation Effects 0.000 claims description 9
- 238000003973 irrigation Methods 0.000 claims description 9
- 238000005477 sputtering target Methods 0.000 claims description 9
- 239000013077 target material Substances 0.000 claims description 9
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 239000005416 organic matter Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract 3
- 230000008878 coupling Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 159
- 125000004429 atom Chemical group 0.000 description 59
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 35
- 238000002484 cyclic voltammetry Methods 0.000 description 22
- 238000004502 linear sweep voltammetry Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 238000012113 quantitative test Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- -1 Platinum metals Chemical class 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a carbon-supported PtCu alloy catalyst with controllable atomic concentration gradient and a preparation method thereof, and belongs to the water electrolysis-organic matter electrocatalytic reduction coupling technical field. The catalyst takes graphite fiber cloth as a carbonaceous carrier, a Pt and Cu spliced target placed on a movable target table is sputtered by ion beams in vacuum, wherein the movement direction of the target table is kept to be perpendicular to a joint line of Pt and Cu on the spliced target; sputtered-out Pt and Cu particles on the spliced target are deposited on a single face of the carbonaceous carrier subjected to ion beam assisted cleaning to form a thin film, and the carbon-supported PtCu alloy catalyst with the controllable atomic concentration gradient is obtained through vacuum heat treatment. The Pt content of the catalyst is 0.075-0.121 mg/cm<2>; adjustment of the movement speed of the target table can directly regulate and control the atomic concentration gradient of Pt in the catalyst, the stable movement speed can allow the Pt atom concentration to be in homogeneous gradient change from the bottom layer of the thin film to the surface of the thin film; and the catalyst has the advantages of low Pt content, relatively good electrochemical activity, simple preparation and the like.
Description
Technical field
The present invention relates to the controlled charcoal of a kind of concentration gradient of atoms and carry PtCu alloy catalyst and preparation method thereof, belong to water electrolysis-organic matter electrical catalyze reduction coupling technique field.
Background technology
Organic matter hydrogenation reaction is the significant process of the production fields such as food, chemical industry, the energy, it is combined hydrogen manufacturing with brine electrolysis likely become following main hydrogen manufacturing mode, utilize water electrolysis-organic matter electrical catalyze reduction coupling process to realize organic matter hydrogenation process and there is reaction condition gentleness, without the feature that hydrogen source is additionally provided.Because it is strong acid corrosion reaction environment, so electrode can only adopt the carrier of carbonaceous material and load precious metals pt and the Au on it, and wherein Pt has the sky of underfill
dtrack and show good catalytic activity and stability, is loaded on carbonaceous carrier surface and forms charcoal and carry Pt catalyst, has obtained compared with high electrode reaction current density and has been used widely.
Because China's Platinum metals resources is deficient, in Pt, containing transition metal forms the development trend that Pt alloy has become charcoal carried Pt-based catalyst at present, and catalyst based corresponding the concentrating on of research focus of Pt improved catalytic activity and reduced Pt content aspect.And the skin of transition metal Cu atom is configured as 3
d 104
s 1, due to 4
swith 3
dthe energy of electronics approaches, equal possibility Cheng Jian during with Pt chemical combination, therefore there is the unsettled space of appraising at the current rate in Cu atom, make it not only can be used as auxiliary agent and participate in catalytic reaction, also can be used as doped chemical to change the distribution of particles of active component Pt, Pt crystal grain is arranged tightr, cloud density increases, and can reduce in conjunction with the required energy barrier of oxygen atom.
Although PtCu alloy catalyst can reduce the Pt content of electrode, improve catalytic activity, at catalyst reaction, the aspect such as selective and stability need to improve.Charcoal carry PtCu alloy catalyst owing to thering is unique catalytic performance for water electrolysis-organic matter electrical catalyze reduction coupling reactions, it is former because catalytic activity depends primarily on concentration and the preferred orientation of catalysis principal phase, one, near fermi level, the catalyst bandwidth that the Pt of take is principal phase is less, Pt (111) crystal face has than other orientation higher density of states and have optimum catalytic performance, it two causes film defects for catalyst surface Pt concentration changes, and is conducive to realize the in-situ control of catalytic activity.
Through the literature search of existing concentration gradient of atoms control technique is found, US Patent No. 4399058 is mixed group vib and VIII family slaine with ammoniacal liquor, add ammoniacal liquor and be adjusted to a certain pH value, heating makes metallic solution, impregnated on carrier metallic solution is saturated again, the method be dried, roasting making carried catalyst, its shortcoming is the active metal component more equal Uniform that distributes on carrier, concentration gradient of atoms is not obvious and be difficult to control; European patent EP 0204314 adopts repeatedly dipping, washing, dry, the roasting method carrying metal component of substep, make the metal component concentration of carried catalyst inside higher than surperficial metal component concentration, exist uneven Uniform to distribute, the corresponding service life that extends catalyst, because its preparation process is complicated, cost significantly improves; Chinese patent CN99113273.4 adopts the unsaturated legal system that sprays for the carried catalyst of inhomogeneous active metal component, reduced the manufacturing cost of catalyst but shortcoming is that active metal component distribution gradient is poor, the gradient of wayward active metal component in catalyst granules distributes; Chinese patent CN200910086745.3 and CN200910086740.0 all adopt the saturated impregnated carrier of metallic solution of enriching progressively or the metal impregnation liquid concentration method of impregnated carrier from low to high, then through dry, calcination process repeatedly, obtain the carried catalyst that active metal component and/or acidic assistant concentration increase distribution in gradient, there is better activity and stability, but in catalyst granules, active metal component concentration distribution presents many stepped form.At present, about active metal component concentration, be the report of carried catalyst and preparation method thereof of homogeneous graded less.
Summary of the invention
For the above-mentioned defect of prior art, the problem such as the present invention will solve the active metal component concentration gradient lack of homogeneity that exists in the Pt base alloy carrier method for preparing catalyst of existing active metal component uneven distribution, preparation process is numerous and diverse, the reaction time is long, remove intermediate reaction thing difficulty, precious metal losses is large.
The object of the present invention is to provide the controlled charcoal of a kind of concentration gradient of atoms to carry PtCu alloy catalyst, described catalyst is for take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, and film catalyst thickness is 30～50nm; In catalyst, Pt content is 0.075～0.121mg/cm
2, Cu content is 0.019～0.074mg/cm
2.
The controlled charcoal of concentration gradient of atoms of the present invention carries in PtCu alloy catalyst, and in described catalyst, the atomic concentration of active component Pt and Cu is homogeneous graded from film bottom to surface, and wherein the atomic concentration of Pt is 26.85～90.42
at.%, the atomic concentration of Cu is 9.58～73.15
at.%, the concentration gradient of atoms of active component Pt and Cu is is directly regulated and controled by target platform translational speed, and in target platform moving range, stable running target platform speed makes the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded.
The controlled charcoal of concentration gradient of atoms of the present invention carries PtCu alloy catalyst, it is characterized in that: described graphite fiber cloth is plain weave propionitrile graphite fiber cloth, and surface density 0.20～0.35g/cm
2.
Another object of the present invention is to provide the described controlled charcoal of concentration gradient of atoms to carry the preparation method of PtCu alloy catalyst, specifically comprise the following steps:
(1) graphite fibre is arranged in to 7 * 10
-3～9 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.6～0.8kV, line are 65～75mA, and pass into the high-purity Ar of 6.5～7.5sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 5～7min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
(2) the pretreatment graphite fibre of step (1) gained is arranged in to 7 * 10
-3～9 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.3～3.6kV, line are 70～90mA, and pass into the high-purity Ar of 7.5～8.5sccm flow, and purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform; Then keep target platform moving direction perpendicular to the jointing line of Pt and Cu on splicing target, regulating target platform translational speed is 5～10mm/min, make the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded, Pt, Cu particle deposition that Pt, Cu splicing target sputters form catalyst film on graphite fiber cloth one side, the ion beam sputtering time is 5～10min, and catalyst film one-tenth-value thickness 1/10 is 30～50nm;
(3) step (2) gained charcoal carried catalyst film is placed in to 7 * 10
-3～9 * 10
-3in the vacuum of Pa, be heated to 350～450 ℃ and be incubated 1.0～2.0h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
Pt, Cu splicing target described in step of the present invention (2) is that the purity of Pt and Cu all >=99.95% by forming the sputtering target material of square shape after a Pt target and a Cu target splicing.
The prepared controlled charcoal of concentration gradient of atoms of the present invention carries PtCu alloy catalyst and has important application value in water electrolysis-organic matter electrical catalyze reduction coupling technique field; By X-ray diffraction (XRD), containing the detection means such as x-ray photoelectron power spectrum (XPS), inductively coupled plasma emission spectrography (ICP-AES), cyclic voltammetry (CV) and linear sweep voltammetry (LSV) of etching attenuate function, characterize atomic concentration, active metal Pt content, electrochemically active specific surface area and the catalyst activity of the extremely surperficial Pt of phase structure, film bottom that the controlled charcoal of concentration gradient of atoms carries PtCu alloy catalyst.
Adopt XRD to identify catalyst phase structure, after the impact of extremely strong characteristic diffraction peak of getting rid of graphite fiber cloth, be about to diffracting spectrum≤2
θbe controlled within the scope of 30 °～90 °, test result shows that this catalyst is for the film containing active metal, and thing is Pt (111), Cu (111), PtCu (111) and PtCu mutually
3(111); Adopt online etching function attenuate catalyst film, in conjunction with XPS, can intuitively characterize catalyst film bottom to the variation of the atomic concentration of surperficial Pt, test result shows that the atomic concentration direct regulation and control scope of Pt is 26.85～90.42
at.%, the atomic concentration direct regulation and control scope of Cu is 9.58～73.15
at.%, and the atomic concentration of Pt, Cu is homogeneous gradient from film bottom to surface and increases gradually or reduce; Adopt the content of active metal Pt, Cu in ICP-AES quantitative test catalyst, test result shows that in the graphite fiber cloth of gained catalyst, Pt content is 0.075～0.121mg/cm
2, Cu content is 0.019～0.074mg/cm
2.
The method of testing of CV is: the three electrode list hermetic electrolyte pond systems of employing are carried out the electrochemically active specific surface area of catalyst and the test of catalytic activity, wherein, the reference electrode of three electrode list hermetic electrolyte pond systems is saturated calomel electrode, to electrode, is platinum plate electrode, the charcoal that the polytetrafluoroethylene (PTFE) ring-type pad of diameter of bore Ф=30mm is pressed in to prepared nano-pore structure carries on PtCu alloy catalyst surface, another side without PtCu alloy catalyst in graphite fiber cloth is pressed on the glass-carbon electrode of Ф=40mm, screw again the polytetrafluoroethylene (PTFE) screw-tightened lid of diameter of bore Ф=40mm, polytetrafluoroethylene (PTFE) screw-tightened is covered, polytetrafluoroethylene (PTFE) ring-type pad, charcoal carries PtCu alloy catalyst and glass-carbon electrode presses and forms working electrode, the response area that diameter of bore by polytetrafluoroethylene (PTFE) ring-type pad can accurately calculate working electrode is 706.5mm
2, in CV test process, electrolyte used is that concentration is the H of 0.50mol/L
2sO
4solution, three electrode list hermetic electrolyte pond systems are furnished with air inlet pipe and escape pipe, detecting instrument are CHI660D electrochemical workstation.
Before carrying out CV test, need carry out pretreatment to glass-carbon electrode and platinum plate electrode, remove oxide, oil stain and the adsorbate on glass-carbon electrode and platinum plate electrode surface, to improve electrode sensitivity and stability, preprocess method: glass-carbon electrode and platinum plate electrode are first used to the polishing step by step of 1#～7# abrasive paper for metallograph successively; Use successively again the Al of 1.0 and 0.3 μ m
2o
3slurry is polished to minute surface on chamois leather, moves into and in ultrasonic water bath, clean 3min after each polishing; Adopting successively concentration is the HNO of 1.0mol/L again
3solution, deionized water and analysis straight alcohol carry out respectively the ultrasonic cleaning of 3min; The H that last glass-carbon electrode and platinum plate electrode are 0.5mol/L in concentration
2sO
4in solution, adopt CV method to activate, sweep limits is-1.5～1.5V, and scanning is until reach stable cyclic voltammogram repeatedly.
Before carrying out CV test, the high-purity N that the flow that also need pass into 15min in electrolyte is 1.0L/min
2, N wherein
2purity>=99.99%, to remove the dissolved oxygen in electrolyte; CV sweep limits is-0.3～1.2V(relative saturation calomel electrode), electric potential scanning speed is 50mV/s; In CV curve, the oxidation desorption peaks that near the peak-0.2V is hydrogen, the integral area at this peak directly reflects surface-active reaction bit quantity, its size representative participate in oxidation reaction electric weight number; According to the integral area of the oxidation desorption peaks of hydrogen in the CV curve of catalyst, can draw the electrochemically active specific surface area of unit mass Pt, see formula (1):
（1）
In formula:
eSAfor the electrochemically active specific surface area of unit mass Pt,
sfor the oxidation desorption peaks integral area of hydrogen,
mfor 1cm
2pt content on working electrode,
νfor sweep speed,
cfor the unit adsorption capacitance (0.21mC/cm of Pt to hydrogen
2).
The method of testing of LSV is: testing arrangement and flow process be identical with CV method all, difference is to apply linear potential at working electrode with between to electrode, be current potential and time to be linear relationship, the curve that the electric current of the working electrode of measuring and obtaining changes with electrode potential, be LSV curve, can characterize intuitively catalyst as the catalytic activity for hydrogen evolution of negative electrode; LSV sweep limits is got the district-0.40～-0.28V(relative saturation calomel electrode that do not overlap in cathodic region) LSV curve, electric potential scanning speed is 50mV/s; According to LSV data and formula (2), ask the exchange current density of calculating working electrode, be the reaction speed of overpotential in 0 o'clock working electrode, can quantitative description working electrode the ability of transmission redox reaction electric current, exchange current density more catalyst activity is higher.
Definition:
According to the logarithm fortran that refoots, obtain:
（2）
In formula:
zfor charge number;
ffor Faraday constant;
rfor gas constant;
tfor electrode reaction temperature;
kfor constant; △
efor overpotential;
i 0for exchange current density.
Beneficial effect of the present invention and advantage are:
(1) the present invention adopts conventional ion beam sputtering, way moving target platform and Pt, Cu splicing target and vacuum heat-treating method, and directly in graphite fiber cloth, preparing the controlled charcoal of concentration gradient of atoms carries PtCu alloy catalyst;
(2) the present invention uses two-step method, first prepare charcoal carried catalyst film, atomic concentration by target platform translational speed and ion beam sputtering time-controllable film bottom to surperficial Pt, carried out again after vacuum heat, through naturally cooling to room temperature, thereby make the controlled charcoal of concentration gradient of atoms, carry PtCu alloy catalyst, and this catalyst can be used as electrode and is directly used in water electrolysis-organic matter electrical catalyze reduction coupling process;
(3) the present invention directly contamination-freely deposits active metal component on the clean activating surface of graphite fiber cloth after the auxiliary cleaning of ion beam sputtering, strengthened the bond strength of catalyst activity metal and graphite fiber cloth, improved the stability of catalyst, meanwhile, the film layer structure that is homogeneous graded from film bottom to surface-active metallic atom concentration has increased substantially catalyst
eSAthereby value strengthens its electro catalytic activity;
(4) the present invention there is short preparation flow, low cost, without features such as intermediate reaction thing pollutions, the controlled charcoal of concentration gradient of atoms of preparation carries PtCu alloy catalyst, there is the advantages such as low Pt content, better electro-chemical activity, will promote the development of water electrolysis-organic matter electrical catalyze reduction coupling technique.
Accompanying drawing explanation
Fig. 1 be target platform moving direction with splicing target on the jointing line schematic diagram of Pt and Cu;
Fig. 2 is that the controlled charcoal of concentration gradient of atoms of embodiment 3 and embodiment 5 preparations carries in PtCu alloy catalyst, and raw catalyst film thickness is 1
s, wherein
sspan be 30～50nm, through online etching, be thinned to 0.33 place (0.33 of former film thickness
s), 0.66 place (0.66
s) and the interface (0 of film and graphite fiber cloth
s), according to 0
s, 0.33
s, 0.66
sand film surface (1
s) the formed gradient stacking chart of atomic concentration value line of Pt;
Fig. 3 is the XRD stack collection of illustrative plates (30 °≤2 that the controlled charcoal of concentration gradient of atoms that the uniform charcoal of active metal atomic concentration prepared by comparative example carries PtCu alloy catalyst and embodiment 1, embodiment 3 and embodiment 5 preparations carries PtCu alloy catalyst
θ≤ 90 °), wherein a, b, c and d represent respectively the XRD collection of illustrative plates of comparative example, embodiment 1, embodiment 3 and embodiment 5;
Fig. 4 is the CV curve comparison figure that the controlled charcoal of concentration gradient of atoms that the uniform charcoal of active metal atomic concentration prepared by comparative example carries PtCu alloy catalyst and embodiment 1, embodiment 3, embodiment 4 and embodiment 5 preparations carries PtCu alloy catalyst, and wherein a, b, c, d and e represent respectively the CV curve of comparative example, embodiment 1, embodiment 3, embodiment 4 and embodiment 5;
Fig. 5 is the cathodic region LSV curve comparison figure that the controlled charcoal of concentration gradient of atoms that the uniform charcoal of active metal atomic concentration prepared by comparative example carries PtCu alloy catalyst and embodiment 1, embodiment 2, embodiment 3 and embodiment 5 preparations carries PtCu alloy catalyst, and wherein a, b, c, d and e represent respectively the cathodic region LSV curve of comparative example, embodiment 1, embodiment 3, embodiment 4 and embodiment 5.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Comparative example
Described in this comparative example, catalyst is that active metal component loads on and on graphite fiber cloth one side, forms the uniform charcoal of active metal atomic concentration and carry PtCu alloy catalyst, and the preparation method of described catalyst, specifically comprises the steps:
A. will be of a size of 80 * 80mm
2, surface density is 0.20g/cm
2graphite fibre be arranged in 8 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.7kV, line are 705mA, and pass into the high-purity Ar of 7.0sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 6min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
B. the pretreatment graphite fibre of steps A gained is arranged in to 8 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.5kV, line are 80mA, and pass into the high-purity Ar of 8.0sccm flow, purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform, and wherein Pt target and Cu target are respectively one, are planar rectangular shape, after splicing, form the sputtering target material of plane square shape, the purity of Pt and Cu all>=99.95%; Then keep target platform not move, Pt, Cu particle deposition that Pt, Cu splicing target is sputtered out form catalyst film on graphite fiber cloth one side, controlling the ion beam sputtering time is 10min, and in conjunction with the thickness show value of thickness on-line detector, catalyst film one-tenth-value thickness 1/10 is controlled at 48nm;
C. step B gained charcoal carried catalyst film is placed in to 8 * 10
-3in the vacuum of Pa, be heated to 400 ℃ and be incubated 1.0h, after naturally cooling to room temperature, obtain the uniform charcoal of active metal atomic concentration and carry PtCu alloy catalyst.
The uniform charcoal of active metal atomic concentration of preparation is carried to PtCu alloy catalyst and be cut into 40 * 40mm
2totally four, sample, adopt respectively XRD, CV and LSV, XPS and ICP-AES, the atomic concentration of carrying out respectively the Pt of phase structure, electrochemically active specific surface area and catalyst activity, catalyst surface characterize and catalyst in the quantitative test of Pt content.
Result: it is 48nm that the charcoal that this comparative example obtains carries PtCu alloy firm catalyst thickness; There is PtCu
3and Cu (111) thing phase (111);
eSAvalue is 21.7723m
2/ g;
i 0 value is 3.320mA/cm
2; The atomic concentration of the Pt of catalyst surface is 57.31
at.%, the atomic concentration of Cu is 42.69
at.%; Pt content is 0.138mg/cm
2, Cu content is 0.043mg/cm
2.
Embodiment 1
Described in the present embodiment, catalyst is for take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, the concentration gradient of atoms of active component Pt and Cu is is directly regulated and controled by target platform translational speed, within the scope of target platform translational speed, stable running target platform speed makes the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded.
Described in the present embodiment, catalyst is that active metal component loads on and on graphite fiber cloth one side, obtains the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst, and the preparation method of described catalyst, specifically comprises the steps:
A. will be of a size of 80 * 80mm
2, surface density is 0.20g/cm
2graphite fibre be arranged in 9 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.6kV, line are 65mA, and pass into the high-purity Ar of 6.5sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 5min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
B. the pretreatment graphite fibre of steps A gained is arranged in to 9 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.3kV, line are 70mA, and pass into the high-purity Ar of 7.5sccm flow, purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform, wherein Pt target and Cu target are respectively one, form the sputtering target material of plane square shape after splicing, and the purity of Pt and Cu all>=99.95%; Then keep target platform moving direction perpendicular to the jointing line of Pt and Cu on splicing target, ion beam incident direction perpendicular to target platform moving direction and with splicing target on the jointing line angle of Pt and Cu be 45 °, regulating target platform translational speed is 10mm/min, Pt, Cu particle deposition that Pt, Cu splicing target is sputtered out form catalyst film on graphite fiber cloth one side, controlling the ion beam sputtering time is 5min, thickness show value in conjunction with thickness on-line detector, catalyst film one-tenth-value thickness 1/10 is controlled at 30nm, as shown in Figure 1;
C. step B gained charcoal carried catalyst film is placed in to 9 * 10
-3in the vacuum of Pa, be heated to 350 ℃ and be incubated 2.0h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
The controlled charcoal of the concentration gradient of atoms of preparation is carried to PtCu alloy catalyst and be cut into 40 * 40mm
2totally four, sample, adopt respectively XRD, CV and LSV, XPS and ICP-AES, carry out respectively phase structure, electrochemically active specific surface area and catalyst activity, catalyst film bottom to the quantitative test of Pt content in the variation sign of the atomic concentration of surperficial Pt and catalyst.
Result: it is 30nm that the controlled charcoal of concentration gradient of atoms that the present embodiment obtains carries PtCu alloy firm catalyst thickness; There is PtCu
3(111), PtCu (111) and Pt (111) thing phase;
eSAvalue is 37.6731m
2/ g;
i 0 value is 4.104mA/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Pt be respectively 20.61
at.%, 42.23
at.%, 63.85
at.% and 85.47
at.%; Pt content is 0.078mg/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Cu be respectively 79.39
at.%, 57.77
at.%, 36.15
at.% and 14.53
at.%; Cu content is 0.055mg/cm
2.
Embodiment 2
Described in the present embodiment, catalyst is for take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, the concentration gradient of atoms of active component Pt and Cu is is directly regulated and controled by target platform translational speed, within the scope of target platform translational speed, stable running target platform speed makes the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded.
Described in the present embodiment, catalyst is that active metal component loads on and on graphite fiber cloth one side, obtains the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst, and the preparation method of described catalyst, specifically comprises the steps:
A. will be of a size of 80 * 80mm
2, surface density is 0.35g/cm
2graphite fibre be arranged in 7 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.8kV, line are 75mA, and pass into the high-purity Ar of 7.5sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 7min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
B. the pretreatment graphite fibre of steps A gained is arranged in to 7 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.6kV, line are 90mA, and pass into the high-purity Ar of 8.5sccm flow, purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform, and wherein Pt target and Cu target are respectively one, are planar rectangular shape, after splicing, form the sputtering target material of plane square shape, the purity of Pt and Cu all>=99.95%; Then keep target platform moving direction perpendicular to the jointing line of Pt and Cu on splicing target, ion beam incident direction perpendicular to target platform moving direction and with splicing target on the jointing line angle of Pt and Cu be 45 °, regulating target platform translational speed is 5mm/min, Pt, Cu particle deposition that Pt, Cu splicing target is sputtered out form catalyst film on graphite fiber cloth one side, controlling the ion beam sputtering time is 10min, in conjunction with the thickness show value of thickness on-line detector, catalyst film one-tenth-value thickness 1/10 is controlled at 50nm;
C. step B gained charcoal carried catalyst film is placed in to 7 * 10
-3in the vacuum of Pa, be heated to 450 ℃ and be incubated 1.0h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
The controlled charcoal of the concentration gradient of atoms of preparation is carried to PtCu alloy catalyst and be cut into 40 * 40mm
2totally four, sample, adopt respectively XRD, CV and LSV, XPS and ICP-AES, carry out respectively phase structure, electrochemically active specific surface area and catalyst activity, catalyst film bottom to the quantitative test of Pt content in the variation sign of the atomic concentration of surperficial Pt and catalyst.
Result: it is 50nm that the controlled charcoal of concentration gradient of atoms that the present embodiment obtains carries PtCu alloy firm catalyst thickness; There is PtCu
3(111), PtCu (111) and Pt (111) thing phase;
eSAvalue is 47.3219m
2/ g;
i 0 value is 3.498mA/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Pt be respectively 46.81
at.%, 54.13
at.%, 61.45
at.% and 68.78
at.%; Pt content is 0.121mg/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Cu be respectively 53.19
at.%, 45.87
at.%, 38.55
at.% and 31.22
at.%; Cu content is 0.074mg/cm
2.
Embodiment 3
Described in the present embodiment, catalyst is for take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, the concentration gradient of atoms of active component Pt and Cu is is directly regulated and controled by target platform translational speed, within the scope of target platform translational speed, stable running target platform speed makes the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded.
Described in the present embodiment, catalyst is that active metal component loads on and on graphite fiber cloth one side, obtains the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst, and the preparation method of described catalyst, specifically comprises the steps:
A. will be of a size of 80 * 80mm
2, surface density is 0.20g/cm
2graphite fibre be arranged in 8 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.7kV, line are 70mA, and pass into the high-purity Ar of 7.0sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 6min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
B. the pretreatment graphite fibre of steps A gained is arranged in to 8 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.5kV, line are 80mA, and pass into the high-purity Ar of 8.0sccm flow, purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform, and wherein Pt target and Cu target are respectively one, are planar rectangular shape, after splicing, form the sputtering target material of plane square shape, the purity of Pt and Cu all>=99.95%; Then keep target platform moving direction perpendicular to the jointing line of Pt and Cu on splicing target, ion beam incident direction perpendicular to target platform moving direction and with splicing target on the jointing line angle of Pt and Cu be 45 °, regulating target platform translational speed is 9mm/min, Pt, Cu particle deposition that Pt, Cu splicing target is sputtered out form catalyst film on graphite fiber cloth one side, controlling the ion beam sputtering time is 6min, in conjunction with the thickness show value of thickness on-line detector, catalyst film one-tenth-value thickness 1/10 is controlled at 32nm;
C. step B gained charcoal carried catalyst film is placed in to 8 * 10
-3in the vacuum of Pa, be heated to 400 ℃ and be incubated 1.0h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
The controlled charcoal of the concentration gradient of atoms of preparation is carried to PtCu alloy catalyst and be cut into 40 * 40mm
2totally four, sample, adopt respectively XRD, CV and LSV, XPS and ICP-AES, carry out respectively phase structure, electrochemically active specific surface area and catalyst activity, catalyst film bottom to the quantitative test of Pt content in the variation sign of the atomic concentration of surperficial Pt and catalyst.
Result: it is 32nm that the controlled charcoal of concentration gradient of atoms that the present embodiment obtains carries PtCu alloy firm catalyst thickness; There is PtCu
3(111), PtCu (111) and Pt (111) thing phase;
eSAvalue is 86.0875m
2/ g;
i 0 value is 4.218 mA/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Pt be respectively 26.85
at.%, 46.83
at.%, 66.86
at.% and 86.84
at.%; Pt content is 0.075mg/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Cu be respectively 73.15
at.%, 53.17
at.%, 33.14
at.% and 13.16
at.%; Cu content is 0.019mg/cm
2.
Embodiment 4
Described in the present embodiment, catalyst is for take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, the concentration gradient of atoms of active component Pt and Cu is is directly regulated and controled by target platform translational speed, within the scope of target platform translational speed, stable running target platform speed makes the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded.
Described in the present embodiment, catalyst is that active metal component loads on and on graphite fiber cloth one side, obtains the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst, and the preparation method of described catalyst, specifically comprises the steps:
A. will be of a size of 80 * 80mm
2, surface density is 0.28g/cm
2graphite fibre be arranged in 7.5 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.6kV, line are 75mA, and pass into the high-purity Ar of 7.5sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 5min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
B. the pretreatment graphite fibre of steps A gained is arranged in to 8.5 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.3kV, line are 70mA, and pass into the high-purity Ar of 7.5sccm flow, purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform, and wherein Pt target and Cu target are respectively one, are planar rectangular shape, after splicing, form the sputtering target material of plane square shape, the purity of Pt and Cu all>=99.95%; Then keep target platform moving direction perpendicular to the jointing line ion beam incident direction of Pt and Cu on splicing target perpendicular to target platform moving direction and be 45 ° with splicing the jointing line angle of Pt and Cu on target, regulating target platform translational speed is 6mm/min, Pt, Cu particle deposition that Pt, Cu splicing target is sputtered out form catalyst film on graphite fiber cloth one side, controlling the ion beam sputtering time is 9min, in conjunction with the thickness show value of thickness on-line detector, catalyst film one-tenth-value thickness 1/10 is controlled at 44nm;
C. step B gained charcoal carried catalyst film is placed in to 8 * 10
-3in the vacuum of Pa, be heated to 350 ℃ and be incubated 1.5h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
The controlled charcoal of the concentration gradient of atoms of preparation is carried to PtCu alloy catalyst and be cut into 40 * 40mm
2totally four, sample, adopt respectively XRD, CV and LSV, XPS and ICP-AES, carry out respectively phase structure, electrochemically active specific surface area and catalyst activity, catalyst film bottom to the quantitative test of Pt content in the variation sign of the atomic concentration of surperficial Pt and catalyst.
Result: it is 44nm that the controlled charcoal of concentration gradient of atoms that the present embodiment obtains carries PtCu alloy firm catalyst thickness; There is PtCu
3(111), PtCu (111) and Pt (111) thing phase;
eSAvalue is 69.3971m
2/ g;
i 0 value is 3.635mA/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Pt be respectively 41.24
at.%, 52.44
at.%, 63.64
at.% and 74.84
at.%; Pt content is 0.119mg/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Cu be respectively 58.76
at.%, 47.56
at.%, 36.36
at.% and 25.16
at.%; Cu content is 0.031mg/cm
2.
Embodiment 5
Described in the present embodiment, catalyst is for take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, the concentration gradient of atoms of active component Pt and Cu is is directly regulated and controled by target platform translational speed, within the scope of target platform translational speed, stable running target platform speed makes the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded.
Described in the present embodiment, catalyst is that active metal component loads on and on graphite fiber cloth one side, obtains the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst, and the preparation method of described catalyst, specifically comprises the steps:
A. will be of a size of 80 * 80mm
2, surface density is 0.20g/cm
2graphite fibre be arranged in 8.5 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.8kV, line are 65mA, and pass into the high-purity Ar of 7.0sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 7min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
B. the pretreatment graphite fibre of steps A gained is arranged in to 7.5 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.6kV, line are 90mA, and pass into the high-purity Ar of 8.5sccm flow, purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform, and wherein Pt target and Cu target are respectively one, are planar rectangular shape, after splicing, form the sputtering target material of plane square shape, the purity of Pt and Cu all>=99.95%; Then keep target platform moving direction perpendicular to the jointing line of Pt and Cu on splicing target, ion beam incident direction perpendicular to target platform moving direction and with splicing target on the jointing line angle of Pt and Cu be 45 °, regulating target platform translational speed is 7mm/min, Pt, Cu particle deposition that Pt, Cu splicing target is sputtered out form catalyst film on graphite fiber cloth one side, controlling the ion beam sputtering time is 8min, in conjunction with the thickness show value of thickness on-line detector, catalyst film one-tenth-value thickness 1/10 is controlled at 41nm;
C. step B gained charcoal carried catalyst film is placed in to 7 * 10
-3in the vacuum of Pa, be heated to 400 ℃ and be incubated 1.5h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
The controlled charcoal of the concentration gradient of atoms of preparation is carried to PtCu alloy catalyst and be cut into 40 * 40mm
2totally four, sample, adopt respectively XRD, CV and LSV, XPS and ICP-AES, carry out respectively phase structure, electrochemically active specific surface area and catalyst activity, catalyst film bottom to the quantitative test of Pt content in the variation sign of the atomic concentration of surperficial Pt and catalyst.
Result: it is 41nm that the controlled charcoal of concentration gradient of atoms that the present embodiment obtains carries PtCu alloy firm catalyst thickness; There is PtCu
3(111), PtCu (111) and Pt (111) thing phase;
eSAvalue is 42.5129m
2/ g;
i 0 value is 3.677mA/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Pt be respectively 39.43
at.%, 56.41
at.%, 73.39
at.% and 90.42
at.%; Pt content is 0.107mg/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Cu be respectively 60.57
at.%, 43.58
at.%, 26.61
at.% and 9.58
at.%; Cu content is 0.023mg/cm
2.
Embodiment 6
Described in the present embodiment, catalyst is for take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, the concentration gradient of atoms of active component Pt and Cu is is directly regulated and controled by target platform translational speed, within the scope of target platform translational speed, stable running target platform speed makes the atomic concentration of Pt and Cu from film bottom to surface, be homogeneous graded.
Described in the present embodiment, catalyst is that active metal component loads on and on graphite fiber cloth one side, obtains the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst, and the preparation method of described catalyst, specifically comprises the steps:
A. will be of a size of 80 * 80mm
2, surface density is 0.35g/cm
2graphite fibre be arranged in 8 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.6kV, line are 75mA, and pass into the high-purity Ar of 7.5sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 5min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
B. the pretreatment graphite fibre of steps A gained is arranged in to 8 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.5kV, line are 85mA, and pass into the high-purity Ar of 8.0sccm flow, purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform, and wherein Pt target and Cu target are respectively one, are planar rectangular shape, after splicing, form the sputtering target material of plane square shape, the purity of Pt and Cu all>=99.95%; Then keep target platform moving direction perpendicular to the jointing line of Pt and Cu on splicing target, ion beam incident direction perpendicular to target platform moving direction and with splicing target on the jointing line angle of Pt and Cu be 45 °, regulating target platform translational speed is 8mm/min, Pt, Cu particle deposition that Pt, Cu splicing target is sputtered out form catalyst film on graphite fiber cloth one side, controlling the ion beam sputtering time is 7min, in conjunction with the thickness show value of thickness on-line detector, catalyst film one-tenth-value thickness 1/10 is controlled at 39nm;
C. step B gained charcoal carried catalyst film is placed in to 8 * 10
-3in the vacuum of Pa, be heated to 450 ℃ and be incubated 1.5h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
The controlled charcoal of the concentration gradient of atoms of preparation is carried to PtCu alloy catalyst and be cut into 40 * 40mm
2totally four, sample, adopt respectively XRD, CV and LSV, XPS and ICP-AES, carry out respectively phase structure, electrochemically active specific surface area and catalyst activity, catalyst film bottom to the quantitative test of Pt content in the variation sign of the atomic concentration of surperficial Pt and catalyst.
Result: it is 39nm that the controlled charcoal of concentration gradient of atoms that the present embodiment obtains carries PtCu alloy firm catalyst thickness; There is PtCu
3(111), PtCu (111) and Pt (111) thing phase;
eSAvalue is 47.3219m
2/ g;
i 0 value is 3.901mA/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Pt be respectively 33.17
at.%, 51.45
at.%, 69.73
at.% and 88.02
at.%; Pt content is 0.092mg/cm
2; 0
s, 0.33
s, 0.66
swith 1
sthe atomic concentration of Cu be respectively 66.83
at.%, 48.55
at.%, 30.27
at.% and 11.98
at.%; Cu content is 0.020mg/cm
2.
Fig. 1～Fig. 5 is described in detail as follows:
Fig. 1 be target platform moving direction with splicing target on the jointing line schematic diagram of Pt and Cu, its platform moving direction that hits is perpendicular to the jointing line of Pt and Cu on splicing target, and ion beam incident direction is 45 ° perpendicular to target platform moving direction and with splicing the jointing line angle of Pt and Cu on target;
Fig. 2 is that the controlled charcoal of concentration gradient of atoms of embodiment 3 and embodiment 5 preparations carries in PtCu alloy catalyst, according to 0
s, 0.33
s, 0.66
swith 1
sthe formed gradient stacking chart of atomic concentration value line of Pt; The prepared catalyst Atom concentration gradient of the present invention is homogeneous and linearity, and concentration gradient of atoms value also can regulate and control; (in Fig. 2, having added abscissa)
Fig. 3 is the XRD stack collection of illustrative plates (30 °≤2 that the controlled charcoal of concentration gradient of atoms that the uniform charcoal of active metal atomic concentration prepared by comparative example carries PtCu alloy catalyst and embodiment 1, embodiment 3 and embodiment 5 preparations carries PtCu alloy catalyst
θ≤ 90 °), wherein a, b, c and d represent respectively the XRD collection of illustrative plates of comparative example, embodiment 1, embodiment 3 and embodiment 5; Can find: after the impact of extremely strong characteristic diffraction peak of getting rid of graphite fiber cloth, in a, have PtCu
3(111) and Cu (111) thing phase, in b, c and d, there is PtCu
3(111), PtCu (111) and Pt (111) thing phase, show that catalyst directly loads on clean graphite fiber cloth surface, pollution without intermediate reaction thing, and the change along with target platform translational speed, there is by force variation in the characteristic diffraction peak of each thing phase, each phase content exists and changes;
Fig. 4 is the CV curve comparison figure that the controlled charcoal of concentration gradient of atoms that the uniform charcoal of active metal atomic concentration prepared by comparative example carries PtCu alloy catalyst and embodiment 1, embodiment 3, embodiment 4 and embodiment 5 preparations carries PtCu alloy catalyst, and wherein a, b, c, d and e represent respectively the CV curve of comparative example, embodiment 1, embodiment 3, embodiment 4 and embodiment 5; Through formula (1), can be calculated, comparative example, embodiment 1, embodiment 3, embodiment 4 and embodiment 5 prepared catalyst
eSAvalue is respectively 21.7723m
2/ g, 37.6731m
2/ g, 86.0875m
2/ g, 69.3971m
2/ g and 42.5129m
2/ g, the prepared catalyst of the present invention can reduce the content of Pt and obviously improve
eSAvalue, thus its electro catalytic activity strengthened;
Fig. 5 is the cathodic region LSV curve comparison figure that the controlled charcoal of concentration gradient of atoms that the uniform charcoal of active metal atomic concentration prepared by comparative example carries PtCu alloy catalyst and embodiment 1, embodiment 2, embodiment 3 and embodiment 6 preparations carries PtCu alloy catalyst, and wherein a, b, c, d and e represent respectively the cathodic region LSV curve of comparative example, embodiment 1, embodiment 2, embodiment 3 and embodiment 6; Can find out, the cathodic region LSV figure of five kinds of catalyst is basic identical, and its numerical value is for negative; Under same current potential, the absolute value of the current density value of the catalyst of embodiment 3 preparation is maximum, and catalytic activity is best, utilizes formula (2) to ask to calculate comparative example, embodiment 1, embodiment 2, embodiment 3 and embodiment 6 prepared catalyst
i 0 value is respectively 3.320mA/cm
2, 4.104mA/cm
2, 3.498mA/cm
2, 4.218mA/cm
2and 3.901mA/cm
2, show that the prepared concentration gradient of atoms of the present invention can the adjusted and controlled catalytic activity that can obviously strengthen catalyst.
Claims (5)
1. the controlled charcoal of concentration gradient of atoms carries PtCu alloy catalyst, it is characterized in that: described catalyst be take graphite fiber cloth as carbonaceous carrier, Pt, Cu particle directly load on graphite fiber cloth one side and form film catalyst, film catalyst thickness is 30～50nm, and in catalyst, Pt content is 0.075～0.121mg/cm
2, Cu content is 0.019～0.074mg/cm
2.
2. the controlled charcoal of concentration gradient of atoms according to claim 1 carries PtCu alloy catalyst, it is characterized in that: in described catalyst, the atomic concentration of active component Pt and Cu is homogeneous graded from film bottom to surface, and wherein the atomic concentration of Pt is 26.85～90.42
at.%, the atomic concentration of Cu is 9.58～73.15
at.%.
3. the controlled charcoal of concentration gradient of atoms according to claim 1 carries PtCu alloy catalyst, it is characterized in that: described graphite fiber cloth is plain weave propionitrile graphite fiber cloth, and surface density 0.20～0.35g/cm
2.
4. the controlled charcoal of concentration gradient of atoms claimed in claim 1 carries the preparation method of PtCu alloy catalyst, it is characterized in that, specifically comprises the following steps:
(1) graphite fibre is arranged in to 7 * 10
-3～9 * 10
-3in the vacuum of Pa, the screen step voltage of controlling Assisted by Ion Beam irrigation source is that 0.6～0.8kV, line are 65～75mA, and pass into the high-purity Ar of 6.5～7.5sccm flow, wherein purity>=99.999% of Ar, carries out after Assisted by Ion Beam is cleaned 5～7min obtaining pretreated graphite fiber cloth to graphite fiber cloth surface;
(2) the pretreatment graphite fibre of step (1) gained is arranged in to 7 * 10
-3～9 * 10
-3in the vacuum of Pa, the screen step voltage of controlling ion beam sputtering source is that 3.3～3.6kV, line are 70～90mA, and pass into the high-purity Ar of 7.5～8.5sccm flow, and purity>=99.999% of Ar wherein, the Ar ion beam bombardment of drawing is placed on Pt, the Cu splicing target on running target platform; Then keep target platform moving direction perpendicular to the jointing line of Pt and Cu on splicing target, regulating target platform translational speed is 5～10mm/min, Pt, Cu particle deposition that Pt, Cu splicing target sputters form catalyst film on graphite fiber cloth one side, the ion beam sputtering time is 5～10min, and catalyst film one-tenth-value thickness 1/10 is 30～50nm;
(3) step (2) gained charcoal carried catalyst film is placed in to 7 * 10
-3～9 * 10
-3in the vacuum of Pa, be heated to 350～450 ℃ and be incubated 1.0～2.0h, after naturally cooling to room temperature, obtain the controlled charcoal of concentration gradient of atoms and carry PtCu alloy catalyst.
5. the controlled charcoal of concentration gradient of atoms according to claim 4 carries the preparation method of PtCu alloy catalyst, it is characterized in that: Pt, the Cu splicing target described in step (2), that the purity of Pt and Cu all >=99.95% by forming the sputtering target material of square shape after a Pt target and a Cu target splicing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410183944.7A CN104001521A (en) | 2014-05-04 | 2014-05-04 | Carbon-supported PtCu alloy catalyst with controllable atomic concentration gradient and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410183944.7A CN104001521A (en) | 2014-05-04 | 2014-05-04 | Carbon-supported PtCu alloy catalyst with controllable atomic concentration gradient and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104001521A true CN104001521A (en) | 2014-08-27 |
Family
ID=51362595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410183944.7A Pending CN104001521A (en) | 2014-05-04 | 2014-05-04 | Carbon-supported PtCu alloy catalyst with controllable atomic concentration gradient and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104001521A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233366A (en) * | 2014-09-16 | 2014-12-24 | 武汉轻工大学 | Preparation method of iridium and copper oxide alloy cathode catalyst |
| CN105709779A (en) * | 2016-02-01 | 2016-06-29 | 山东大学 | Nano porous copper/platinum core-shell structure catalytic electrode and preparation method thereof |
| CN108754529A (en) * | 2018-05-23 | 2018-11-06 | 昆明理工大学 | A kind of gradient platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen |
| RU2677283C1 (en) * | 2018-06-18 | 2019-01-16 | Анастасия Анатольевна Алексеенко | Bimetallic catalysts with platinum based gradient structure production method |
| CN109888317A (en) * | 2019-03-19 | 2019-06-14 | 苏州钧峰新能源科技有限公司 | A kind of direct methanol fuel cell catalyst and preparation method thereof |
| CN114318409A (en) * | 2021-12-28 | 2022-04-12 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Catalyst electrode for electrochemical reduction of carbon dioxide to synthesize dicarbon products |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517604A (en) * | 2011-12-15 | 2012-06-27 | 昆明理工大学 | Carbon-carrying core-shell type platinoid-platinum catalyst for indirect electrolytic hydrogen production and preparation method thereof |
| CN103143717A (en) * | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Platinoid bimetallic nanometer material and preparation method and application thereof |
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
-
2014
- 2014-05-04 CN CN201410183944.7A patent/CN104001521A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143717A (en) * | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Platinoid bimetallic nanometer material and preparation method and application thereof |
| CN102517604A (en) * | 2011-12-15 | 2012-06-27 | 昆明理工大学 | Carbon-carrying core-shell type platinoid-platinum catalyst for indirect electrolytic hydrogen production and preparation method thereof |
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
Non-Patent Citations (1)
| Title |
|---|
| 杨滨: "复合多相Pt基REOx载体膜电极的结构与析氢性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233366A (en) * | 2014-09-16 | 2014-12-24 | 武汉轻工大学 | Preparation method of iridium and copper oxide alloy cathode catalyst |
| CN104233366B (en) * | 2014-09-16 | 2017-01-25 | 武汉轻工大学 | Preparation method of iridium and copper oxide alloy cathode catalyst |
| CN105709779A (en) * | 2016-02-01 | 2016-06-29 | 山东大学 | Nano porous copper/platinum core-shell structure catalytic electrode and preparation method thereof |
| CN108754529A (en) * | 2018-05-23 | 2018-11-06 | 昆明理工大学 | A kind of gradient platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen |
| RU2677283C1 (en) * | 2018-06-18 | 2019-01-16 | Анастасия Анатольевна Алексеенко | Bimetallic catalysts with platinum based gradient structure production method |
| CN109888317A (en) * | 2019-03-19 | 2019-06-14 | 苏州钧峰新能源科技有限公司 | A kind of direct methanol fuel cell catalyst and preparation method thereof |
| CN109888317B (en) * | 2019-03-19 | 2022-06-07 | 苏州钧峰新能源科技有限公司 | Direct methanol fuel cell catalyst and preparation method thereof |
| CN114318409A (en) * | 2021-12-28 | 2022-04-12 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Catalyst electrode for electrochemical reduction of carbon dioxide to synthesize dicarbon products |
| CN114318409B (en) * | 2021-12-28 | 2023-10-24 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Catalyst electrode for synthesizing two-carbon product by electrochemical reduction of carbon dioxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104001521A (en) | Carbon-supported PtCu alloy catalyst with controllable atomic concentration gradient and preparation method thereof | |
| Liu et al. | Ti 3 C 2 MXene as an excellent anode material for high-performance microbial fuel cells | |
| Qiao et al. | Interfacial electron transfer of Shewanella putrefaciens enhanced by nanoflaky nickel oxide array in microbial fuel cells | |
| Wu et al. | Acceleration of the redox kinetics of VO 2+/VO 2+ and V 3+/V 2+ couples on carbon paper | |
| Erikson et al. | Oxygen reduction on Nafion-coated thin-film palladium electrodes | |
| Alvisi et al. | Sputter deposition of Pt nanoclusters and thin films on PEM fuel cell electrodes | |
| CN104001522B (en) | The charcoal of a kind of nano-pore structure carries PtCu alloy catalyst and preparation method thereof | |
| CN104894595B (en) | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof | |
| Döner et al. | Electrocatalysis of Ni-promoted Cd coated graphite toward methanol oxidation in alkaline medium | |
| Zheng et al. | Multiple effects driven by AC magnetic field for enhanced electrocatalytic oxygen evolution in alkaline electrolyte | |
| Zhang et al. | Preparation of Pt catalysts decorated TiO2 nanotube arrays by redox replacement of Ni precursors for proton exchange membrane fuel cells | |
| Zeng et al. | Ag-doped manganese oxide prepared by electrochemical deposition on carbon fiber for supercapacitors | |
| CN104511276A (en) | Platinum based oxygen reaction reduction catalyst | |
| CN105895385A (en) | Titanium oxide columnar array/two-dimensional lamellar titanium carbide electrode material and preparation and application thereof | |
| Kim et al. | Oxygen reduction reaction of Ta-CN prepared by reactive sputtering with heat treatment | |
| US20190112720A1 (en) | Pulsed current catalyzed gas diffusion electrodes for high rate, efficient co2 conversion reactors | |
| CN102517604B (en) | Carbon-carrying core-shell type platinoid-platinum catalyst for indirect electrolytic hydrogen production and preparation method thereof | |
| US7501050B2 (en) | Method of making metal-coated carbon surfaces for use in fuel cells | |
| Zhang et al. | Highly active Ag nanoparticle electrocatalysts toward V2+/V3+ redox reaction | |
| Cheng et al. | Dynamic hydrogen bubble template electrodeposited Bi on graphite felt and the effect of its post-processing in vanadium redox flow batteries | |
| Floner et al. | Homogeneous coating of graphite felt by nickel electrodeposition to achieve light nickel felts with high surface area | |
| Geuß et al. | Investigation of Iridium-Based OER Catalyst Layers in a GDE Half-Cell Setup: Opportunities and Challenges | |
| Daudt et al. | Fabrication of NbN-coated porous titanium sheets for PEM electrolyzers | |
| Wei et al. | The correlation of the nickel (1 1 1) facet with the hydrogen evolution performance of Ni electrodes in alkaline solutions | |
| Poplavsky et al. | Ion-beam formation of electrocatalysts for fuel cells with polymer membrane electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140827 |
|
| RJ01 | Rejection of invention patent application after publication |