CN110444773A - Preparation method of ultra-thin tremelliform palladium nano sheet catalyst and products thereof and application - Google Patents

Preparation method of ultra-thin tremelliform palladium nano sheet catalyst and products thereof and application Download PDF

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Publication number
CN110444773A
CN110444773A CN201910863573.XA CN201910863573A CN110444773A CN 110444773 A CN110444773 A CN 110444773A CN 201910863573 A CN201910863573 A CN 201910863573A CN 110444773 A CN110444773 A CN 110444773A
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tremelliform
ultra
thin
palladium
nano sheet
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张连营
王硕
欧阳伊睿
巩玉燕
吴棣本
王峰乾
蒋孟超
李智
张哲�
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Qingdao University
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Qingdao University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to direct methanoic acid fuel cell elctro-catalyst technical fields, are related to ultra-thin tremelliform palladium nano sheet method for preparing catalyst and products thereof and application.It is uniformly mixed method includes the following steps: chlorine palladium acid sodium is added in methanol by (1), obtains mixture；(2) inert gas will be passed through in step (1) in obtained mixture and excludes oxygen, mixture is then heated, is finally passed through CO (3) and product made from step (2) is cleaned；(4) by after cleaning product and carbon black be added in ethyl alcohol carry out ultrasonic mixing it is uniform, be then dried in vacuo, obtain ultra-thin tremelliform palladium nano sheet catalyst.Ultra-thin tremelliform palladium nano sheet catalyst of the invention is compared with being commercialized palladium-carbon catalyst, with the cyclical stability that bigger electrochemically active specific surface area, higher Formic Acid Catalytic Oxidation are active and more excellent, alternative commercialization palladium-carbon catalyst is applied to direct methanoic acid fuel cell and other energy conversion fields.

Description

Preparation method of ultra-thin tremelliform palladium nano sheet catalyst and products thereof and application
Technical field
The invention belongs to direct methanoic acid fuel cell elctro-catalyst technical fields, are related to ultra-thin tremelliform palladium nano sheet catalysis Agent preparation method and products thereof and application.
Background technique
Direct methanoic acid fuel cell (DFAFCs) has energy conversion efficiency is high, environmental-friendly, easy to operate, noise is small etc. Advantage, and formic acid is used as food additives through Food and Drug Administration's license in the U.S., it is seen that the safety of formic acid； DFAFCs as automobile power and in terms of be with a wide range of applications.Formic acid electroxidation is DFAFCs Essential anode-catalyzed reaction, at present, common palladium/carbon catalyst.However, its electro-chemical activity specific surface Product is smaller, the higher surface of Pd nano particle is readily susceptible to reunion etc., causes to Formic Acid Catalytic Oxidation activity and cyclical stability not It is enough excellent, it is difficult to meet the needs of Current commercial.For the commercialization process for accelerating DFAFCs, efficient stable is studied and prepared Formic Acid Catalytic Oxidation agent is particularly important.
Ultra-thin two-dimension material causes the very big research interest of people, In with its unique anisotropy and Electronic Performance The fields such as energy storage and conversion and biosensor show potential huge applications prospect.Ultra-thin palladium nano sheet has super High specific surface area, so as to expose more surface atoms, in the electrochemically active specific surface area for showing superelevation Meanwhile more active sites can be provided.Meanwhile unique two-dimensional structure helps to inhibit high potential lower surface former The dissolution of son and Oswald that moral curing, this is of great significance for the promotion of electro catalytic activity and stability.With regard to mesh Before for, the preparation of ultra-thin palladium nano sheet is involved in polyvinylpyrrolidone (PVP) (Nature Nanotechnology, 2011,6,28.), cetab (CTAB) (Applied Catalysis B: Environmental, 2018,237,866.) use of surface active materials such as, however above-mentioned material is readily adsorbed in preparation Palladium nano sheet surface is difficult to clean off, so that the active site of covering part, causes its electrocatalysis characteristic to be difficult to give full play to. Therefore, under conditions of not adding the materials such as PVP, CTAB, prepare clean surface ultra-thin palladium nano sheet be always challenge and Not yet realize.A kind of ultra-thin palladium nano sheet of clean surface of easy to operate, suitable large-scale production is studied as high-performance formic acid Oxidation catalyst, this is of great significance for accelerating the commercialized development of DFAFCs.
Summary of the invention
It is an object of the invention to overcome defect existing for existing palladium-carbon catalyst, a kind of ultra-thin tremelliform palladium nanometer is provided The preparation method of piece catalyst, this method is not related to the use of the surface active materials such as PVP, CTAB, easy to operate, repeatability Height is suitble to large scale preparation；Catalyst surface made from the preparation method is clean, and comparing with commercialization palladium-carbon catalyst has more The active and more excellent cyclical stability of big electrochemically active specific surface area, higher Formic Acid Catalytic Oxidation；Of the invention is another One is designed to provide application of the catalyst in Oxidation of Formic Acid electrocatalytic reaction.
The present invention, which is that the following technical solution is employed, to be realized:
The present invention provides a kind of preparation methods of ultra-thin tremelliform palladium nano sheet catalyst, comprising the following steps:
(1) chlorine palladium acid sodium is added in methanol and is uniformly mixed, obtain mixture；
(2) inert gas will be passed through to remove the oxygen dissolved in solution, then in obtained mixture in step (1) Mixture is heated, carbon monoxide is finally passed through；
(3) product made from step (2) is cleaned；
(4) by after cleaning product and carbon black be added in ethyl alcohol carry out ultrasonic mixing it is uniform, be then dried in vacuo, obtain The ultra-thin tremelliform palladium nano sheet catalyst.
Specifically, in step (1) methanol chlorine palladium acid sodium 0.5~4.0mg/mL of final concentration, stirring rate be 600~ 1000r/min, mixing time are 10~45min.
Specifically, heating temperature range is 30 DEG C~80 DEG C in the step (2), heating time is 5~20min.
Wherein, ultrasonic power is 100~600W in the step (4), and ultrasonic time is 20~30min；Vacuum drying temperature Degree is 25 DEG C~80 DEG C, and drying time is 10~20h.
Wherein, the carbon black in the step (4) is XC-27.Metal Palladium quality after cleaning on product accounts for addition carbon black powder The 25~35% of last mixture gross mass percentage.
The present invention also provides a kind of ultra-thin tremelliform palladium nano sheet catalyst prepared using above-mentioned preparation method.
The present invention also provides above-mentioned ultra-thin tremelliform palladium nano sheet catalyst to be used for Oxidation of Formic Acid electrocatalytic reaction.
The beneficial effects of the present invention are: the invention discloses a kind of preparation sides of ultra-thin tremelliform palladium nano sheet catalyst Method obtains ultra-thin this two-dimensional material of tremelliform palladium nano sheet, formic acid electro catalytic activity and stability is effectively promoted.System The ultra-thin tremelliform palladium nano sheet catalyst obtained not only has bigger electro-chemical activity ratio compared with being commercialized palladium-carbon catalyst Surface area, and more active sites can be shown, the effective of electrocatalytic reaction is promoted to carry out and kinetics of electrode process It improves, i.e., higher Oxidation of Formic Acid catalytic activity；Ultra-thin tremelliform nanometer sheet is cross-linked with each other simultaneously, to maintain higher knot Structure stability, in conjunction with the stronger anti-Oswald of two-dimensional material itself, your moral cures performance, to open up in formic acid electro-oxidation process Higher cyclical stability is shown, alternative commercialization palladium-carbon catalyst is applied to DFAFCs and other energy storages and conversion Field has higher practical value；And the method for the present invention is not related to the use of the surface active materials such as PVP, CTAB, operation Simplicity, repeatability is high, can prepare with scale, there is potential important application prospect.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.
In the accompanying drawings:
Fig. 1 is the transmission electron microscope picture of ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 1.
Fig. 2 is ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 1 and commercialization palladium-carbon catalyst in 0.5M H2SO4Cyclic voltammetry curve in solution compares figure.
Fig. 3 is ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 1 and commercialization palladium-carbon catalyst in 0.5M H2SO4Catalytic activity in+0.5M HCOOH solution compares figure.
Fig. 4 is ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 1 and commercialization palladium-carbon catalyst in 0.5M H2SO4Stability test in+0.5M HCOOH solution compares figure.
Fig. 5 is the transmission electron microscope picture of ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 2.
Fig. 6 is ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 2 and commercialization palladium-carbon catalyst in 0.5M H2SO4Cyclic voltammetry curve in solution compares figure.
Fig. 7 is ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 2 and commercialization palladium-carbon catalyst in 0.5M H2SO4Catalytic activity in+0.5M HCOOH solution compares figure.
Fig. 8 is ultra-thin tremelliform palladium nano sheet catalyst made from embodiment 2 and commercialization palladium-carbon catalyst in 0.5M H2SO4Stability test in+0.5M HCOOH solution compares figure.
Specific embodiment
In order to which the object of the invention, technical solution is more clearly understood, with reference to the accompanying drawing, the present invention is made further detailed It describes in detail bright.Experimental method described in following embodiments is unless otherwise specified conventional method；It is not specified in embodiment specific Technology or conditions person described technology or conditions or carries out according to the literature in the art according to product description；It is described Reagent and material commercially obtain unless otherwise specified.
Commercialization palladium-carbon catalyst is product number P116795, is purchased from Aladdin company.
For the inert gas that the following example uses for nitrogen, the purity of nitrogen is 99.999% (O2It≤0.001%) is, height Pure nitrogen gas rank, the purity of CO are 99.999%, and the flow of two kinds of gases is respectively 60mL/min.
Embodiment 1
(1) 35mg chlorine palladium acid sodium is added to stirring 10min in 50mL methanol to be uniformly mixed, stirring rate 1000r/ min；
(2) mixture is transferred in bis- neck flask of 100mL, and is warming up to 100 DEG C after being passed through nitrogen 15min, then existed Carbon monoxide 10min is passed through under conditions of stirring；
(3) by products therefrom through eccentric cleaning；
(4) sample of preparation and 30mg XC-72 carbon being added in ethyl alcohol and carries out ultrasound, power 100W carries out 30min, It is uniformly mixed, is then dried in vacuo in -40 DEG C of dry 20h.
Fig. 1 is the transmission electron microscope picture of ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 1；It can be clear from figure Find out that the ultra-thin tremelliform palladium nano sheet catalyst of preparation has apparent tremelliform flake structure clearly.
Prepare 0.5M H2SO4Solution is passed through nitrogen into the solution ten minutes as electrolyte solution, then protects in nitrogen Under shield, it is respectively inserted into reference electrode (saturated calomel electrode), to electrode (platinum electrode) and working electrode (respectively the present embodiment Catalyst and commercialization palladium-carbon catalyst)；Adjust the cyclic voltammetry condition of scanning: minimum scanning voltage -0.25V, maximum scan Voltage 1.1V, scanning speed 50mV/s；Then start recording cyclic voltammetry curve, as shown in Figure 2.With commercialization palladium-carbon catalyst Compared to (41.5m2·g-1), it is living that ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 1 shows higher electrochemistry Property specific surface area (107.8m2·g-1), illustrate ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 1 and commercialization palladium C catalyst, which is compared, has more active sites.
Prepare 0.5M H2SO4+ 0.5M HCOOH solution is passed through nitrogen into the solution ten minutes as electrolyte solution, Then under nitrogen protection, it is inserted into reference electrode (saturated calomel electrode) respectively, to electrode (platinum electrode) and working electrode (difference For the catalyst and commercialization palladium-carbon catalyst of the present embodiment)；Adjust the cyclic voltammetry condition of scanning: minimum scanning voltage- 0.25V, maximum scan voltage 1.1V, scanning speed 50mV/s；Then start recording cyclic voltammetry curve, top institute in curve Corresponding current density and current potential are exactly peak current density and spike potential.As shown in figure 3, being compared with commercialization palladium-carbon catalyst (519.6mA·mg-1 pd), it is close that ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 1 shows bigger peak current Spend (2066.5mAmg-1 pd), while it has also been found that spike potential (0.11V) ratio of tremelliform palladium nano sheet catalyst is commercialized palladium carbon Catalyst (0.18V) is small, illustrates ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 1 and commercialization palladium-carbon catalyst Compared to higher Formic Acid Catalytic Oxidation activity.
Prepare 0.5M H2SO4+ 0.5M HCOOH solution is passed through nitrogen into the solution ten minutes as electrolyte solution, Then under nitrogen protection, it is inserted into reference electrode (saturated calomel electrode) respectively, to electrode (platinum electrode) and working electrode (difference For the catalyst and commercialization palladium-carbon catalyst of the present embodiment)；Then curve when start recording ampere meter, as shown in Figure 4.
When running at the beginning, the current density 519.7mAmg of ultra-thin tremelliform palladium nano sheet catalyst-1, and be commercialized The current density of palladium-carbon catalyst only has 124.6mAmg-1, after running 5000s, the electricity of ultra-thin tremelliform palladium nano sheet catalyst Flow close 90.3mAmg-1, and the current density for being commercialized palladium-carbon catalyst only has 27.5mAmg-1, illustrate prepared by embodiment 1 Ultra-thin tremelliform palladium nano sheet catalyst for Formic Acid Catalytic Oxidation compared with being commercialized palladium-carbon catalyst have higher first Surface acidity and better cyclical stability.
Above-mentioned experimental data shows that ultra-thin tremelliform palladium nano sheet catalyst is for Catalyzed by Formic Acid made from the present embodiment 1 Oxidation has bigger electrochemically active specific surface area, higher Formic Acid Catalytic Oxidation activity compared with being commercialized palladium-carbon catalyst With excellent cyclical stability, thus alternative commercialization palladium-carbon catalyst be applied to direct methanoic acid fuel cell and other energy Source conversion art.
Embodiment 2
(1) 20mg chlorine palladium acid sodium is added to stirring 20min in 30mL methanol to be uniformly mixed, stirring rate 600r/ min；
(2) mixture is transferred in bis- neck flask of 100mL, and is warming up to 40 DEG C after being passed through nitrogen 25min, then stirred Carbon monoxide 5min is passed through under conditions of mixing；
(3) by products therefrom through eccentric cleaning；
(4) sample of preparation and 30mg XC-72 carbon being added in ethyl alcohol and carries out ultrasound, power 100W carries out 30min, It is uniformly mixed, is then dried in vacuo in -40 DEG C of dry 20h.
Fig. 5 is the transmission electron microscope picture of ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 2；It can be clear from figure Find out that the ultra-thin tremelliform palladium nano sheet catalyst of preparation has apparent tremelliform flake structure clearly.
Using detection method same as Example 1, carries out the present embodiment 2 and ultra-thin tremelliform palladium nano sheet catalyst is made Performance detection.
Fig. 6 is ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 2 and commercialization palladium-carbon catalyst in 0.5M H2SO4Cyclic voltammetry curve in solution compares figure；It was found that comparing (41.5m with commercialization palladium-carbon catalyst2·g-1), this implementation Ultra-thin tremelliform palladium nano sheet catalyst made from example 2 shows bigger electrochemically active specific surface area (104.6m2·g-1), Illustrate that ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 2 is compared to have with commercialization palladium-carbon catalyst more to urge Change active site.
Fig. 7 is ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 2 and commercialization palladium-carbon catalyst in 0.5M H2SO4Catalytic activity in+0.5M HCOOH solution compares figure；It was found that comparing (518.7mAmg with commercialization palladium-carbon catalyst-1 Pd), ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 2 shows higher peak current density (2054.3mA mg-1 Pd), while it has also been found that spike potential (0.12V) ratio of ultra-thin tremelliform palladium nano sheet catalyst is commercialized palladium-carbon catalyst (0.19V) is small, illustrates that ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 2 compares tool with commercialization palladium-carbon catalyst There is higher Formic Acid Catalytic Oxidation activity.
Fig. 8 is ultra-thin tremelliform palladium nano sheet catalyst made from the present embodiment 2 in 0.5M H2SO4+ 0.5M HCOOH is molten The stability test of liquid compares figure；When running at the beginning, the current density 521.4mA of ultra-thin tremelliform palladium nano sheet catalyst mg-1, and the current density for being commercialized palladium-carbon catalyst only has 118.6mAmg-1, after running 5000s, ultra-thin tremelliform palladium is received The close 27.2mAmg of electric current of rice piece catalyst-1, and the current density for being commercialized palladium-carbon catalyst only has 87.8mAmg-1, say Ultra-thin tremelliform palladium nano sheet catalyst prepared by bright embodiment 2 is for Formic Acid Catalytic Oxidation compared with being commercialized palladium-carbon catalyst With higher Catalyzed by Formic Acid activity and better cyclical stability.
Certainly, these are only the preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of preparation method of ultra-thin tremelliform palladium nano sheet catalyst, which comprises the following steps:
(1) chlorine palladium acid sodium is added in methanol and is uniformly mixed, obtain mixture；
(2) inert gas will be passed through in obtained mixture in step (1) to remove the oxygen dissolved in solution, then heat Mixture is finally passed through carbon monoxide；
(3) product made from step (2) is cleaned；
(4) by after cleaning product and carbon black be added in ethyl alcohol that carry out ultrasonic mixing uniform, be then dried in vacuo, obtain described Ultra-thin tremelliform palladium nano sheet catalyst.
2. the preparation method of ultra-thin tremelliform palladium nano sheet catalyst according to claim 1, which is characterized in that the step Suddenly in (1) methanol chlorine palladium acid sodium 0.5~4.0mg/mL of final concentration, stirring rate is 600~1000r/min, and mixing time is 10~45min.
3. the preparation method of ultra-thin tremelliform palladium nano sheet catalyst according to claim 1, which is characterized in that the step Suddenly heating temperature range is 30 DEG C~80 DEG C in (2), and heating time is 5~20min.
4. the preparation method of ultra-thin tremelliform palladium nano sheet catalyst according to claim 1, which is characterized in that the step Suddenly ultrasonic power is 100~600W in (4), and ultrasonic time is 20~30min；Vacuum drying temperature is 25 DEG C~80 DEG C, dry Time is 10~20h.
5. the preparation method of ultra-thin tremelliform palladium nano sheet catalyst according to claim 1, which is characterized in that the step Suddenly the carbon black in (4) is XC-27.
6. a kind of ultra-thin tremelliform palladium nano sheet catalyst, which is characterized in that the ultra-thin tremelliform palladium nano sheet catalyst by The described in any item methods of claim 1-5 are prepared.
7. a kind of application of ultra-thin tremelliform palladium nano sheet catalyst, which is characterized in that ultra-thin tremelliform palladium described in claim 6 Nanometer sheet catalyst is used for Oxidation of Formic Acid electrocatalytic reaction.
CN201910863573.XA 2019-09-12 2019-09-12 Preparation method of ultra-thin tremelliform palladium nano sheet catalyst and products thereof and application Withdrawn CN110444773A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111785981A (en) * 2020-06-30 2020-10-16 青岛大学 Palladium-palladium-tungsten-chromium nano catalyst and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111785981A (en) * 2020-06-30 2020-10-16 青岛大学 Palladium-palladium-tungsten-chromium nano catalyst and preparation method and application thereof
CN111785981B (en) * 2020-06-30 2022-03-18 青岛大学 Palladium-palladium-tungsten-chromium nano catalyst and preparation method and application thereof

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Application publication date: 20191112