CN110227442A - Nano porous bismuth catalyst and preparation method thereof - Google Patents
Nano porous bismuth catalyst and preparation method thereof Download PDFInfo
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- CN110227442A CN110227442A CN201910601453.2A CN201910601453A CN110227442A CN 110227442 A CN110227442 A CN 110227442A CN 201910601453 A CN201910601453 A CN 201910601453A CN 110227442 A CN110227442 A CN 110227442A
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- bismuth
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 84
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 39
- 239000000956 alloy Substances 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 29
- SKKNACBBJGLYJD-UHFFFAOYSA-N bismuth magnesium Chemical compound [Mg].[Bi] SKKNACBBJGLYJD-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229920000557 Nafion® Polymers 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000006229 carbon black Substances 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001238 wet grinding Methods 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007783 nanoporous material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 3
- 238000003723 Smelting Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 12
- 239000008103 glucose Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229940049676 bismuth hydroxide Drugs 0.000 description 4
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012935 Averaging Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910017625 MgSiO Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nano porous bismuth catalyst and a preparation method thereof, belonging to the field of nano porous materials. The preparation method of the nano porous bismuth catalyst comprises the following steps: smelting to prepare a magnesium-bismuth precursor alloy, and carrying out dealloying treatment on the magnesium-bismuth precursor alloy by adopting weak acid to obtain nano porous bismuth; grinding the nano porous bismuth into powder, mixing the powder with Nafion solution, deionized water and carbon black carrier uniformly by ultrasonic waves to obtain catalyst suspension, dripping the catalyst suspension on a conductive substrate, and airing at room temperature to obtain the catalyst film electrode. The nano porous bismuth catalyst prepared by the method has the advantages of low cost, high catalytic efficiency, no pollution to the environment and the like. The aperture of the nano porous bismuth can be regulated and controlled by controlling parameters such as the component content of the magnesium bismuth precursor alloy, the dealloying solution and the concentration thereof, and the specific surface area is changed, so that the catalytic performance is further improved. Compared with commercial electrode catalyst materials, the nano-porous bismuth catalyst provided by the invention can obviously improve the catalytic efficiency.
Description
Technical field
The invention belongs to nano-porous materials fields, and in particular to a kind of nanoporous bismuth catalyst and preparation method thereof.
Background technique
Nano porous metal material is made of the hole and metal ligament of nanoscale, there is three-dimensional doubly-linked to lead to nanometer more
The porous metal material of pore network shape structure is a kind of new function material being concerned in recent years.It is a kind of metal material
Material, physics, chemistry and mechanical property with metal.It or a kind of nano material have small specific to nano material
The characteristics such as dimensional effect, skin effect and quantum size effect, thus also with unique in terms of magnetics, optics, electricity
Performance.Due to its unique structure, keep its large specific surface area, density low and save raw material, be expected to be applied to catalysis, sensing,
The fields such as filtering and plasma resonance.
Nowadays, application of the nano porous metal as catalyst in fuel cell is pursued, and people are constantly more to nanometer
It the preparation of hole noble metal catalyst and realizes that its excellent electro catalytic activity and stability are studied, chemically erodes to electrification
Corrosion is learned, single step corrosion is eroded to from multistep, reduces catalyst cost, this has great meaning for energy saving and environmental protection
Justice.Glucose fuel cell can be divided into direct fuel cell and two kinds of implantable battery according to its existence form.And glucose
Common precious metals pt, Pd catalyst have the defects that at high cost, easy CO poisoning, Chen (Chen J., Zhao in fuel cell
C.X., Zhi M.M., et al., Alkaline direct oxidation glucose fuel cellsystem using
Silver/nickel foams as electrodes [J] .Electrochimica Acta, 2012,66 (13): 133-
138.) it finds that the insertion of Bi atom makes Pd/Bi catalyst have preferable resisting CO poison ability, is considered a kind of substitution
Pt appropriate catalyst, but Pd is expensive, does not have apparent advantage still.So the present invention inquired into it is a kind of have it is low at
Originally, the nanoporous bismuth catalyst of high catalytic performance.
Summary of the invention
The present invention aiming at the shortcomings in the prior art, provides a kind of nanoporous bismuth catalyst and preparation method thereof, should
Catalyst has many advantages, such as to prepare simple, low cost, high catalytic performance.
Nanoporous bismuth catalyst, it is made of nanoporous bismuth, Nafion solution, water and carbon black；The nanometer
Porous bismuth is three-dimensional co-continuous nano-porous structure, aperture 30-100nm, hole wall 20-50nm, porosity 30-90%.
The preparation method of the nanoporous bismuth catalyst, comprising the following steps:
(1) magnesium the preparation of magnesium bismuth presoma alloy: is prepared by well formula crucible electrical resistance furnace melting or vacuum induction melting
Then magnesium bismuth alloy is machined to sheet using cutting by bismuth alloy, and use alcohol wet-milling to a thickness of 80-100 μ on sand paper
M obtains magnesium bismuth presoma alloy；
(2) the de- alloy of chemistry: step (1) the magnesium bismuth presoma alloy sheet is put into weak acid solution and carries out magnesium
Dissolution, until bubble-free is emerged again, de- alloy reaction terminates, and obtains nanoporous bismuth；
(3) it the preparation of nanoporous bismuth catalyst: by nanoporous bismuth described in step (2), is washed with deionized, puts
Enter oven drying；Nanoporous bismuth mortar grind into fine powder after drying；By powdered nanoporous bismuth, Nafion solution, go
Ionized water and carbon black-supported ultrasonic mixing are formed uniformly catalyst suspension, obtain nanoporous bismuth catalyst；
(4) prepared by electrode: nanoporous bismuth catalyst suspension being added dropwise on conducting base, room temperature is urged after drying
Agent membrane electrode.
The atomic ratio of bismuth and magnesium is 1 in magnesium bismuth alloy in the step (1): (1.8-99).
Weak acid solution is citric acid, hydrofluoric acid, malic acid, gluconic acid, formic acid, lactic acid, benzene first in the step (2)
One of acid, acrylic acid, acetic acid, propionic acid, stearic acid, carbon acid solution.
Weak acid solution concentration is 1-3wt.% in the step (2), and solution temperature is room temperature, and dissolution time is that 6-18 is small
When.
Drying temperature is 150 DEG C in the step (3), 1-2 hours dry.
By the porous bismuth of 1mg powder nanometer, the 5%Nafion solution of 2 μ l, 1ml deionized water and 2mg in the step (3)
Carbon black-supported mixing, and ultrasonic wave separating apparatus ultrasonic disperse 30-60min is used, 30 DEG C of ultrasonic temperature <.
Nanoporous bismuth catalyst prepared by the present invention has the advantages that
1, preparation method of the present invention is environment friendly and pollution-free, and magnesium elements are widely distributed in nature, and the fusing point of magnesium is low, current potential compared with
It is negative, it easily dissolves, to human body and environmentally friendly.
2, the ore reserve of bismuth are big, cheap market price, therefore compared with other methods prepare porous bismuth, magnesium bismuth alloy takes off alloy
The cost for preparing porous bismuth can be relatively low.
3, the nanoporous bismuth aperture prepared of the present invention is adjustable, by control magnesium bismuth presoma alloy component content,
The de- parameters such as alloy solution and its concentration, it may be convenient to regulate and control the aperture size of nanoporous bismuth, changes specific surface area, thus
Further increase catalytic performance.
4, the peak current density of nanoporous bismuth catalyst of the invention is up to 5.7mA/cm2, compared to commercial Pt/C
The peak current density 3mA/cm of catalyst2It significantly improves, electrochemical surface area (ECSA) is the 1.32 of business Pt/C catalyst
Times, synthesis is compared, and the catalytic performance of nanoporous bismuth catalyst is better than the catalytic performance of business Pt/C catalyst.
Detailed description of the invention
Fig. 1 is that the SEM of 1 gained nanoporous bismuth of embodiment schemes
Fig. 2 is that the SEM of 2 gained nanoporous bismuth of embodiment schemes
Fig. 3 is that the SEM of 3 gained nanoporous bismuth of embodiment schemes
Fig. 4 is application examples nanoporous bismuth catalyst following in the glucose of 50mmol/L and the NaOH solution of 0.1mol/L
Ring volt-ampere curve
Specific embodiment
In order to facilitate the understanding of those skilled in the art, be described in further detail by the following examples and attached drawing, it is public
It opens the purpose of the present invention and is intended to protect all changes and improvements in the scope of the invention, the present invention does not limit to following implementation
Example.
Embodiment 1
(1) preparation of magnesium bismuth presoma alloy:
A material prepares: successively weighing pure Mg, pure Bi by atomic percent Bi: Mg=1.12: 98.88, nominal takes 100g.
Configure coating, configuration coverture.The wherein MgSiO that paint ingredient is 35%3, 5% Na2SiO3Water with 60%, configures temperature
It is 60 DEG C；The ingredient of coverture be 7% KCl, 7% NaCl, 3% CaF2, 10% BaCl2, 6% CaCl2, 34%
MgCO3, remaining all MgCl2。
The preparation of b tool: coating is coated uniformly on graphite crucible, stirring rod, spoon of skimming, on metal die, is then put
Enter in baking oven, is dried 1 hour at 150 DEG C.
The melting of c alloy: casting mold is placed on after being preheated to 250 DEG C in the same resistance furnace and is taken out, and mold is put
It is placed in a smooth place for future use.With resistance stove heating crucible to after 400 DEG C, MAG block and coverture are sequentially added, then
720 DEG C, soaking time 20min are warming up to, it is molten with one layer of magnesium melt surface in Slag Tool removal crucible after all fusings
Pure Bi particle is added in slag, places into the pure MAG block of a fritter, under the gravity of its pure MAG block, Bi particle can be made sufficiently to incorporate
Magnesium melt homogenizes alloying component, then adds coverture again, after furnace temperature rises to 720 DEG C, keeps the temperature 15min.Take magnesium off
After melt contacts the slag generated with air, crucible is taken out, is poured into the mold for being preheating to 200 DEG C or so in advance.Wait cast
It is opened after the complete cooled and solidified of part, takes out casting.SF6 protective gas is passed through in melting overall process always.
The processing of d alloy: being machined to sheet using cutting for magnesium bismuth alloy, then with alcohol wet-milling to 80- on sand paper
100 μm, obtain magnesium bismuth presoma alloy.
(2) step (1) the magnesium bismuth presoma alloy sheet the de- alloy of chemistry: is put into the acetic acid that concentration is 1wt.%
The dissolution of magnesium is carried out in solution, dissolution time is 16 hours at room temperature, until bubble-free is emerged again, de- alloy reaction terminates.
(3) it the preparation of nanoporous bismuth catalyst: by nanoporous bismuth described in step (2), is washed with deionized, puts
Enter oven drying, 150 DEG C of drying temperature, drying time 1 hour；Nanoporous bismuth mortar grind into fine powder after drying；By 1mg
Powdered nanoporous bismuth, the 5%Nafion solution of 2 μ l, 1ml deionized water and 2mg carbon black-supported use ultrasonic wave separating apparatus
30 DEG C of ultrasonic disperse 30-60min, ultrasonic temperature <, obtain nanoporous bismuth catalyst,
Fig. 1 is the SEM microscopic appearance figure that magnesium bismuth alloy takes off the nanoporous bismuth formed after alloy, it can be seen from the figure that
Alloy obtained by the present embodiment has three-dimensional co-continuous porous structure, and the aperture averaging of nanoporous bismuth is 20nm, the average thickness of hole wall
Degree is 30nm, porosity 80%.
Embodiment 2
(1) preparation of magnesium bismuth presoma alloy:
A material prepares: successively weighing pure Mg, pure Bi by atomic percent Bi: Mg=16: 84, nominal takes 150g.Configuration applies
Material, configuration coverture.The wherein MgSiO that paint ingredient is 35%3, 5% Na2SiO3With 60% water, configuration temperature is 60
℃；The ingredient of coverture be 7% KCl, 7% NaCl, 3% CaF2, 10% BaCl2, 6% CaCl2, 34%
MgCO3, remaining all MgCl2。
The preparation of b tool: coating is coated uniformly on graphite crucible, stirring rod, spoon of skimming, on metal die, is then put
Enter in baking oven, is dried 1 hour at 150 DEG C.
The melting of c alloy: casting mold is placed on after being preheated to 250 DEG C in the same resistance furnace and is taken out, and mold is put
It is placed in a smooth place for future use.With resistance stove heating crucible to after 400 DEG C, MAG block and coverture are sequentially added, then
720 DEG C, soaking time 20min are warming up to, it is molten with one layer of magnesium melt surface in Slag Tool removal crucible after all fusings
Pure Bi particle is added in slag, places into the pure MAG block of a fritter, under the gravity of its pure MAG block, Bi particle can be made sufficiently to incorporate
Magnesium melt homogenizes alloying component, then adds coverture again, after furnace temperature rises to 720 DEG C, keeps the temperature 15min.Take magnesium off
After molten surface contacts the slag generated with air, crucible is taken out, is poured into the mold for being preheating to 200 DEG C or so in advance.
It is opened after the complete cooled and solidified of casting, takes out casting.SF6 protective gas is passed through in melting overall process always.
The processing of d alloy: being machined to sheet using cutting for magnesium bismuth alloy, then with alcohol wet-milling to 80- on sand paper
100 μm, obtain magnesium bismuth presoma alloy.
(2) step (1) the magnesium bismuth presoma alloy sheet the de- alloy of chemistry: is put into the acetic acid that concentration is 1wt.%
The dissolution of magnesium is carried out in solution, dissolution time is 10 hours at room temperature, until bubble-free is emerged again, de- alloy reaction terminates.
(3) it the preparation of nanoporous bismuth catalyst: by nanoporous bismuth described in step (2), is washed with deionized, puts
Enter oven drying, 150 DEG C of drying temperature, drying time 1 hour；Nanoporous bismuth mortar grind into fine powder after drying；By 1mg
Powdered nanoporous bismuth, the 5%Nafion solution of 2 μ l, 1ml deionized water and 2mg carbon black-supported use ultrasonic wave separating apparatus
30 DEG C of ultrasonic disperse 30-60min, ultrasonic temperature <, obtain nanoporous bismuth catalyst.
Fig. 2 is the SEM microscopic appearance figure that magnesium bismuth alloy takes off the nanoporous bismuth formed after alloy, it can be seen from the figure that
Alloy obtained by the present embodiment has three-dimensional co-continuous porous structure, and the aperture averaging of nanoporous bismuth is 50nm, the average thickness of hole wall
Degree is 40nm, porosity 70%.
Embodiment 3
In addition to successively weighing pure Mg by atomic percent Bi: Mg=35: 65, pure Bi nominal takes 250g, other processes and reality
Apply that example 2 is identical, the aperture averaging of gained nanoporous bismuth is 70nm, and hole wall average thickness is 30nm, porosity 60%.
Embodiment 4
Except chemistry takes off in alloy component, finished presoma alloy sheet is put into the oxalic acid solution of 1wt.% and is carried out
The dissolution of magnesium, other processes are identical as with embodiment 3.
Embodiment 5
Except chemistry takes off in alloy component, finished presoma alloy sheet is put into the oxalic acid solution of 3wt.% and is carried out
The dissolution of magnesium, other processes are identical as with embodiment 3.
Embodiment 6
Except chemistry takes off in alloy component, finished presoma alloy sheet is put into the carbon acid solution of 3wt.% and is carried out
The dissolution of magnesium, other processes are identical as with embodiment 3.
Application examples
In order to test the electrochemical catalysis performance of catalyst prepared by the present invention, using nanoporous bismuth catalyst as grape
Sugared fuel battery anode catalyst carries out catalysis glucose experiment, nanometer prepared by embodiment 1, embodiment 2 and embodiment 3
Steps are as follows for porous bismuth catalyst performance test:
(1) Al by glass-carbon electrode on chamois leather with 0.05 μm2O3After suspension wet-milling is clean, rinsed with deionized water dry
Only, ultrasonic 30s.Electrode is taken out, can be used after natural drying.6 μ L nanoporous bismuth catalysts are taken to be added dropwise on glass-carbon electrode,
Room temperature obtains working electrode after drying.
(2) the cyclic voltammetry test of catalyst is carried out using three-electrode system, auxiliary electrode is graphite electrode, work electricity
The glass-carbon electrode of nanoporous bismuth catalyst is extremely added, reference electrode is saturation mercuric oxide electrode.Electrolyte is 0.1mol/L
NaOH+50mmol/L C6H12O6Solution, sweep speed 50mV/s, scanning range are -0.8-0.4V.
Experiment gained nanoporous bismuth catalyst cyclic voltammetry curve as shown in figure 4, lower current potential oxidation peak
It is the surface that glucose is adsorbed onto porous bismuth, and the bismuth in nanoporous bismuth generates hydrogen-oxygen in conjunction with the hydroxide ion in solution
Change bismuth, absorption bismuth hydroxide and absorption glucose response make glucose lose proton generation intermediate, therefore current density starts
Increase.With the progress of reaction, the intermediate of generation occupies the active site on nanoporous bismuth surface, at this time oxidation current
Density starts to reduce.With continuing growing for current potential, the bismuth hydroxide for reacting generation is continuously increased, and bismuth hydroxide is to glucose
Intermediate product have good catalytic effect, so glucose intermediate product can and bismuth hydroxide reaction take place, oxidation
The current density at peak starts to increase again.The reaction process of nanoporous bismuth catalytic oxidation of glucose in alkaline solution are as follows:
Bi+OH-→Bi-(OH)ads(1-λ)+λe-
C6H12O6+Bi-(OH)ads→Bi-(C6H11O6)ads+H2O
Bi-(C6H11O6)ads→C6H10O6+Bi+e-+H+
It is to be shown in Table 1 using result:
Table 1
Embodiment 1, embodiment 2 and embodiment 3 are respectively in the NaOH solution of the glucose of 50mmol/L and 0.1mol/L
Peak current density be respectively 2.5mA/cm2、5.2mA/cm2And 5.7mA/cm2, the electrochemical surface area of three kinds of catalyst
(ECSA) value can be obtained by aoxidizing calculated by peak area in figure, and formula is ECSA=Q/ (LS), and Q is bismuth oxidation peak in CV curve
Area；S is the quality of the catalyst loaded on electrode；L is 420 μ C/cm of constant2；The wherein electrochemical surface area of embodiment 3
It is the ECSA (8.21m of business Pt/C catalyst2·g-1) 1.32 times, illustrate nanoporous bismuth catalyst have good catalysis
Performance.
Claims (7)
1. a kind of nanoporous bismuth catalyst, it is characterised in that: it is by nanoporous bismuth, Nafion solution, water and carbon black group
At；The nanoporous bismuth is three-dimensional co-continuous nano-porous structure, aperture 30-100nm, hole wall 20-50nm, hole
Rate is 30-90%.
2. the preparation method of nanoporous bismuth catalyst according to claim 1, it is characterised in that: the method includes with
Lower step:
(1) preparation of magnesium bismuth presoma alloy: magnesium bismuth is prepared by well formula crucible electrical resistance furnace melting or vacuum induction melting and is closed
Then magnesium bismuth alloy is machined to sheet using cutting by gold, and use alcohol wet-milling to a thickness of 80-100 μm on sand paper, is obtained
To magnesium bismuth presoma alloy；
(2) the de- alloy of chemistry: step (1) the magnesium bismuth presoma alloy sheet is put into weak acid solution and carries out the molten of magnesium
Solution, until bubble-free is emerged again, de- alloy reaction terminates, and obtains nanoporous bismuth；
(3) preparation of nanoporous bismuth catalyst: nanoporous bismuth described in step (2) is washed with deionized, is put into baking
Case is dry；Nanoporous bismuth mortar grind into fine powder after drying；By powdered nanoporous bismuth, Nafion solution, deionization
Water and carbon black-supported ultrasonic mixing are formed uniformly catalyst suspension, obtain nanoporous bismuth catalyst；
(4) prepared by electrode: nanoporous bismuth catalyst being added dropwise on conducting base, room temperature obtains catalyst film electricity after drying
Pole.
3. the preparation method of nanoporous bismuth catalyst according to claim 2, it is characterised in that: step (1) described magnesium
The atomic ratio of bismuth and magnesium is 1 in bismuth alloy: (1.8-99).
4. the preparation method of nanoporous bismuth catalyst according to claim 2, it is characterised in that: weak acid in step (2)
Solution concentration is 1-3wt.%, and dissolution time is 6-18 hours at room temperature.
5. the preparation method of nanoporous bismuth catalyst according to claim 2, it is characterised in that: dry in step (3)
Temperature is 150 DEG C, 1-2 hours dry.
6. the preparation method of nanoporous bismuth catalyst according to claim 2, it is characterised in that: by 1mg in step (3)
The porous bismuth of powder nanometer, the 5%Nafion solution of 2 μ l, 1ml deionized water and the mixing of 2mg carbon black-supported, and use ultrasonic wavelength-division
Scattered instrument ultrasonic disperse 30-60min, 30 DEG C of ultrasonic temperature <.
7. the preparation method of nanoporous bismuth catalyst according to claim 4, it is characterised in that: step (2) is described weak
Acid solution is citric acid, hydrofluoric acid, malic acid, gluconic acid, formic acid, lactic acid, benzoic acid, acrylic acid, acetic acid, propionic acid, tristearin
One of acid, carbon acid solution.
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| CN114551849A (en) * | 2022-01-12 | 2022-05-27 | 苏州新中能源科技有限公司 | Porous bismuth-carbon fiber composite lithium ion negative electrode material and preparation method thereof |
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