CN105771974A - Catalyst for producing hydrogen by catalyzing decomposition of formate at room temperature - Google Patents
Catalyst for producing hydrogen by catalyzing decomposition of formate at room temperature Download PDFInfo
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- CN105771974A CN105771974A CN201610281077.XA CN201610281077A CN105771974A CN 105771974 A CN105771974 A CN 105771974A CN 201610281077 A CN201610281077 A CN 201610281077A CN 105771974 A CN105771974 A CN 105771974A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Hydrogen, Water And Hydrids (AREA)
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Abstract
The invention particularly relates to a titanium dioxide nanorod palladium-supported (Pd) nanoparticle catalyst for formate decomposition reaction. A titanium dioxide nanorod is used as a support, nano Pd is supported to the surface of the support by means of surface modified in-situ reduction to obtain the supported catalyst. By using the supported catalyst for producing hydrogen by decomposing a formate at room temperature, efficient catalytic decomposition of all formats can be achieved at room temperature, and pure H2 is produced without other gases.
Description
Technical field
The present invention relates to catalyst technical field, particularly to a kind of titanium dioxide nano-rod loaded palladium catalyst decomposing for room temperature catalysis formates and producing hydrogen.
Background technology
Hydrogen is extensively paid attention to as a kind of clean energy resource, and the general power source as fuel cell.Hydrogen or the main raw material of industry, it is used as the raw material of synthesis ammonia, synthesizing methanol, synthetic hydrochloric acid, for hydrogen desulfurization agent in petroleum refining etc., have a wide range of applications in petrochemical industry, electronics industry, metallurgical industry, food processing, Minute Organic Synthesis, Aero-Space etc..
The method of traditional industrial hydrogen production mainly has: water electrolysis hydrogen production, water gas method hydrogen manufacturing or petroleum cracking hydrogen manufacturing.Electrolysis water needs certain electricity input, and water gas method and petroleum cracking process need hot conditions, and therefore these methods have the shortcoming that investment is big, energy consumption is high.Furthermore it is possible to utilize regenerative resource such as sunlight, wind energy etc. to prepare hydrogen, but the hydrogen generation efficiency of these methods is non-normally low at present.So, the concern of people is received in recent years with hydrogen-containing compounds such as formic acid/sodium formates for raw material for preparing hydrogen, formic acid has advantage stable under nontoxic, room temperature, and hydrogen content is up to 4.4wt%, 56g/L, is excellent hydrogen storage material.Formic acid is the by-product that light oil aoxidizes acetic acid processed simultaneously, is recycled and all has very high using value for environment and commercial production, and sodium formate can also be prepared by simple carbon monoxide synthetic method.Hydrogen is produced in decomposition for formates, and catabolite is bicarbonate and hydrogen.This process does not produce other gases, is absent from side reaction simultaneously yet, therefore, it is possible to obtain pure hydrogen, is widely used for fuel cell field at present.Metal Palladium (Pd) is because of the performance of its uniqueness, the concern of people is had been subjected to as the catalyst of a kind of very excellent catalytic hydrogen evolution reaction, but the catalyst that at present catalysis formic acid/formates decomposes is it is generally required to higher load capacity, and this adds preparation cost undoubtedly；The catalyst that simultaneously currently used catalysis formates decomposes is without room temperature activity, it is necessary to could produce when heating and discharge hydrogen.Therefore, by the technology of preparing of regulating catalyst and synthetic method, prepare under room temperature condition, it becomes possible to efficient catalytic formates decomposes the catalyst producing hydrogen becomes the focus that people pay close attention to.
Summary of the invention
The purpose of the present invention: a kind of catalyst decomposing for efficient room temperature catalysis formates and producing hydrogen is provided
In order to achieve the above object, present invention employs following scheme to realize:
Select titanium dioxide nano-rod as carrier, first weigh titanium dioxide carrier material and be dispersed in a certain amount of deionized water, be subsequently adding a certain amount of Pd presoma (PdCl2Or Na2PdCl4), with catalyst weight for 100% so that presoma (with Pd mass meter) mass ratio is for 0.1-4%.It is subsequently added appropriate Na3C6H5O7, equally with catalyst weight for 100% so that Na3C6H5O7Mass ratio is 2.0-20%.It is eventually adding excessive NaBH4Solution reduction, products therefrom is collected by vacuum filtration or centrifugation, washing, dry, and calcining can obtain final catalyst.
There is advantages that
Formates decomposition in solution is produced hydrogen via catalytic dehydrogenation mechanism by described titanium dioxide nano-rod supported palladium nanoparticle catalyst, utilize titanium dioxide nano-rod for carrier, palladium nano-particles, as catalytic active component, has higher catalytic efficiency compared to presently used catalyst.Additionally, this catalyst preparation process is simple, environmental friendliness, catalyst uses condition simple, easy to operate.
Detailed description of the invention
In order to make technical scheme and the beneficial effect reached more preferably clear, below in conjunction with case study on implementation, the present invention being further elaborated, (experimental technique in following embodiment if no special instructions, is conventional method.Test material in following embodiment, if no special instructions, is and is commercially available from conventional chemical reagent shop).Should be appreciated that and described herein be embodied as case only in order to explain the present invention, be not intended to limit the present invention.
Case study on implementation one:
(1) preparation of titanium dioxide nano-rod load P d nanoparticle catalyst
Weigh 1.0g titanium dioxide nano-rod carrier material after 100mL deionized water for ultrasonic is disperseed, add the Na of 100mL, 0.02mM2PdCl4Aqueous solution, is subsequently adding the Na of 0.02g3C6H5O7, it is sufficiently stirred for and makes it dissolve and Homogeneous phase mixing.4mL0.02g/mLNaBH is added after continuing stirring 30min4Solution, stops after continuing stirring 30min, isolates catalyst by high speed centrifugation, after washing, alcohol wash three times, calcines, can obtain titanium dioxide nano-rod supported palladium nanoparticle catalyst after 50 DEG C of dried overnight.
(2) activity rating that catalyst aqueous phase formates decomposes
Taking 0.1g titanium dioxide nano-rod supported palladium nanoparticle catalyst, be placed in glass reaction container and test under normal temperature and pressure, experimentation is as follows: reaction solution consists of 20mL formates aqueous solution, and concentration is 1M.In course of reaction, catalytic reaction temperature is room temperature (25 DEG C), and reaction pressure is atmospheric pressure (1atm).The volume minimum gas volume measurement device producing gas carries out detection in real time and collects, and within 1 hour, can produce about 80mL hydrogen.Gas composition detects through GC, only H2Produce.
Case study on implementation two:
(1) preparation of titanium dioxide nano-rod load P d nanoparticle catalyst
Weigh 1.0g titanium dioxide nano-rod carrier material after 200mL deionized water for ultrasonic is disperseed, add 100mL, 0.02mMNa2PdCl4Aqueous solution, is subsequently adding the Na of 0.05g3C6H5O7, it is sufficiently stirred for and makes it dissolve and Homogeneous phase mixing.10mL0.01g/mLNaBH is added after continuing stirring 30min4Solution, stops after continuing stirring 30min, isolates catalyst by high speed centrifugation, after washing, alcohol wash three times, calcines, can obtain titanium dioxide nano-rod supported palladium nanoparticle catalyst after 50 DEG C of dried overnight.
(2) activity rating that catalyst aqueous phase formates decomposes
Taking 0.1g titanium dioxide nano-rod supported palladium nanoparticle catalyst, be placed in glass reaction container and test under normal temperature and pressure, experimentation is as follows: reaction solution consists of 10mL formates aqueous solution, and concentration is 2M.In course of reaction, catalytic reaction temperature is room temperature (25 DEG C), and reaction pressure is atmospheric pressure (1atm).The volume minimum gas volume measurement device producing gas carries out detection in real time and collects, and within 1 hour, can produce about 100mL hydrogen.Gas composition detects through GC, only H2Produce.
Case study on implementation three:
(1) preparation of titanium dioxide nano-rod load P d nanoparticle catalyst
Weigh 1.0g titanium dioxide nano-rod carrier material after 200mL deionized water for ultrasonic is disperseed, add 100mL, 0.04mMNa2PdCl4Aqueous solution, is subsequently adding the Na of 0.2g3C6H5O7, it is sufficiently stirred for and makes it dissolve and Homogeneous phase mixing.10mL0.02g/mLNaBH is added after continuing stirring 30min4Solution, stops after continuing stirring 30min, isolates catalyst by high speed centrifugation, after washing, alcohol wash three times, calcines, can obtain titanium dioxide nano-rod supported palladium nanoparticle catalyst after 50 DEG C of dried overnight.
(2) activity rating that catalyst aqueous phase formates decomposes
Step (2) with case study on implementation two.
Claims (4)
1. the present invention is a kind of titanium dioxide nano-rod supported palladium nanoparticle catalyst decomposing for room temperature catalysis formates and producing hydrogen, it is characterised in that employing titanium dioxide nano-rod is carrier, and carried metal palladium nano-particles is as active component.
2. catalyst described in claim 1, it is characterised in that catalyst preparing comprises the following steps:
Weigh a certain amount of titanium dioxide nano-rod carrier material ultrasonic disperse in appropriate deionized water, add a certain amount of Pd presoma (PdCl2Or Na2PdCl4), it is stirring evenly and then adding into a certain amount of lemon Na3C6H5O7, after continuing stirring a period of time, add excessive NaBH4Solution reduction, products therefrom is collected by vacuum filtration or centrifugation, washing, dry, and calcining can obtain the palladium catalyst of titanium dioxide nano-rod load.
3. catalyst described in claim 2, it is characterised in that with catalyst weight for 100%, presoma (with Pd mass meter) mass ratio is for 0.1-4%.
4. the purposes of titanium dioxide nano-rod loaded palladium catalyst described in claim 1, it is characterised in that formates, under normal temperature and pressure conditions, can be decomposed the hydrogen producing high-purity by described catalyst efficiently.
Priority Applications (1)
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| CN201610281077.XA CN105771974A (en) | 2016-05-03 | 2016-05-03 | Catalyst for producing hydrogen by catalyzing decomposition of formate at room temperature |
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| CN201610281077.XA CN105771974A (en) | 2016-05-03 | 2016-05-03 | Catalyst for producing hydrogen by catalyzing decomposition of formate at room temperature |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248680A (en) * | 2018-09-28 | 2019-01-22 | 浙江理工大学 | Low-energy-consumption chemical field-driven organic pollutant degradation catalyst and application thereof |
| CN109553067A (en) * | 2017-09-25 | 2019-04-02 | 国家纳米科学中心 | A kind of method of photocatalysis Decomposition formic acid |
| CN110292937A (en) * | 2018-03-21 | 2019-10-01 | 天津大学 | A kind of Rh base catalyst and its preparation method and application being carried on titanium dioxide nano-rod |
| CN110612159A (en) * | 2017-05-01 | 2019-12-24 | 帝斯曼知识产权资产管理有限公司 | Improved method for depositing PD nanoparticles |
| CN114466816A (en) * | 2019-09-26 | 2022-05-10 | 日东电工株式会社 | Hydrogen production method and hydrogen production system |
| CN114787076A (en) * | 2019-12-09 | 2022-07-22 | 日东电工株式会社 | Hydrogen storage method, hydrogen production method, and hydrogen production system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110612159A (en) * | 2017-05-01 | 2019-12-24 | 帝斯曼知识产权资产管理有限公司 | Improved method for depositing PD nanoparticles |
| CN109553067A (en) * | 2017-09-25 | 2019-04-02 | 国家纳米科学中心 | A kind of method of photocatalysis Decomposition formic acid |
| CN109553067B (en) * | 2017-09-25 | 2022-01-14 | 国家纳米科学中心 | Method for decomposing formic acid by photocatalysis |
| CN110292937A (en) * | 2018-03-21 | 2019-10-01 | 天津大学 | A kind of Rh base catalyst and its preparation method and application being carried on titanium dioxide nano-rod |
| CN109248680A (en) * | 2018-09-28 | 2019-01-22 | 浙江理工大学 | Low-energy-consumption chemical field-driven organic pollutant degradation catalyst and application thereof |
| CN109248680B (en) * | 2018-09-28 | 2021-06-15 | 浙江理工大学 | Low-energy-consumption chemical field-driven organic pollutant degradation catalyst and application thereof |
| CN114466816A (en) * | 2019-09-26 | 2022-05-10 | 日东电工株式会社 | Hydrogen production method and hydrogen production system |
| CN114787076A (en) * | 2019-12-09 | 2022-07-22 | 日东电工株式会社 | Hydrogen storage method, hydrogen production method, and hydrogen production system |
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