CN108505064A - A kind of platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen - Google Patents
A kind of platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen Download PDFInfo
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- CN108505064A CN108505064A CN201810342965.7A CN201810342965A CN108505064A CN 108505064 A CN108505064 A CN 108505064A CN 201810342965 A CN201810342965 A CN 201810342965A CN 108505064 A CN108505064 A CN 108505064A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000001257 hydrogen Substances 0.000 title claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000012528 membrane Substances 0.000 title claims abstract description 41
- 150000001875 compounds Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 33
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 28
- 239000000956 alloy Substances 0.000 claims abstract description 28
- 238000007731 hot pressing Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003610 charcoal Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000010304 firing Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 6
- 238000005087 graphitization Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- -1 perfluorinated sulfonic acid salt ions Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 210000004379 membrane Anatomy 0.000 abstract description 27
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 210000002469 basement membrane Anatomy 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 32
- 229920000557 Nafion® Polymers 0.000 description 16
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention discloses the method that a kind of platinum base membrane electrode catalysis unsaturated compounds add hydrogen, belongs to electrolytic hydrogen production organic matter electro-catalysis hydrogen storage technology field.Pt basement membranes electrode of the present invention（SPEME）The single side progress hot pressing that PtTi alloy catalysts and solid polymer dielectric film are carried for charcoal obtains, SPEME is placed between adjacent anode chamber and cathode chamber and compresses three, the two-sided anodic-cathodics of close attachment respectively of SPEME are to ensure charge-exchange, hydrogen is added to separate in two reative cells electrolytic hydrogen production and unsaturated compounds, and it is independently carried out under the normal pressure operating mode not higher than 80 DEG C, regulate and control hydrogen manufacturing respectively by response voltage and add the reaction selectivity of hydrogen, adds hydrogen current efficiency and target product yield to enhance unsaturated compounds；The method of the invention is simple for process general, easy to operate, and reaction is safe and efficient, and low energy consumption, and environmental pollution is small.
Description
Technical field
The present invention relates to the methods that a kind of platinum base membrane electrode catalysis unsaturated compounds add hydrogen, and it is organic to belong to electrolytic hydrogen production-
Object electro-catalysis hydrogen storage technology field.
Background technology
Under the dual background of global energy crisis and environmental pressure, haulagman of the countries in the world to high-effect low dirty discharge
The demand of tool fuel is more urgent.China will start automobile-used 6 standard of petrol and diesel oil state executed in 2019（GB17930-
2016）In, it is specified that aromatic hydrocarbons（Containing benzene）And the volume fraction maximum value of the unsaturated compounds such as alkene on the basis of 5 standard of state again
20% is reduced, this is to unsaturated compounds hydrotreating techniques and reaction system in safety in production, low pollution emission, high reaction production
Object rate, low energy consumption cost, working service convenience etc. propose requirements at the higher level.
Hydrogen it is cheap produce, safety in transportation and storage, efficient application be always hydrogen utilization key link, before making the present invention,
Hydrogen manufacturing, hydrogen storage and hydrogen addition technology and device have had many research and implementation, but there are different disadvantages：N. Itoh et al.
The research of [Int. J. Catalysis Today, 2000,56 (1-3)] to " water electrolysis-organic matter electro-catalysis reduction coupling "
Show that higher electrode reaction current density and reaction selectivity can be obtained, but inhale hydrogen release complex process, organic compound follows
Ring utilization rate is low；The hydrogen adsorption process of ZL200510111758.3 is difficult to control, and can introduce the foreign gases such as oxygen, and hydrogen
Bubble can be ruptured by slight perturbations to be unfavorable for transporting；Flow rate of carrier gas is very fast in ZL200410033882.8, and reaction is insufficient, adds
Actual production requirement is not achieved in hydrogen efficiency and target product content；In ZL201010001103.1 and CN201310206899.8
Pressure-resistant performance is relatively low, and equipment investment and energy consumption are higher, and practical operation danger is larger.
In short, the studies above and technology are implemented, there is less economical, high energy consumption in various degree（300~350℃）, evaporation
Loss is big, long flow path, work are dangerous（5~6MPa）The shortcomings of.Therefore, research and probe reaction is mild, is not necessarily to additional hydrogen source, is short
Flow, low energy consumption, low stain electrolytic hydrogen production-unsaturated compounds electrocatalytic hydrogenation technology, for fields such as the energy, chemical industry
Skill upgrading shows profound significance.
Invention content
Add defect existing for hydrogen storage for traditional organic matter, the purpose of the present invention is to provide a kind of platinum base membrane electrodes to urge
Change the method that unsaturated compounds add hydrogen, detailed process is：Using heat pressing process, charcoal load PtTi alloy catalysts are compressed on solid
Body polymer dielectric（SPE）Platinum base membrane electrode is made on the single side of film（SPEME）, by platinum base membrane electrode（SPEME）It is placed in phase
Three is compressed between adjacent anode chamber and cathode chamber, the charcoal being attached on platinum base membrane electrode carries PtTi alloy catalysts as cloudy
The working electrode of pole room, the another side of platinum base membrane electrode are contacted with the carbonaceous electrode seal of anode chamber；By the electrolysis system of anode chamber
Hydrogen process and the unsaturated compounds hydrogenation process of cathode chamber separate and independently carry out, and control anode chamber and cathode chamber is anti-respectively
Voltage is answered, to regulate and control the reaction selectivity of electrolytic hydrogen production and unsaturated compounds hydrogenation process.
It is the Ti targets that Pt is inlayed by ion beam sputtering that charcoal of the present invention, which carries PtTi alloy catalysts, is deposited on heating charcoal
Obtained on carrier, gained charcoal carry Pt based alloy catalysts catalysis layer thickness 30~100nm, Pt carrying capacity 0.008~
0.025mg/cm2。
The unsaturated compounds hydrogenation reaction temperature of cathode chamber of the present invention is 60~80 DEG C.
Carbonaceous electrode of the present invention is plain weave propionitrile graphite fiber cloth, surface degree of graphitization >=99%, surface density 0.20
~0.35g/cm2。
High-area carbon of the present invention be plain weave propionitrile graphite fiber cloth, surface degree of graphitization >=99%, surface density 0.20~
0.35g/cm2。
Solid polymer dielectric film of the present invention is perfluorinated sulfonate ion exchange（Nafion）Film transmits proton
Ability is strong.
Preferably, the present invention prepares SPEME using heat pressing process, specifically includes following steps：
（1）It prepares platinum base membrane electrode and handles soak, soak is 5~25% perfluorinated sulfonic acid salt ions by mass percent concentration
The ratio that liquid, the PTFE solution that mass percent concentration is 5~25% and deionized water are 1 ︰, 1 ︰ 1 by volume is exchanged to mix
It arrives；
（2）Charcoal load PtTi alloy catalysts are placed in step（1）In the soak of preparation, wherein 30~50 DEG C of soak temperature,
5~10min of soaking time, natural air drying after taking-up；
（3）By step（2）Gained charcoal carries PtTi alloy catalysts and is fired in Muffle furnace, firing condition：Firing temperature 500~
700 DEG C, 20~60s of firing time；
（4）Solid polymer dielectric film is immersed in 10 in the hydrogen peroxide of the dilute sulfuric acid containing 0.1~0.5mol/L~for 24 hours；
（5）By step（3）Gained charcoal carries PtTi alloy catalysts and step（4）Obtained solid polymer dielectric film carries out heat
Pressure, hot pressing condition are：125~225 DEG C, 10~20MPa of hot pressing pressure, 2~10min of hot pressing time of hot pressing temperature.
Anode chamber's electrolyte inside of the present invention is the dilute sulfuric acid or dilute nitric acid solution of 0.5~1.0mol/L, in cathode chamber
Unsaturated compounds are mononuclear aromatic, alkene or alkynes of the carbon atom number of liquid between 5~16.
Carbonaceous cathode passes through the proton of Nafion membrane directly to exist directly next in Nafion membrane surface in anode chamber of the present invention
Catalysis layer surface completes unsaturated compounds catalytic hydrogenation reaction in cathode chamber.
Beneficial effects of the present invention：
（1）In the reaction of unsaturated compounds electrocatalytic hydrogenation, Ti can improve the hydrogen adsorptive capacity of membrane electrode and increase to unsaturation
The absorption of organic molecule shows promoting catalysis with raising plus hydrogen current efficiency；It is prepared using ion beam sputtering technology
PtTi alloy catalysts, Catalytic Layer is uniform, and particle dispersion is good, can reduce the dosage of Pt to greatest extent；Using heat pressing process
SPE membrane electrodes are prepared, bond strength is high, is not easily disconnected from, to realize that short route processes efficient electrocatalytic hydrogenation Pt basement membrane electrodes.
（2）Pt basement membranes electrode proposed by the present invention is installed in the reaction unit for realizing the present invention, graphite in anode chamber
Fiber cloth cathode advantageously reduces voltage drop caused by mass transfer resistance, improves and penetrate directly next in Nafion membrane surface
Nafion membrane diffuses to the proton quantity of hydrogenation catalyst layer, and the proton across Nafion membrane is directly urged in the PtTi alloys of cathode chamber
Unsaturated compounds catalytic hydrogenation reaction is completed on agent surface, can reduce mass transfer diffusional resistance, is improved and is added hydrogen current efficiency, reaction
It is mild condition, low without additional hydrogen source, overall energy consumption.
（3）Cathode chamber is controlled respectively by electrochemical workstation and direct-flow voltage regulation source adds hydrogen potential（Add hydrogen main reaction current potential
About -0.5V, liberation of hydrogen side reaction current potential are about -0.2V）, anode chamber's evolving hydrogen reaction current potential（About 1.6V）, can fully press down
The liberation of hydrogen side reaction on the PtTi alloy catalysts surface of the SPEME of cathode chamber processed, the corresponding yield for improving target product；By following
Loop back path can supplement reaction solution and carry out cycle hydrogenation reaction to unsaturated compounds, and the collection of gas reception device is not participated in anti-
The hydrogen and reaction solution boil-off gas answered so that the target yield of the method for the present invention and safe, environmental pollution is small, operation letter
Single, easy to maintain, service life is long.
Description of the drawings
Fig. 1 is the XRD superposition collection of illustrative plates of SPEME prepared by embodiment 1 and embodiment 4（）；
Fig. 2 is that analysis chart is swept in the faces EDS on SPEME Electrocatalytic Layers surface prepared by embodiment 4；
Fig. 3 is the content histogram of the benzene electrocatalytic hydrogenation product of the cathode chamber of embodiment 1 ~ 5.
Specific implementation mode
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
The implementation process of the present invention：By dilute acid soln（0.5~1.0mol/L dilute sulfuric acids or dust technology）It is pumped into and full of sun
Pole room, by unsaturated compounds（Such as benzole soln）It is pumped into and is full of cathode chamber, control obtains the best hydrogenation reaction temperature of cathode chamber
Degree（60~80℃）；By electrochemical workstation and direct-flow voltage regulation source, cathode chamber hydrogenation reaction current potential -0.5V, and sun are controlled respectively
The current potential 1.6V of pole room evolving hydrogen reaction；In continuous work, the reaction solution concentration of anode chamber had both been maintained by circulation loop, also will
Mixing unsaturated compounds containing target product（Such as benzene+cyclohexene+hexamethylene）Cycle is pumped into cathode chamber, and carrying out unsaturation has
The cycle hydrogenation reaction of machine object, until reaching the content requirement of target product；It can be collected in anode chamber by gas reception device
The hydrogen for not participating in reaction being precipitated also can collect reaction solution boil-off gas in cathode chamber by another set of gas reception device
（Benzene）And side reaction product（Hydrogen）, then unsaturated compounds hydrogenation reaction raw material is used as after liquefaction is handled, to enhance this hair
Bright economy.
Embodiment 1
（1）Charcoal is prepared using ion beam sputtering technology and carries PtTi alloy catalysts：High-area carbon is 0.35g/cm2The 100 of surface density
×100mm2Graphite fiber cloth, be placed in the sulfuric acid solution of 0.5mol/L and be cleaned by ultrasonic 3min, then be cleaned by ultrasonic through acetone
6min, deionized water are cleaned by ultrasonic 3min, and finally 50 DEG C of dry 30min in drying box, obtain pretreated graphite fibre
Cloth high-area carbon.
（2）By step（1）Gained high-area carbon is placed on ion beam sputtering sample stage, and sample stage is warming up to 300 DEG C, works as vacuum
Degree reaches 8 × 10-4When Pa, Assisted by Ion Beam first is carried out to graphite fiber cloth and cleans 6min, ion beam sputtering is then carried out and inlays
The purity of the Ti targets of Pt, Pt and Ti >=99.95%, PtTi alloy catalyst thicknesses of layers 100nm, vacuum decay warms to room temperature,
Pt carrying capacity 0.025mg/cm2。
（3）At ambient temperature, by step（2）Obtained charcoal load PtTi alloy catalysts are placed in group and are divided into 5%Nafion
10min in 30 DEG C of soaks of Ye ︰ 5%PTFE ︰ deionized waters=1 ︰, 1 ︰ 1, then takes out natural air drying.
（4）By step（3）Gained charcoal carries PtTi alloy catalysts and is fired in Muffle furnace, firing condition：Firing temperature 500
DEG C, firing time 20s.
（5）Nafion membrane is immersed in 10h in the hydrogen peroxide of the dilute sulfuric acid containing 0.5mol/L, then with step（4）It obtains
Charcoal carries the progress hot pressing of PtTi alloy catalysts and obtains SPEME, hot pressing condition：225 DEG C, hot pressing pressure 20MPa of hot pressing temperature, hot pressing
Time 10min.
（6）By step（5）Obtained SPEME is placed between adjacent anode chamber and cathode chamber, the charcoal being attached on SPEME
Carry working electrode of the PtTi alloy catalysts as cathode chamber, the another side of platinum base membrane electrode and the carbonaceous electrode seal of anode chamber
Contact；The unsaturated compounds hydrogenation process of the electrolytic hydrogen production process of anode chamber and cathode chamber is separated and is independently carried out；Reaction
Temperature 60 C；Reaction medium：Cathode chamber is the mixed solution of benzene and cetyl trimethylammonium bromide, mass ratio 25:1,
Anode chamber is 1.0mol/L sulfuric acid, is electrolysed under the voltage of 1.6V；
In Fig. 1（Wherein a represents the XRD diagram of SPEME prepared by pure Pt, b embodiment 1）Show SPEME's manufactured in the present embodiment
XRD diagram after PDF objects phase standard card, it is found that there is only PtTi, Pt in the catalyst film layer of Pt basement membrane electrodes by contrast5Ti3With
Pt3Ti alloy phases；Cathode chamber reaction product utilizes chromatographic mass spectrometry（GC-MS）It is analyzed, the product hexamethylene of benzene hydrogenation can be obtained
Alkane, while there is also byproduct hydrogen gas, current efficiency shows that hexamethylene and hydrogen content are respectively up to 36.22%, Fig. 3
0.029wt.% and 0.153wt.% illustrates that a kind of platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen to be practical
's.
Embodiment 2
（1）The step of using embodiment 1（1）, difference：The surface density 0.20g/cm of high-area carbon2。
（2）The step of using embodiment 1（2）, difference：PtTi alloy catalyst thicknesses of layers 30nm, Pt carrying capacity
0.008mg/cm2。
（3）The step of using embodiment 1（3）, difference：Soak group is divided into 25%Nafion liquid ︰ 25%PTFE ︰ deionized waters
5min in 50 DEG C of soaks of 1 ︰ 1 of=1 ︰.
（4）The step of using embodiment 1（4）, difference：600 DEG C of firing temperature, firing time 60s.
（5）The step of using embodiment 1（5）, difference：Nafion membrane is immersed in the hydrogen peroxide of the dilute sulfuric acid containing 0.1mol/L
In for 24 hours, 125 DEG C, hot pressing pressure 10MPa, hot pressing time 2min of hot pressing temperature.
（6）The step of using embodiment 1（6）, difference：65 DEG C of reaction temperature, anode chamber are 0.8mol/L sulfuric acid.
Cathode chamber reaction product utilizes chromatographic mass spectrometry（GC-MS）It is analyzed, the product hexamethylene of benzene hydrogenation can be obtained, together
When there is also byproduct hydrogen gas, current efficiency shows that the content of hexamethylene and hydrogen is respectively 0.086wt.% up to 36.94%, Fig. 3
And 0.185wt.%, this illustrates that a kind of platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen to be practicable.
Embodiment 3
（1）The step of using embodiment 1（1）, difference：The surface density 0.30g/cm of high-area carbon2。
（2）The step of using embodiment 1（2）, difference：PtTi alloy catalyst thicknesses of layers 70nm, Pt carrying capacity
0.019mg/cm2。
（3）The step of using embodiment 1（3）, difference：Soak group is divided into 25%Nafion liquid ︰ 5%PTFE ︰ deionized waters
8min in 40 DEG C of soaks of 1 ︰ 1 of=1 ︰.
（4）The step of using embodiment 1（4）, difference：700 DEG C of firing temperature, firing time 40s.
（5）The step of using embodiment 1（5）, difference：Nafion membrane is immersed in the hydrogen peroxide of the dilute sulfuric acid containing 0.3mol/L
Middle 20h, 175 DEG C, hot pressing pressure 15MPa, hot pressing time 5min of hot pressing temperature.
（6）The step of using embodiment 1（6）, difference：70 DEG C of reaction temperature, anode chamber are 0.5mol/L sulfuric acid.
Cathode chamber reaction product utilizes chromatographic mass spectrometry（GC-MS）It is analyzed, the product hexamethylene of benzene hydrogenation can be obtained, together
When there is also byproduct hydrogen gas, current efficiency shows that the content of hexamethylene and hydrogen is respectively 0.527wt.% up to 88.62%, Fig. 3
And 0.203wt.%, this illustrates that a kind of platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen to be practicable.
Embodiment 4
（1）The step of using embodiment 1（1）, difference：The surface density 0.25g/cm of high-area carbon2。
（2）The step of using embodiment 1（2）, difference：PtTi alloy catalyst thicknesses of layers 30nm, Pt carrying capacity
0.008mg/cm2。
（3）The step of using embodiment 1（3）, difference：Soak group be divided into 5%Nafion liquid ︰ 5%PTFE ︰ deionized waters=
8min in 40 DEG C of soaks of 1 ︰, 1 ︰ 1.
（4）The step of using embodiment 1（4）, difference：600 DEG C of firing temperature, firing time 40s.
（5）The step of using embodiment 1（5）, difference：Nafion membrane is immersed in the hydrogen peroxide of the dilute sulfuric acid containing 0.3mol/L
Middle 10h, 200 DEG C, hot pressing pressure 20MPa, hot pressing time 6min of hot pressing temperature.
（6）The step of using embodiment 1（6）, difference：75 DEG C of reaction temperature, anode chamber are 0.5mol/L sulfuric acid.
Fig. 1（Wherein a represents the XRD diagram of SPEME prepared by pure Pt, c embodiment 4）Middle display is manufactured in the present embodiment
The XRD diagram of SPEME is by contrast after PDF objects phase standard card, it is again seen that there is only PtTi, Pt in film layer5Ti3And Pt3Ti alloys
Phase；Fig. 2 is that analysis chart is swept in the faces EDS on SPEME Electrocatalytic Layers surface prepared by embodiment 4, it is found that Catalytic Layer component element is whole
It is evenly distributed, particle dispersion is good.
Cathode chamber reaction product utilizes chromatographic mass spectrometry（GC-MS）It is analyzed, the product hexamethylene of benzene hydrogenation can be obtained, together
When there is also byproduct hydrogen gas, current efficiency is in peak up to 91.82% in 5 embodiments, and Fig. 3 shows hexamethylene and hydrogen
The content of gas is respectively 1.040wt.% and 0.278wt.%；This illustrates that a kind of platinum base membrane electrode catalysis unsaturated compounds add hydrogen
Method is practicable.
Embodiment 5
（1）The step of using embodiment 1（1）, difference：The surface density 0.25g/cm of high-area carbon2。
（2）The step of using embodiment 1（2）, difference：PtTi alloy catalyst thicknesses of layers 50nm, Pt carrying capacity
0.013mg/cm2。
（3）The step of using embodiment 1（3）, difference：Soak group is divided into 5%Nafion liquid ︰ 25%PTFE ︰ deionized waters
8min in 50 DEG C of soaks of 1 ︰ 1 of=1 ︰.
（4）The step of using embodiment 1（4）, difference：600 DEG C of firing temperature, firing time 40s.
（5）The step of using embodiment 1（5）, difference：Nafion membrane is immersed in the hydrogen peroxide of the dilute sulfuric acid containing 0.3mol/L
Middle 18h, 150 DEG C, hot pressing pressure 15MPa, hot pressing time 8min of hot pressing temperature.
（6）The step of using embodiment 1（6）, difference：80 DEG C of reaction temperature, anode chamber are 0.5mol/L sulfuric acid.
Cathode chamber reaction product utilizes chromatographic mass spectrometry（GC-MS）It is analyzed, the product hexamethylene of benzene hydrogenation can be obtained, together
When there is also byproduct hydrogen gas, current efficiency shows that the content of hexamethylene and hydrogen is respectively 0.033wt.% up to 21.80%, Fig. 3
And 0.355wt.%, this illustrates that a kind of platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen to be practicable.
Claims (8)
1. a kind of platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen, it is characterised in that：Using heat pressing process, charcoal is carried
PtTi alloy catalysts, which are compressed on the single side of solid polymer dielectric film, is made platinum base membrane electrode, and platinum base membrane electrode is placed in
It is compressed between adjacent anode room and cathode chamber and by three, the charcoal being attached on platinum base membrane electrode carries PtTi alloy catalyst conducts
The working electrode of cathode chamber, the another side of platinum base membrane electrode are contacted with the carbonaceous electrode seal of anode chamber；By the electrolysis of anode chamber
The unsaturated compounds hydrogenation process of hydrogen production process and cathode chamber separates and independently carries out, respectively control anode chamber and cathode chamber
Response voltage, to regulate and control the reaction selectivity of electrolytic hydrogen production and unsaturated compounds hydrogenation process.
2. platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen according to claim 1, it is characterised in that：The charcoal
It is the Ti targets that Pt is inlayed by ion beam sputtering to carry PtTi alloy catalysts, is deposited on heating high-area carbon and obtains, gained charcoal
Carry 0.008~0.025mg/cm of catalysis layer thickness 30~100nm, Pt carrying capacity of Pt based alloy catalysts2。
3. platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen according to claim 1, it is characterised in that：Described the moon
The unsaturated compounds hydrogenation reaction temperature of pole room is 60~80 DEG C.
4. platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen according to claim 1, it is characterised in that：The charcoal
Matter electrode is plain weave propionitrile graphite fiber cloth, surface degree of graphitization >=99%, 0.20~0.35g/cm of surface density2。
5. platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen according to claim 2, it is characterised in that：The charcoal
Carrier is plain weave propionitrile graphite fiber cloth, surface degree of graphitization >=99%, 0.20~0.35g/cm of surface density2。
6. platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen according to claim 1, it is characterised in that：It is described solid
Body polymer dielectric film is perfluorinated sulfonate amberplex.
7. platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen according to claim 1, which is characterized in that hot pressing work
Skill detailed process is as follows：
（1）It prepares platinum base membrane electrode and handles soak, soak is 5~25% perfluorinated sulfonic acid salt ions by mass percent concentration
The ratio that liquid, the PTFE solution that mass percent concentration is 5~25% and deionized water are 1 ︰, 1 ︰ 1 by volume is exchanged to mix
It arrives；
（2）Charcoal load PtTi alloy catalysts are placed in step（1）In the soak of preparation, wherein 30~50 DEG C of soak temperature,
5~10min of soaking time, natural air drying after taking-up；
（3）By step（2）Gained charcoal carries PtTi alloy catalysts and is fired in Muffle furnace, firing condition：Firing temperature 500~
700 DEG C, 20~60s of firing time；
（4）Solid polymer dielectric film is immersed in 10 in the hydrogen peroxide of the dilute sulfuric acid containing 0.1~0.5mol/L~for 24 hours；
（5）By step（3）Gained charcoal carries PtTi alloy catalysts and step（4）Obtained solid polymer dielectric film carries out heat
Pressure, hot pressing condition are：125~225 DEG C, 10~20MPa of hot pressing pressure, 2~10min of hot pressing time of hot pressing temperature.
8. platinum base membrane electrode catalysis unsaturated compounds add the method for hydrogen according to claim 1, it is characterised in that：Anode chamber
Electrolyte inside is the dilute sulfuric acid or dilute nitric acid solution of 0.5~1.0mol/L, and unsaturated compounds are that the carbon of liquid is former in cathode chamber
Mononuclear aromatic, alkene or alkynes of the subnumber between 5~16.
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