CN114433082A - Enhanced pore type Pt-based alloy membrane catalyst and preparation method thereof - Google Patents
Enhanced pore type Pt-based alloy membrane catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000012528 membrane Substances 0.000 title claims abstract description 93
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 239000011148 porous material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000001659 ion-beam spectroscopy Methods 0.000 claims abstract description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 9
- 125000004334 oxygen containing inorganic group Chemical group 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 229910000905 alloy phase Inorganic materials 0.000 claims abstract description 4
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000010884 ion-beam technique Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 208000005156 Dehydration Diseases 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 229910000636 Ce alloy Inorganic materials 0.000 description 52
- 238000012360 testing method Methods 0.000 description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 238000002484 cyclic voltammetry Methods 0.000 description 17
- 238000004502 linear sweep voltammetry Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000009616 inductively coupled plasma Methods 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 8
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- -1 anion inorganic acid Chemical class 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910002462 C-Pt Inorganic materials 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention discloses a reinforced pore type Pt-based alloy membrane catalyst and a preparation method thereof, belonging to the technical field of water electrolysis-organic matter electrocatalysis reduction coupling. The invention takes Pt as a main phase element, a transition metal element as an alloy phase and a rare earth element as a catalytic assistant, prepares a Pt-based alloy membrane catalyst on a carbon carrier by adopting an ion beam sputtering technology of vacuum thermal deposition, and carries out electrochemical corrosion on the Pt-based alloy membrane catalyst twice by adopting inorganic acid to obtain the enhanced pore type Pt-based alloy membrane catalyst. The invention increases the number of surface active sites of the catalyst by modifying the surface of the catalyst with oxygen-containing inorganic acid, and obtains high active specific surface area; obtaining a pore type structure by acid etching of inorganic acid without oxygen, and increasing the specific surface area of the pore type structure; the Pt ion mobility is controlled by controlling different inorganic acid concentrations, corrosion temperatures and corrosion times, and the enhanced porosity Pt-based alloy membrane catalyst with high catalytic activity and low Pt content is obtained.
Description
Technical Field
The invention belongs to the technical field of water electrolysis-organic matter electrocatalysis reduction coupling, and particularly relates to a reinforced pore type Pt-based alloy membrane catalyst and a preparation method thereof.
Background
Hydrogen energy is an efficient and clean energy source, and at present, hydrogen is industrially produced in a large scale in a mode of producing hydrogen by electrolyzing water and the like. Storage of hydrogen gas remains a challenge. The liquid organic hydrogen storage technology has the advantages of high hydrogen storage density, low technical cost, convenient transportation and the like, and becomes a feasible hydrogen storage mode at present. Therefore, the water electrolysis hydrogen production technology and the organic electro-catalytic reduction technology are coupled, so that hydrogen production and storage are integrated. The process has the advantages of mild reaction conditions and high hydrogen storage efficiency, and the core of the process lies in a membrane catalyst, and the membrane catalyst with high hydrogenation efficiency is generally synthesized by selecting Pt-based alloy with good stability and high catalytic activity.
In the design and preparation of the Pt-based catalyst, the high geometric Specific Surface Area (SSA) and electrochemical activity specific surface area (ESA) are beneficial to improving the catalytic efficiency of the catalyst in the aspect of catalytic hydrogenation. The improvement of the prior high SSA and ESA is obtained, for example, in Chinese patent CN10924482A, a chemical deposition method is adopted to prepare the catalyst, and an acid etching method is adopted to remove alloying, so that redundant alloy components in the catalyst powder can be removed, and the stability and the activity are effectively improved. For example, chinese patent CN113658810A adopts a self-activation method to prepare the catalyst, which has the advantages of short preparation time and no need of complex equipment, but the process for obtaining high SSA is complex, and the substrate and the catalytic layer need to be separated, which may cause the catalytic layer loss. For example, the catalyst synthesized by the Chinese patent CN113083308B by an impregnation method has the advantages of high selectivity and high yield, but the preparation time is long.
Therefore, it is desired to provide a new method for obtaining high SSA and ESA to improve the catalytic activity thereof, and to solve the problems of long preparation time, complicated process, high precious metal loss, etc.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a reinforced pore type Pt-based alloy membrane catalyst and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the first technical scheme is as follows: a pore-enhanced Pt-based alloy membrane catalyst is prepared by taking Pt as a main phase element, a transition metal element as an alloy phase and a rare earth element as a catalytic aid, preparing the Pt-based alloy membrane catalyst on a carbon carrier by adopting an ion beam sputtering technology of vacuum thermal deposition, and then carrying out electrochemical corrosion on the obtained Pt-based alloy membrane catalyst twice by adopting inorganic acid to obtain the pore-enhanced Pt-based alloy membrane catalyst.
Further, the transition metal element is one of Ti, Ni or Cu; the rare earth element includes Ce or La.
Further, the carbonaceous carrier is one of graphite fiber cloth, carbon paper or graphite sheets.
Further, the inorganic acid is an oxygen-free inorganic acid or an oxygen-containing inorganic acid.
Further, the oxygen-free inorganicThe acid is HCl or HBr, and the oxygen-containing inorganic acid is HClO4Or H2SO4。
Further, the concentration of the inorganic acid without oxygen is 0.5-1.0 mol/L; the concentration of the oxygen-containing inorganic acid is 0.25-0.75 mol/L.
The two times of electrochemical corrosion specifically comprise the following steps: firstly, carrying out electrochemical corrosion on inorganic acid without oxygen, and then carrying out electrochemical corrosion on inorganic acid with oxygen after being washed by deionized water at room temperature; or firstly carrying out oxygen-containing inorganic acid electrochemical corrosion, and then carrying out oxygen-free inorganic acid electrochemical corrosion after being washed by room temperature deionized water.
Further, the electrochemical corrosion temperature is 30-60 ℃, and the corrosion time is 5-60 min.
Further, the geometric specific surface area of the enhanced pore type Pt-based alloy membrane catalyst is 81.1-265m2(ii)/g, the specific surface area of electrochemical activity is 734-1183m2/g。
The second technical scheme is as follows: the preparation method of the enhanced pore type Pt-based alloy membrane catalyst comprises the following steps:
1) immersing the carbon carrier in 1.0mol/L H2SO4In the solution, washing with deionized water after ultrasonic cleaning for 8min, then putting into acetone solution for ultrasonic cleaning for 15min, then washing with deionized water, and then carrying out drying and dehydration treatment for 45min to obtain a pretreated carbonaceous carrier;
2) placing the pretreated carbon carrier obtained in the step 1) on a sample table of an ion beam sputtering device, then installing a Pt target, a transition metal target and a rare earth target on a target table of the ion beam sputtering device, and vacuumizing to 8.0x10-4Pa, and reached 2.0x10 in vacuum-3And when Pa is needed, heating the sample table to 200-350 ℃, cleaning for 6min by using an ion beam auxiliary sputtering device, and preparing the Pt-based alloy membrane catalyst by using an ion beam sputtering target.
The noble metal Pt has good catalytic performance in the aspect of liquid organic hydrogen storage, but the noble metal Pt is expensive, pure Pt is easy to generate CO poisoning inactivation when being used as a cathode material, and the addition of the second element can not only reduce the Pt loading capacity, but also improve the catalytic activity and stability of the Pt. According to the invention, the Pt is doped with transition metal elements, such as Ti with electronegativity lower than that of Pt, and electrons can be transferred from Ti to Pt, so that the electron cloud density of Pt is increased. The rare earth catalytic promoter such as Ce has good synergistic effect with Pt, so that the formed ternary alloy catalyst can improve the CO poisoning resistance and catalytic activity of Pt and reduce the Pt loading capacity.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts ion beam sputtering deposition, vacuum heat treatment technology and different anion inorganic acid two-step acid etching methods to carry out electrochemical combined corrosion to prepare the enhanced pore type Pt-based alloy membrane catalyst.
2. The two-step acid etching method adopted by the invention can sequentially control the Pt atomic mobility on the surface of the Pt-based alloy membrane catalyst so as to obtain the enhanced pore type Pt-based alloy membrane catalyst with high SSA and ESA, increase the reaction area of the membrane catalyst and the contact liquid, simultaneously regulate and control the number of active sites participating in hydrogen evolution reaction, and improve the hydrogen evolution catalytic performance. Thereby being directly applied to the technical field of water electrolysis-organic electro-catalytic reduction coupling.
3. The invention adopts different anionic inorganic acids for electrochemical modification. H in inorganic non-oxyacids (e.g. HCl)+Higher concentration and Cl-The diffusion rate of Ce and Ti atoms can be greatly enhanced, so that the SSA of the catalyst is improved; and inorganic oxyacids (e.g., HClO)4) The number of active sites participating in the hydrogen evolution reaction can be regulated, so that the ESA of the catalyst is improved, and the hydrogen evolution reaction rate of the catalyst is increased.
4. The carbon carrier adopted by the invention can be cleaned by ion beam assistance, and the bonding strength of the Pt-based alloy catalyst membrane layer and the carbon carrier and the conductivity of the carbon carrier can be enhanced, so that the electrocatalytic activity of the pore type Pt-based alloy membrane catalyst is enhanced.
5. The preparation process of the invention is simple and convenient, and has no intermediate pollutant.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an XRD stack pattern (30 DEG 2 theta 100 DEG) of porous Pt-Ti-Ce alloy membrane catalysts prepared in control, example 6 and example 4, wherein a, b and e represent XRD patterns of control, example 6 and example 4, respectively;
FIG. 2 is a graph comparing CV curves of porous Pt-Ti-Ce alloy membrane catalysts prepared in control, example 6, example 8, example 2 and example 4, wherein a, b, c, d and e represent CV curves of control, example 6, example 8, example 2 and example 4, respectively; the inset is a partial enlarged CV curve of the porous Pt-Ti-Ce alloy membrane catalyst, in which S1、S2、S3、S4And S5Integrated areas of desorption peaks of hydrogen in the control group, example 6, example 8, example 2 and example 4, respectively;
FIG. 3 is a comparison of LSV curves for the porous Pt-Ti-Ce alloy membrane catalysts prepared in control, example 6, example 8, example 2 and example 4, where a, b, c, d and e represent the LSV curves for the control, example 6, example 8, example 2 and example 4, respectively;
FIG. 4 is a STEM photograph of the surface of a Pt-Ti-Ce alloy membrane catalyst prepared in a control;
FIG. 5 is a STEM photograph of the surface of a porous Pt-Ti-Ce alloy membrane catalyst prepared in example 6;
FIG. 6 is a STEM photograph of the surface of the porous Pt-Ti-Ce alloy membrane catalyst prepared in example 4.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The pore type Pt-based alloy membrane catalyst prepared in each embodiment of the present invention can be evaluated for its phase composition, element content, SSA, and surface morphology using an X-ray diffractometer (XRD), an inductively coupled plasma optical spectrum analyzer (ICP-OES), a nitrogen adsorption specific surface area analyzer (BET), a Scanning Transmission Electron Microscope (STEM), and the like.
The pore type Pt-based alloy membrane catalyst prepared by the invention can be evaluated by using a three-electrode sealed electrolytic cell system matched with an electrochemical workstation and adopting Cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV) and the likeIts ESA and exchange current density (i)0)。
Wherein: the test solution was 0.5mol/L H at 30 ℃ after removal of dissolved oxygen2SO4The potential scanning range of the solution for CV test is-0.35 to 1.2V (relative to a saturated calomel electrode), and the scanning speed is 50 mV/s. From the integrated area of the desorption peak of hydrogen in the CV curve (directly reflecting the number of surface active reaction sites), the ESA per unit mass of Pt can be obtained. See formula (1):
in the formula: ESA-electrochemically active specific surface area per unit mass of Pt; integral area of desorption peak of S-hydrogen; m-1cm2The content of Pt on the working electrode; v-scan rate; specific adsorption capacitance of C-Pt to hydrogen (0.21 mc/cm)2)
The LSV test scanning interval is-0.40V to-0.28V (relative to a saturated calomel electrode), the scanning speed is 50mv/s, and i is obtained by the formula (2)0To evaluate the catalytic efficiency of the membrane electrode.
lgA＝KΔE+lgi0 (2)
Wherein
In the formula: a K-constant; Δ E-overpotential; i all right angle0-exchange current density; F-Faraday constant; r-gas constant; t-electrode reaction temperature; z-number of charges.
Example 1
1) The size of the steel wire is 100 multiplied by 100mm2The graphite fiber cloth is immersed in 1.0mol/L of H at room temperature2SO4Ultrasonically cleaning the graphite cloth in the solution for 8min, then washing the graphite cloth with deionized water, then placing the graphite cloth in an acetone solution for ultrasonically cleaning for 15min, then washing the graphite cloth with deionized water, and then carrying out drying and dehydrating treatment for 45min to obtain pretreated graphite fiber cloth;
2) placing the graphite fiber cloth obtained in the step 1) on a sample table of an ion beam sputtering device, and then placing a Pt targetTi target and Ce target are mounted on the target platform of ion beam sputtering device, and vacuum-pumped to 8.0x10-4Pa, and reached 2.0x10 in vacuum- 3At Pa, the sample stage was initially heated to 350 ℃. At 350 deg.C and 8.0 × 10-4After the vacuum of Pa is cleaned for 6min with the assistance of ion beams, high-purity Ar of 6sccm is introduced, the sputtering screen pressure is controlled to be 2kV, the beam current is controlled to be 60mA, ion beams are generated to sputter a Pt target, a Ti target and a Ce target (50 wt%: 20 wt%: 30 wt%) for 15min, and then the Pt-Ti-Ce alloy membrane catalyst is obtained after natural cooling to the room temperature in the same vacuum degree;
3) cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2Any four samples are respectively put into 0.1mol/L HCl solution at 50 ℃ for acid etching for 30min, washed by room temperature deionized water after the acid etching is finished, and then put into 0.75mol/L HClO at 60 DEG C4And (4) carrying out acid etching in the solution for 10min, and washing the acid-etched sample by using room-temperature deionized water to obtain the pore type Pt-Ti-Ce alloy membrane catalyst.
The obtained pore type Pt-Ti-Ce alloy membrane catalyst is subjected to BET test, CV test, LSV test and ICP test to obtain SSA, ESA and i0And the element content.
As a result: the SSA of the porous Pt-Ti-Ce alloy membrane catalyst of the embodiment is 265m2The concentration is improved by 472 percent compared with a control group; ESA 1152m2The concentration is increased by 180 percent compared with the control group; the efficiency of increase of ESA per SSA was 38%; i.e. i0Is 3.223mA/cm2(ii) a The Pt content is 0.061mg/cm2。
Example 2
The difference from example 1 is that step 3) is specifically operated as: cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2Any four samples are respectively put into 0.1mol/L HCl solution at 50 ℃ for acid etching for 30min, washed by room temperature deionized water after the acid etching is finished, and then put into 0.75mol/L HClO at 60 DEG C4And (4) carrying out acid etching in the solution for 5min, and washing the acid-etched sample by using room-temperature deionized water to obtain the pore type Pt-Ti-Ce alloy membrane catalyst.
The obtained porous Pt-Ti-Ce alloy membrane catalyst is subjected to BET testCV test, LSV test and ICP test to obtain SSA, ESA, i thereof0And the element content.
As a result: the SSA of the porous Pt-Ti-Ce alloy membrane catalyst of the embodiment is 242.913m2The concentration is 433 percent higher than that of a control group; ESA 1163m2The concentration is 181 percent higher than that of a control group; the efficiency of increase of ESA per SSA was 41%; i.e. i0Is 3.817mA/cm2(ii) a The Pt content is 0.065mg/cm2。
Example 3
The difference from example 1 is that step 3) is specifically operated as: cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2Any four samples are put into 0.75mol/L HClO at 60 DEG C4And (3) carrying out acid etching in the solution for 20min, washing the solution with room-temperature deionized water after the acid etching is finished, then putting the solution into 1.0mol/L HCl solution at 50 ℃ for acid etching for 8min, and washing the sample subjected to acid etching with room-temperature deionized water to obtain the porous Pt-Ti-Ce alloy membrane catalyst.
The obtained pore type Pt-Ti-Ce alloy membrane catalyst is subjected to BET test, CV test, LSV test and ICP test to obtain SSA, ESA and i0And the element content.
As a result: the SSA of the Pt-Ti-Ce alloy membrane catalyst of this example was 140m2The concentration is increased by 249 percent compared with a control group; ESA 1019m2The concentration is 159 percent higher than that of a control group; the efficiency of increase of ESA per SSA was 63%; i.e. i0Is 3.798mA/cm2(ii) a The Pt content is 0.086mg/cm2。
Example 4
The difference from example 3 is that the HCl concentration in stage 3) is 0.1 mol/L.
The obtained pore type Pt-Ti-Ce alloy membrane catalyst is subjected to BET test, CV test, LSV test and ICP test to obtain SSA, ESA and i0And the element content.
As a result: in the XRD pattern of the porous Pt-Ti-Ce alloy membrane catalyst of the embodiment, PtTi (111) and Pt exist5Ti3(022) And a characteristic diffraction peak of Pt (111); SSA 196.35m2The concentration is increased by 350 percent compared with the control group; ESA 1183m2The concentration is increased by 184 percent compared with that of a control group; the efficiency of increase of ESA per SSA was 52%; i all right angle0Is 3.803mA/cm2(ii) a The Pt content is 0.0750mg/cm2。
Example 5
The difference from example 1 is that step 3) is specifically operated as: cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2And (3) respectively putting any four of the samples into 0.75mol/L HCl solution at 40 ℃ for acid etching for 60min, and washing the acid-etched samples by using room-temperature deionized water to obtain the porous Pt-Ti-Ce alloy membrane catalyst.
The obtained porous Pt-Ti-Ce alloy membrane catalyst is subjected to BET test, CV test, LSV test and ICP test to obtain SSA, ESA and i0And the element content.
As a result: the SSA of the porous Pt-Ti-Ce alloy membrane catalyst of this example was 196.3m2The concentration is 349 percent higher than that of a control group; ESA 967m2The concentration is increased by 151 percent compared with the control group; the efficiency of increase of ESA per SSA was 43%; i.e. i0Is 3.376mA/cm2(ii) a The Pt content is 0.059mg/cm2。
Example 6
The difference from example 1 is that step 3) is specifically operated as: cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2And (3) respectively putting any four of the samples into 1.0mol/L HCl solution at 50 ℃ for acid etching for 30min, and washing the acid etched samples by using room-temperature deionized water to obtain the porous Pt-Ti-Ce alloy membrane catalyst.
The obtained pore type Pt-Ti-Ce alloy membrane catalyst is subjected to BET test, CV test, LSV test and ICP test to obtain SSA, ESA and i0And the element content.
As a result: in the XRD pattern of the porous Pt-Ti-Ce alloy membrane catalyst of the embodiment, PtTi (111) and Pt exist5Ti3(022) And a characteristic diffraction peak of Pt (111); SSA 222.1m2The concentration is 395 percent higher than that of a control group; ESA 1180m2The concentration is increased by 184 percent compared with that of a control group; the efficiency of increase of unit SSA to ESA is 46%; i.e. i03.747 mA-cm2(ii) a The Pt content is 0.069mg/cm2。
Example 7
The difference from example 1 is that step 3) is specifically operated as: cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2Any four samples are put into 0.5mol/L HClO at 50 DEG C4And (4) carrying out acid etching in the solution for 60min, and washing the acid-etched sample by using room-temperature deionized water to obtain the pore type Pt-Ti-Ce alloy membrane catalyst.
The obtained pore type Pt-Ti-Ce alloy membrane catalyst is subjected to BET test, CV test, LSV test and ICP test to obtain SSA, ESA and i0And the element content.
As a result: the SSA of the porous Pt-Ti-Ce alloy membrane catalyst of this example was 81.1m2The concentration is 144 percent higher than that of a control group; ESA 734m2The concentration is improved by 114 percent compared with that of a control group; the efficiency of increase of ESA per SSA was 79%; i all right angle0Is 3.509mA/cm2(ii) a The Pt content was 0.102mg/cm2。
Example 8
The difference from example 1 is that step 3) is specifically operated as: cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2Any four samples are put into 0.75mol/L HClO at 60 DEG C4And (4) carrying out acid etching in the solution for 20min, and washing the acid-etched sample by using room-temperature deionized water to obtain the pore type Pt-Ti-Ce alloy membrane catalyst.
The obtained pore type Pt-Ti-Ce alloy membrane catalyst is subjected to BET test, CV test, LSV test and ICP test to obtain SSA, ESA and i0And the element content.
As a result: the SSA of the porous Pt-Ti-Ce alloy membrane catalyst of the embodiment is 86m2The concentration is 153 percent higher than that of a control group; ESA 770m2The concentration is increased by 120 percent compared with the control group; the efficiency of increase of ESA per SSA was 78%; i.e. i0Is 3.577mA/cm2(ii) a The Pt content was 0.098mg/cm2。
The difference from example 1 is that step 3) is specifically performedComprises the following steps: cutting the Pt-Ti-Ce alloy membrane catalyst prepared in the step 2) into 15 x 15mm2Any four of the samples (A) to (B) were subjected to BET test, CV test, LSV test and ICP test, respectively, to obtain SSA, ESA and i0And the element content.
As a result: PtTi (111) and Pt exist in XRD pattern of Pt-Ti-Ce alloy membrane catalyst of the control group5Ti3(022) And a characteristic diffraction peak of Pt (111), SSA is 56.1m2G, ESA 640m2/g，i0Is 2.997mA/cm2The Pt content is 0.115mg/cm2。
FIGS. 1-6 show the results of XRD, CV, LSV and STEM tests of the control and examples:
in fig. 1, a, b and e are XRD lines of the control group, example 6 and example 4, respectively. PtTi (111), Pt appear5Ti3(022)、Pt5Ti3(004)、Pt5Ti3(231) And a characteristic diffraction peak of Pt (111), indicating that the catalyst is pure and free of impurity elements. In FIG. 1a, PtTi (111), Pt appear5Ti3(022)、Pt5Ti3(004) And Pt5Ti3(231) The characteristic diffraction peak of (2) shows that PtTi forms an alloy phase during heat treatment, and the contents of Pt and Ti are very small. In comparison of the b and e lines in FIG. 1 with the a line, a Pt (111) peak appears, indicating that a large amount of Ti is corroded and a Pt-rich phase appears.
In fig. 2, a, b, c, d and e are CV curves of the control group, example 6, example 8, example 2 and example 4, respectively. FIG. 2 is an inset showing a partial enlargement of the CV curve for the porous Pt-Ti-Ce alloy membrane catalyst, wherein S1、S2、S3、S4And S5The integrated areas of the desorption peaks of hydrogen in the control, example 6, example 8, example 2, and example 4 were obtained. The ESA values of the control, example 6, example 8, example 2 and example 4 were 640m, respectively, using the formula (1)2/g、1180m2/g、770m2/g、1163m2(iv)/g and 1183m2G, indicating that high ESA can be obtained by acid etching with a combination of different anionic mineral acids. The hydrogen evolution performance of the control group was weaker than that of the control groupIn examples 2 and 4, the Ti is etched by the combination of different anionic inorganic acids, so that the number of active sites is increased, and the catalytic performance is improved.
In fig. 3, a, b, c, d and e are LSV curves of the control group, example 6, example 8, example 2 and example 4, respectively. The formula (2) was used to obtain i of the control, example 6, example 8, example 2 and example 40Respectively is 2.997mA/cm2、3.747mA/cm2、3.577mA/cm2、3.817mA/cm2And 3.803mA/cm2It is shown that the hydrogen evolution performance of the pore type Pt-Ti-Ce alloy membrane catalyst can be improved by combining acid etching with different anion inorganic acids.
Fig. 4 is a STEM photograph of the control group, which shows that the film is uneven and has few holes.
FIG. 5 is a STEM photograph of a porous Pt-Ti-Ce alloy membrane catalyst prepared in example 6. The surface of the material is volcano structure, and pores with diameter less than 10nm appear.
FIG. 6 is a STEM photograph of a porous Pt-Ti-Ce alloy membrane catalyst prepared in example 4. The surface of the alloy is a porous structure, the aperture is greatly increased to about 100nm compared with that of the embodiment 6, the PtTi alloy is mainly used, and a Pt-rich phase appears.
Example 9
The difference from example 4 is that Ti was replaced with Ni to obtain a porous Pt-Ni-Ce alloy membrane catalyst.
As a result: the SSA of the porous Pt-Ni-Ce alloy membrane catalyst of the embodiment is 172m2The concentration is 306 percent higher than that of a control group; ESA 973m2The concentration is increased by 152 percent compared with that of a control group; the efficiency of increase of ESA per SSA was 49%; i.e. i0Is 3.753mA/cm2(ii) a The Pt content is 0.0695mg/cm2。
Example 10
The difference from example 4 is that Ti was replaced by Cu, and a porous Pt-Cu-Ce alloy membrane catalyst was obtained.
As a result: the SSA of the porous Pt-Cu-Ce alloy membrane catalyst of the example is 169.1m2The concentration is 300 percent higher than that of a control group; ESA 1103m2G, comparison with control groupLifting by 172%; the efficiency of increase of ESA per SSA was 57%; i.e. i0Is 3.752mA/cm2(ii) a The Pt content was 0.0737mg/cm2。
Example 11
The difference from example 4 is that the porous Pt-Ti-Ce alloy membrane catalyst is obtained by replacing the graphite fiber cloth with carbon paper.
As a result: the SSA of the porous Pt-Ti-Ce alloy membrane catalyst of the embodiment is 183.42m2The concentration is 326 percent higher than that of a control group; ESA 1172m2The concentration is 183 percent higher than that of a control group; the efficiency of increase of ESA per SSA was 56%; i.e. i0Is 3.679mA/cm2(ii) a The Pt content is 0.0784mg/cm2。
Example 12
The difference from example 4 is that in step 3) the oxygen-containing mineral acid is replaced by H2SO4And replacing the oxygen-free inorganic acid with HBr to obtain the porous Pt-Ti-Ce alloy membrane catalyst.
As a result: the SSA of the porous Pt-Ti-Ce alloy membrane catalyst of the embodiment is 189.1m2The concentration is 337 percent higher than that of a control group; ESA 1083m2The concentration is 169 percent higher than that of a control group; the efficiency of increase of ESA per SSA was 50%; i.e. i0Is 3.631mA/cm2(ii) a The Pt content was 0.0642mg/cm2。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A reinforced pore type Pt-based alloy membrane catalyst is characterized in that Pt is used as a main phase element, a transition metal element is used as an alloy phase, a rare earth element is used as a catalytic auxiliary agent, the Pt-based alloy membrane catalyst is prepared on a carbon carrier by adopting an ion beam sputtering technology of vacuum thermal deposition, and then inorganic acid is adopted to carry out electrochemical corrosion on the obtained Pt-based alloy membrane catalyst for two times, so that the reinforced pore type Pt-based alloy membrane catalyst is obtained.
2. The enhanced pore type Pt-based alloy membrane catalyst according to claim 1, wherein the transition metal element is one of Ti, Ni or Cu; the rare earth element includes Ce or La.
3. The reinforced pore type Pt-based alloy membrane catalyst according to claim 1, wherein the carbonaceous support is one of a graphite fiber cloth, a carbon paper, or a graphite sheet.
4. The reinforced pore type Pt-based alloy membrane catalyst according to claim 1, wherein the inorganic acid is an oxygen-free inorganic acid or an oxygen-containing inorganic acid.
5. The reinforced porous Pt-based alloy membrane catalyst of claim 4, wherein the non-oxygen containing inorganic acid is HCl or HBr and the oxygen containing inorganic acid is HClO4Or H2SO4。
6. The enhanced pore type Pt-based alloy membrane catalyst according to claim 4, wherein the oxygen-free inorganic acid concentration is 0.5 to 1.0 mol/L; the concentration of the oxygen-containing inorganic acid is 0.25-0.75 mol/L.
7. The enhanced pore type Pt-based alloy membrane catalyst according to claim 1, wherein the electrochemical etching temperature is 30 to 60 ℃ and the etching time is 5 to 60 min.
8. The enhanced pore type Pt-based alloy membrane catalyst according to claim 1, wherein the enhanced pore type Pt-based alloy membrane catalyst has a geometric specific surface area of 81.1 to 265m2(ii)/g, the specific surface area of electrochemical activity is 734-1183m2/g。
9. A method of making a reinforced pore type Pt-based alloy membrane catalyst according to any one of claims 1 to 8 which comprises the steps of:
1) mixing the carbonThe substrate was immersed in 1.0mol/L H2SO4In the solution, washing with deionized water after ultrasonic cleaning for 8min, then putting into acetone solution for ultrasonic cleaning for 15min, then washing with deionized water, and then carrying out drying and dehydration treatment for 45min to obtain a pretreated carbonaceous carrier;
2) placing the pretreated carbon carrier obtained in the step 1) on a sample table of an ion beam sputtering device, then installing a Pt target, a transition metal target and a rare earth target on a target table of the ion beam sputtering device, and vacuumizing to 8.0x10-4Pa, and reached 2.0x10 in vacuum-3And when Pa, heating the sample platform to 200-350 ℃, cleaning for 6min by using an ion beam auxiliary sputtering device, and preparing the Pt-based alloy membrane catalyst by using an ion beam sputtering target.
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| WO2012102715A1 (en) * | 2011-01-26 | 2012-08-02 | Blue Nano, Inc. | A membrane electrode assembly for fuel cells |
| CN105648478A (en) * | 2016-01-13 | 2016-06-08 | 大连理工大学 | Preparation method of magnetic nano porous Fe-Pt alloy with electro-oxidation catalytic performance |
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| WO2012102715A1 (en) * | 2011-01-26 | 2012-08-02 | Blue Nano, Inc. | A membrane electrode assembly for fuel cells |
| CN105648478A (en) * | 2016-01-13 | 2016-06-08 | 大连理工大学 | Preparation method of magnetic nano porous Fe-Pt alloy with electro-oxidation catalytic performance |
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