CN1327958C - Method for preparing transition metal phosphide - Google Patents
Method for preparing transition metal phosphide Download PDFInfo
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- CN1327958C CN1327958C CNB2004100213729A CN200410021372A CN1327958C CN 1327958 C CN1327958 C CN 1327958C CN B2004100213729 A CNB2004100213729 A CN B2004100213729A CN 200410021372 A CN200410021372 A CN 200410021372A CN 1327958 C CN1327958 C CN 1327958C
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- phosphide
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract 7
- 150000001261 hydroxy acids Chemical class 0.000 claims abstract 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 229910052750 molybdenum Inorganic materials 0.000 claims description 19
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 238000002161 passivation Methods 0.000 claims description 11
- 235000015165 citric acid Nutrition 0.000 claims description 10
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000001630 malic acid Substances 0.000 claims description 9
- 235000011090 malic acid Nutrition 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 108010010803 Gelatin Proteins 0.000 abstract 3
- 229920000159 gelatin Polymers 0.000 abstract 3
- 239000008273 gelatin Substances 0.000 abstract 3
- 235000019322 gelatine Nutrition 0.000 abstract 3
- 235000011852 gelatine desserts Nutrition 0.000 abstract 3
- -1 phosphorus compound Chemical class 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 15
- 239000011733 molybdenum Substances 0.000 description 15
- 150000001735 carboxylic acids Chemical class 0.000 description 14
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 7
- 235000019838 diammonium phosphate Nutrition 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000005352 clarification Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000002050 diffraction method Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GNTCPDPNMAMZFW-UHFFFAOYSA-N ferrous phosphide Chemical compound [Fe]=P#[Fe] GNTCPDPNMAMZFW-UHFFFAOYSA-N 0.000 description 3
- 229940049920 malate Drugs 0.000 description 3
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZXQSZWCAMQTGFB-UHFFFAOYSA-N C(CC(O)(C(=O)O)CC(=O)O)(=O)O.C(C(O)C(O)C(=O)O)(=O)O.C(C(O)C)(=O)O.C(CC(O)(C(=O)O)CC(=O)O)(=O)O.C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.C(C(O)C(O)C(=O)O)(=O)O.C(C(O)C)(=O)O.C(CC(O)(C(=O)O)CC(=O)O)(=O)O.C(CC(O)(C(=O)O)CC(=O)O)(=O)O ZXQSZWCAMQTGFB-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 244000089742 Citrus aurantifolia Species 0.000 description 1
- HHXNHLJPIRSOPK-UHFFFAOYSA-N P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+] Chemical compound P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+] HHXNHLJPIRSOPK-UHFFFAOYSA-N 0.000 description 1
- MUXRPZMVVZJIHR-UHFFFAOYSA-N P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+] Chemical compound P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+].P(=O)(O)([O-])[O-].[NH4+].[NH4+] MUXRPZMVVZJIHR-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to preparation of a metal phosphorus compound, particularly to a method for preparing transition metal phosphide with a large specific surface area. The main operation processes comprise: phosphorus source substances of the stoichiometric ratio of target phosphide and soluble metal salt are dissolved in water, hydroxy acid is added, and the dosage molar ratio of the hydroxy acid to metal is 0.2 to 4.5; gelatin is obtained by a reaction system at the temperature of 70 to 90 DEG C, the gelatin is foamed and solidified at the temperature of 100 to 160 DEG C, and finally the gelatin is roasted at the temperature of 500 DEG C for more than 4 hours, and a target phosphide precursor is prepared; then program temperature raising reduction technique is used to deoxidize the prepared precursor, the prepared precursor is passivated at room temperature, and phosphide with a large specific surface area is obtained. The phosphide prepared by the method has high specific surface area which is more than ten times of that of original phosphide, and the phosphide has the advantages of convenient operation, low cost, no pollution, good repetitiveness, easy large scale preparation, etc.
Description
Invention field
The present invention relates to the preparation of metal phosphorizing compound, is a kind of preparation method of Large ratio surface transition metal phosphide specifically.
Background technology
Phosphide has the precious metal catalyst characteristic, is a kind of new catalytic material after transition metal carbide, nitride, successfully is applied to the deep hydrodesulfurizationof of gasoline, and the hydrodenitrogeneration reaction has alternative existing C o (Ni) MoS/Al
2O
3Commercial potentiality with catalyst.It is reported that such novel substance is with a wide range of applications in a lot of hydrogen-involved reactions, as hydrogenation reaction, ammonia synthesis, the reduction of NO and electrochemical reducting reaction etc.MoP wherein, WP, Ni
2P all is catalyst preferably.
The method for preparing phosphide that twentieth century three, the forties grow up is a kind of metallurgical method that is similar to.As metal molybdenum and hydrogen phosphide are formed (Izd.Nauka.Kiev, 1961,48) in high temperature (850 ℃) calcining, or with red phosphorus 1000 ℃ of reactions two days under vacuum condition, and at room temperature keep one day (Acta.Chem.Scand.Ser A, 1985,39,199).The phosphorus reaction of nickel carbonyl and fusion makes NiP and Ni
4The mixture of P (J.Chem.Soc., 1932,2543).Because this class methods toxicity is big, thereby is not widely used.
1998 (Chem.Lett., 1998,207) such as S.T.Oyama have invented a kind of phosphatic temperature programming method of directly reducing under nitrogen atmosphere.Earlier diammonium hydrogen phosphate and ammonium molybdate are total to molten aqueous solution evaporate to dryness, at 500 ℃ of roasting 6h, back utilization temperature programmed reduction technology, (650 ℃) make the phosphatization molybdenum (MoP) of pure phase under lower temperature.Adopt this method, prepared tungsten phosphide (WP), nickel phosphide (Ni in succession
2P), phosphatization cobalt (CoP, Co
2P), iron phosphide (Fe
2P) and phosphatization cobalt molybdenum (CoMoP), nickel phosphide molybdenum two yuan or ternary phosphide (J.Catal., 2002,202,187 such as (NiMoP); J.Catal., 2002,208,321).Generally speaking, the specific area of these phosphides is at 1-15m
2In/g the scope.
Generally speaking, as a class catalyst, have big specific area and just have more active sites.And generally less with two yuan of prior art for preparing or ternary phosphide specific area, make their further research and practical application is restricted.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of transition metal phosphide.
The objective of the invention is to be achieved through the following technical solutions:
This phosphide is to have AP (or B
2P) binary compound of structure, wherein A is Mo, W, Co, B is Ni, Co, Fe; Or the ternary compound with CDP structure, wherein C is Ni, Co, D is Mo; It is characterized in that: operate as follows:
1) preparation of target phosphide presoma:
Press AP (or B
2P) or the CDP molecular formula determine the target phosphide that will prepare, accurately take by weighing the phosphorus source material and the soluble metal salt of target phosphide stoichiometric proportion, soluble in water, add carboxylic acid, the mol ratio of carboxylic acid and metal consumption is 0.2-4.5, and reaction system is become gel under 70-90 ℃, at 110-160 ℃ of following foamed solidification, more than 400-600 ℃ of following roasting 5h of moving air atmosphere, promptly get target phosphide presoma at last.
2) preparation of target phosphide:
Employing temperature programmed reduction technology is with the presoma reduction that makes, and passivation at room temperature, promptly obtains the phosphide of Large ratio surface.
Described phosphorus source is a phosphoric acid, phosphorus pentoxide or ammonium phosphate salt; Soluble metal salt is the ammonium salt of Mo, W, the nitrate of Ni, Co, Fe; Carboxylic acid is a citric acid, lactic acid, malic acid or tartaric acid; Described temperature programmed reduction technology is: under hydrogen atmosphere, with grinding, compressing tablet, the 20-60 purpose predecessor particle that obtains that sieves rises to 300 ℃ at 0.5-1.5h, speed with 0.5-2 ℃/min rises to 500-750 ℃ again, keeping under this temperature more than the 1h, obtain the phosphide of fresh attitude, be cooled to room temperature then; Described passivating process is: use O
2/ N
2Be the gaseous mixture of 0.5-1.5% (V/V), with fresh attitude phosphide surface passivation 0.5-2.5h.
The present invention has target phosphide specific surface height, easy and simple to handle, low cost and other advantages.The present invention adopts the hydroxyl acid system to combine with temperature-programmed technique, has the feature that reacts at molecular scale, synthesis temperature is low, helps the preparation of many metal cations complex chemical compound, and is easy and simple to handle, cost is low, pollution-free, good reproducibility, be easy to mass preparation; Synthetic product chemical composition is even, the little and narrowly distributing of particle.The specific area height of target phosphide generally is more than ten times of compound with the art methods preparation.
The specific embodiment
Embodiment 1 is that carboxylic acid prepares phosphatization molybdenum (MoP) with the citric acid.
(molybdenum: ammonium molybdate 8.85g phosphorus=1: 1) mixes with diammonium hydrogen phosphate 6.65g and is dissolved in the 60ml water, to the solution clarification, obtains phosphorus-molybdenum aqueous solution to take by weighing target phosphide (MoP) stoichiometric proportion.The ratio of citric acid and metal foundation 0.4: 1 (mol ratio) is joined above-mentioned solution, and citric acid is dissolved to the solution clarification fully, obtains colloidal sol, obtain gel at 90 ℃ then, solidify foaming at 120 ℃, at last under moving air atmosphere, 500 ℃ of calcining 6h obtain presoma.With predecessor grinding, compressing tablet, sieve, obtain 24-32 purpose particle.Under nitrogen atmosphere, predecessor is raised to 300 ℃ in 0.5h from room temperature, the speed with 1 ℃/min is raised to 650 ℃ again, and keeps 2h under this temperature, after be cooled to room temperature.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before the sample ingress of air, uses O earlier
2/ N
2Passivating gas passivation 2h (1%V/V).Show the phosphide structure that has formed pure phase through XRD powder diffraction method mensuration.The ratio table of this material and long-pending be 30m
2/ g.
Embodiment 2 is the phosphatization molybdenum (MoP) of carboxylic acid preparation with citric acid, malic acid, lactic acid, tartaric acid, tungsten phosphide (WP).
The preparation method is with embodiment 1.Preparation condition and resultant target phosphide (MoP, specific area WP) is listed in table 1, and wherein tungsten salt adopts metatungstic acid:
The MoP of table 1 carboxylic acid method preparation, the specific area of WP
| Phosphide | The phosphorus source | Carboxylic acid | Acid/metal molar ratio | Specific area m 2/g |
| MoP MoP MoP MoP WP WP | Diammonium hydrogen phosphate diammonium hydrogen phosphate diammonium hydrogen phosphate diammonium hydrogen phosphate diammonium hydrogen phosphate diammonium hydrogen phosphate | The acid of citric acid citric acid lactic acid tartaric acid citrate malate | 2 4 1 2 4 2 | 130 40 19 34 23 38 |
Comparative example one
According to the method for Oyama, prepare phosphatization molybdenum (MoP), tungsten phosphide (WP) with the phosphatic method of direct reduction.
To contain molybdenum (or tungsten) and the aqueous solution evaporate to dryness of the equimolar ammonium molybdate of phosphorus (or ammonium metatungstate) with diammonium hydrogen phosphate, the white powder that obtains obtains predecessor at 500 ℃ of roasting 6h, the method that adopts temperature programmed reduction is with the predecessor reduction that makes, and passivation at room temperature.Specific area is 15m
2/ g (MoP), 10m
2/ g (WP).
Embodiment 3 is the nickel phosphide (Ni of carboxylic acid preparation with the citric acid
2P).
Take by weighing target phosphide (Ni
2P) (nickel: nickel nitrate 14.6g phosphorus=2: 1) mixes with diammonium hydrogen phosphate 3.3g and is dissolved in the 60ml water stoichiometric proportion, with the ratio (mol ratio of citrate certificate with metal, 2: 1) join above-mentioned solution, citric acid is dissolved to the solution clarification fully, obtains colloidal sol, obtains gel at 90 ℃ then, solidify foaming at 120 ℃, under moving air atmosphere, 480 ℃ of calcining 6h obtain presoma at last.With predecessor grinding, compressing tablet, sieve, obtain 40-60 purpose particle.Under nitrogen atmosphere, predecessor is raised to 300 ℃ from room temperature in 0.5h, the speed with 2 ℃/min is raised to 550 ℃ again, and keeps 2h under this temperature, is cooled to room temperature then.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before ingress of air, uses O earlier
2/ N
2Passivating gas passivation 0.5h (1%V/V).Phosphide is measured through the XRD powder diffraction method and is shown the nickel phosphide structure that has formed pure phase.The specific area of this material is 68m
2/ g.
Embodiment 4 is that carboxylic acid prepares nickel phosphide (Ni with citric acid, malic acid, lactic acid, tartaric acid
2P), phosphatization cobalt (Co
2P), iron phosphide (Fe
2P).
The preparation method is with example three, resultant phosphide (Ni
2P, Co
2P, Fe
2P) specific area is listed in table 2.Wherein, cobalt salt is a cobalt nitrate, and molysite is a ferric nitrate.
The Ni of table 2 carboxylic acid method preparation
2P, Co
2P, Fe
2The specific area of P
| Phosphide | The phosphorus source | Carboxylic acid | Acid/metal molar ratio | Specific area m 2/g |
| Ni 2P Ni 2P Co 2P Co 2P Fe 2P | Diammonium hydrogen phosphate diammonium hydrogen phosphate diammonium hydrogen phosphate diammonium hydrogen phosphate diammonium hydrogen phosphate | Citrated milk sour lime acid tartaric acid malic acid | 4 1 2 1 2 | 18 15 18 15 42 |
Comparative example two
According to the method for Oyama, prepare nickel phosphide (Ni with the phosphatic method of direct reduction
2P), phosphatization cobalt (Co
2P), iron phosphide (Fe
2P).
To contain nickel, cobalt, iron and phosphorus mol ratio are 2 nitrate (nickel nitrate, cobalt nitrate, ferric nitrate) water-soluble with diammonium hydrogen phosphate, after the precipitation drying that obtains, obtain predecessor at 500 ℃ of roasting 6h, the method that adopts temperature programmed reduction is with the predecessor reduction that makes, and passivation at room temperature.Specific area is respectively 1m
2/ g (Ni
2P), 3m
2/ g (Co
2P) and 2.7m
2/ g (Fe
2P).
Embodiment 5 is that carboxylic acid prepares nickel phosphide molybdenum (NiMoP) with the citric acid.
(nickel: molybdenum: nickel nitrate 14.6g phosphorus=1: 1: 1), ammonium molybdate 4.4g mix with diammonium hydrogen phosphate 3.3g and are dissolved in the 60ml water to take by weighing target phosphide (NiMoP) stoichiometric proportion.Citrate joins above-mentioned solution to clarification according to the ratio (mol ratio, 2: 1) with metal, obtains colloidal sol, obtains gel at 90 ℃ then, solidifies foaming at 150 ℃, and under moving air atmosphere, 550 ℃ of calcining 7h obtain presoma at last.With predecessor grinding, compressing tablet, sieve, obtain 20-30 purpose particle.Under nitrogen atmosphere, predecessor is raised to 300 ℃ from room temperature in 1.5h, be raised to 650 ℃ with the speed of 0.5 ℃/min, and under this temperature, keep 3h, be cooled to room temperature then.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before ingress of air, uses O earlier
2/ N
2Passivating gas passivation 0.5h (1%V/V).Phosphide is measured through the XRD powder diffraction method and is shown and formed the phosphide structure.The specific area of this material is 52m
2/ g
Embodiment 6 is the nickel phosphide molybdenum (NiMoP) of carboxylic acid preparation with the malic acid.
(nickel: molybdenum: nickel nitrate 14.6g phosphorus=1: 1: 1), ammonium molybdate 4.4g mix with phosphoric acid 2.45g and are dissolved in the 60ml water, and malate is added according to the ratio (mol ratio, 2: 1) with metal to take by weighing target phosphide (NiMoP) stoichiometric proportion.Malic acid is dissolved to clarification fully, obtains colloidal sol, obtains gel at 70 ℃ then, solidifies foaming at 120 ℃, and under moving air atmosphere, 550 ℃ of calcining 6h obtain presoma at last.With predecessor grinding, compressing tablet, sieve, obtain 24-32 purpose particle.Under nitrogen atmosphere, predecessor is raised to 300 ℃ from room temperature in 1h, the speed with 1 ℃/min is raised to 750 ℃ again, and keeps 2h under this temperature, is cooled to room temperature then.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before ingress of air, uses O earlier
2/ N
2Passivating gas passivation 0.5h (1%V/V).Phosphide is measured through the XRD powder diffraction method and is shown and formed the phosphide structure.The ratio table of this material and long-pending be 32m
2/ g.
Embodiment 7 is the phosphatization cobalt molybdenum (CoMoP) of carboxylic acid preparation with the malic acid.
Take by weighing target phosphide (CoMoP) stoichiometric proportion (cobalt: molybdenum: cobalt nitrate 7.2g phosphorus=1: 1: 1), ammonium molybdate 4.4g mixes with phosphorus pentoxide 1.76g and is dissolved in the 60ml water, malate is joined above-mentioned solution according to the ratio (mol ratio, 2: 1) with metal, and malic acid is dissolved to clarification fully, obtain colloidal sol, obtain gel at 70 ℃ then, solidify foaming at 120 ℃, at last under moving air atmosphere, 550 ℃ of calcining 6h obtain presoma.With predecessor grinding, compressing tablet, sieve, obtain 24-32 purpose particle.Under nitrogen atmosphere, in 1.5h inner room temperature rise to 300 ℃, the speed with 0.5 ℃/min is raised to 750 ℃ again, and keeps 2h under this temperature, is cooled to room temperature then with predecessor.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before ingress of air, uses O earlier
2/ N
2Passivating gas passivation 0.5h (1%V/V).Phosphide is measured through the XRD powder diffraction method and is shown and formed the phosphide structure.The specific area of this material is 32m
2/ g.
Comparative example three
According to the method for Oyama, prepare nickel phosphide molybdenum (NiMoP), phosphatization cobalt molybdenum (CoMoP) with the phosphatic method of direct reduction.
To contain nickel or cobalt, molybdenum and phosphorus mol ratio are 1: 1: 1 nitrate (nickel nitrate or cobalt nitrate), ammonium molybdate and diammonium hydrogen phosphate water-soluble, after the precipitation drying that obtains, obtain predecessor at 500 ℃ of roasting 6h, the method that adopts temperature programmed reduction is with the predecessor reduction that makes, and passivation at room temperature.Specific area is respectively 5m
2/ g (NiMoP), 8m
2/ g (CoMoP).
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| CN101912787B (en) * | 2010-07-29 | 2012-11-07 | 南昌大学 | Preparation of tungsten phosphide catalyst and application of tungsten phosphide in reforming methane and carbon dioxide |
| CN101898141B (en) * | 2010-07-29 | 2012-11-21 | 南昌大学 | Preparation of molybdenum phosphide catalyst and application in methane carbon dioxide reforming |
| CN103084192B (en) * | 2011-10-28 | 2015-05-27 | 中国科学院大连化学物理研究所 | Cobalt phosphide catalyst for preparing 3-pentanone and propanal from hydrogen, carbon monoxide and ethylene |
| CN102631941B (en) * | 2012-03-07 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing ethanol as well as preparation method and application of catalyst |
| CN102690171B (en) * | 2012-05-23 | 2014-07-09 | 中国科学院山西煤炭化学研究所 | Process for preparing ethanol from synthesis gas via methyl alcohol |
| CN103721368B (en) * | 2014-01-02 | 2016-08-03 | 东南大学 | A kind of method of trichloro ethylene hydrogenation-dechlorination |
| CN105384155A (en) * | 2015-12-25 | 2016-03-09 | 陕西科技大学 | Method for preparing cobalt-molybdenum phosphide nano material of hexagonal phase structure |
| CN105819418A (en) * | 2016-03-07 | 2016-08-03 | 常州大学 | Method for loading nanometer metal phosphide on porous carbon |
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