CN104743529B - Synthesis method of tungsten nitride with high catalytic performance - Google Patents
Synthesis method of tungsten nitride with high catalytic performance Download PDFInfo
- Publication number
- CN104743529B CN104743529B CN201510128005.7A CN201510128005A CN104743529B CN 104743529 B CN104743529 B CN 104743529B CN 201510128005 A CN201510128005 A CN 201510128005A CN 104743529 B CN104743529 B CN 104743529B
- Authority
- CN
- China
- Prior art keywords
- powder
- tungsten nitride
- tungsten
- raw material
- catalytic performance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a method for preparing nano tungsten nitride, belonging to the technical field of powder metallurgy preparation. The method comprises the following steps: synthesizing and preparing a tungsten oxide precursor through a solution method; and nitriding the tungsten oxide precursor in ammonia gas to obtain nanocrystalline tungsten nitride powder, wherein the particle size of the powder is 30-120nm. By virtue of the method disclosed by the invention, the problems that ultrafine nanocrystalline powder can be difficultly prepared by a traditional preparation method and the preparation time is long in the traditional preparation method can be solved. The tungsten nitride powder prepared by using the method disclosed by the invention is controllable in particle size, low in cost and high in utilization rate of raw material powder and has remarkable catalytic performance.
Description
Technical field
The invention belongs to powder metallurgy preparing technical field, specifically provides a kind of preparation side of nanocrystalline nitridation tungsten powder
Method.
Background technology
Refractory metals tungsten not only has outstanding performance, its compound oxidation tungsten, tungsten sulfide, nitridation when as simple substance
Tungsten also has quite varied application.Wherein tungsten nitride is a kind of new catalytic material, is had in hydrodesulfurization, hydrodenitrogeneration
The performance more superior than sulfide catalyst, the sulphur pollution brought because of industrial catalyst presulfurization not only can be avoided,
Also there is very high selectivity to the hydrogenolysis of heteroatomic ring, the hydrogen consumption during can substantially reducing, with larger industrial significance.This
A little conventionally used noble metals of process are used as catalyst.Therefore, the hope of noble metal is replaced to promote people's research using nitride
The synthesis and catalytic action of such catalyst.
Meanwhile, current research shows, when material reaches nano-scale, its optics, calorifics, electricity, magnetics, power
Learn or even chemical property also just correspondingly occurs very significant change, with the unexistent superior function of general material.Equally,
When tungsten nitride crystallite dimension reaches Nano grade, its catalytic performance is greatly enhanced.On the other hand as purple tungsten is in tungsten
Oxide in there is highest Lacking oxygen defect, surface activity is high, so being now widely used for preparing ultrafine tungsten powder, hard
Alloy WC etc..Therefore prepare nanocrystalline tungsten nitride and purple tungsten can be prepared by preferential, then obtain through subsequent nitridation.
At present, the preparation method of nanoscale tungsten nitride is mainly by sol-gal process, spray pyrolysis, rotary furnace calcination method
Etc. tungsten oxide presoma is prepared, nitrogenize in being then passed through ammonia again.Liu Bing sends out (University Of Nanchang's journal:Industry science version, 2006,28
(3):235-238.) with ammonium metatungstate as raw material, using mist projection granulating and then the method calcined, it is 0.64 μm to prepare mean diameter
WO3Precursor powder, then filter out the granule of 100nm or so and nitrogenize under the conditions of pure ammonia.Although the method can be prepared and is less than
The nitridation tungsten powder of 100nm, but powder rate processed is very low.Chen(Journal of Solid State Chemistry,2011,
184(2):Wolframic acid and octylame are mixed into 24h 455-462.), then ammonia is passed through after reaction in 48 hours, 650～800
Calcining under the conditions of DEG C prepares WN.The WN that the method is prepared is corynebacterium, and crystal grain is tiny, but preparation time is oversize, and is prepared
It is relatively costly.Accordingly, it would be desirable to develop a kind of new preparation method with high catalytic performance tungsten nitride.
The content of the invention
It is an object of the invention to provide a kind of new method for preparing nano silicon nitride tungsten, solution preparation time is oversize, and makes
Standby relatively costly problem.
The present invention directly adopts tungstates ammonium metatungstate for raw material, with short route, it is inexpensive the characteristics of, and prepare
Tungsten nitride size it is controllable, catalytic performance is excellent.
The process step of the invention is as follows：
1st, raw material：The raw material for being adopted has ammonium metatungstate, ammonium nitrate, adjuvant and ethylenediaminetetraacetic acid；
2nd, solution is prepared：Selected raw material is dissolved in into water, mix homogeneously according to certain proportioning；
3rd, prepared by presoma：The aqueous solution heating that step (2) is obtained, with the volatilization of aqueous solution, solution is dense in generation
Bubbling after contracting, releases substantial amounts of gas, and vigorous oxidation reduction reaction occurs in tens seconds, precursor powder is generated.
4th, the preparation of tungsten nitride：The predecessor that step (3) is obtained is forged in ammonia atmosphere at a temperature of 650 DEG C～900 DEG C
Burn, the time is 1～2 hour, obtains the nano silicon nitride tungsten powder of pure, porosity and size tunable.
Wherein in step (2), ammonium nitrate and the mol ratio in tungsten source are 12～36；The mol ratio in adjuvant and tungsten source is 5～
15；Ethylenediaminetetraacetic acid is 0.5～1 with tungsten source mol ratio.
It is an advantage of the invention that：
1st, tungstates ammonium metatungstate is directly adopted for raw material, short route, low cost, simple process, quick, suitable scale
Production；
2nd, can pass through to control the species and proportioning of raw material, control course of reaction prepared by presoma, control presoma
Particle diameter, pore structure；
3rd, a large amount of gases are produced in course of reaction of the present invention, is effectively controlled connecing for reactant and oxygen in course of reaction
Touch, to generating presoma purple tungsten powder important role；
4th, precursor powder reactivity is high, it is possible to decrease heat treatment temperature, and improves thermal treatment rate；
5th, can be by the nitriding temperature of ammonia, the granularity of tungsten nitride, pore structure obtained by controlling.So as to reach raising
The purpose of catalytic performance.
Description of the drawings
Fig. 1 is the XRD spectrum for nitrogenizing tungsten powder；
Fig. 2 is nitridation tungsten powder scanning electron microscopic observation photo (wherein a is x2, and 000, b is x9,000 times).
Specific embodiment
Embodiment 1
Ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, ammonium nitrate (NH4NO3) 0.24mol,
Carbamide (CO (NH2)2) 0.072mol, ethylenediaminetetraacetic acid (EDTA) 0.005mol.Material powder is dissolved in into appropriate deionized water
In stir to after being completely dissolved, the heating of 200 DEG C of constant temperature, solution react after being evaporated and obtain predecessor tungsten oxide powder.Will be front
Thing 650 DEG C of nitridations in ammonia are driven, insulation obtains the tungsten nitride of a diameter of 30～80nm for 2 hours.
Embodiment 2
Ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, ammonium nitrate (NH4NO3) 0.24mol,
Carbamide (CO (NH2)2) 0.072mol, ethylenediaminetetraacetic acid (EDTA) 0.005mol.Material powder is dissolved in into appropriate deionized water
In stir to after being completely dissolved, the heating of 200 DEG C of constant temperature, solution react after being evaporated and obtain predecessor tungsten oxide powder.Will be front
Thing 750 DEG C of nitridations in ammonia are driven, insulation obtains the tungsten nitride of a diameter of 30～100nm for 2 hours.
Embodiment 3
Ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, ammonium nitrate (NH4NO3) 0.3mol,
Citric acid (C6H8O7) 0.072mol, ethylenediaminetetraacetic acid (EDTA) 0.005mol.Material powder is dissolved in into appropriate deionized water
In stir to after being completely dissolved, the heating of 200 DEG C of constant temperature, solution react after being evaporated and obtain predecessor tungsten oxide foam.Will be front
Thing 900 DEG C of nitridations in ammonia are driven, insulation obtains the tungsten nitride of a diameter of 50～100nm for 1 hour.
Embodiment 4
Ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, ammonium nitrate (NH4NO3) 0.24mol,
Citric acid (C6H8O7) 0.1mol, ethylenediaminetetraacetic acid (EDTA) 0.005mol.Material powder is dissolved in appropriate deionized water
Stir to after being completely dissolved, 200 DEG C of heating of constant temperature, solution react after being evaporated and obtain predecessor tungsten oxide powder.By forerunner
Thing 650 DEG C of nitridations in ammonia, insulation obtain the tungsten nitride of a diameter of 50～80nm for 2 hours.
Embodiment 5
Ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, ammonium nitrate (NH4NO3) 0.24mol,
Glycine (C2H5NO2) 0.072mol, ethylenediaminetetraacetic acid (EDTA) 0.005mol.Material powder is dissolved in into appropriate deionization
Stir in water to after being completely dissolved, 200 DEG C of heating of constant temperature, solution react after being evaporated and obtain predecessor tungsten oxide powder.Will
Predecessor 750 DEG C of nitridations in ammonia, insulation obtain the tungsten nitride of a diameter of 50～100nm for 2 hours.
Claims (2)
1. a kind of synthetic method of high catalytic performance tungsten nitride, it is characterised in that with following steps：
(1) raw material：With ammonium metatungstate, ammonium nitrate, adjuvant and ethylenediaminetetraacetic acid as raw material；
(2) solution is prepared：Selected raw material is dissolved in into water, mix homogeneously according to certain proportioning；Ammonium nitrate is rubbed with ammonium metatungstate
You are than being 12～36；Adjuvant is 5～15 with the mol ratio of ammonium metatungstate；Ethylenediaminetetraacetic acid with ammonium metatungstate mol ratio is
0.5～1；
(3) prepared by presoma：The aqueous solution heating that step (2) is obtained, with the volatilization of aqueous solution, after it there is concentration in solution
Bubbling, releases substantial amounts of gas, and vigorous oxidation reduction reaction occurs in seconds, a kind of presoma powder body of porous is formed；
(4) preparation of tungsten nitride：The predecessor that step (3) is obtained is nitrogenized under ammonia atmosphere, obtains pure, porosity and grain
The controllable nano silicon nitride tungsten powder in footpath；Under ammonia atmosphere, nitriding temperature is 650 DEG C～900 DEG C, and the time of nitridation is 1～2h.
2. the synthetic method of a kind of high catalytic performance tungsten nitride according to claim 1, it is characterised in that in step (1)
Adjuvant is carbamide, glycine, malic acid, thiourea, citric acid at least one therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510128005.7A CN104743529B (en) | 2015-03-23 | 2015-03-23 | Synthesis method of tungsten nitride with high catalytic performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510128005.7A CN104743529B (en) | 2015-03-23 | 2015-03-23 | Synthesis method of tungsten nitride with high catalytic performance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104743529A CN104743529A (en) | 2015-07-01 |
| CN104743529B true CN104743529B (en) | 2017-04-26 |
Family
ID=53583903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510128005.7A Active CN104743529B (en) | 2015-03-23 | 2015-03-23 | Synthesis method of tungsten nitride with high catalytic performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104743529B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915212B (en) * | 2016-10-08 | 2020-12-22 | 中国科学院大连化学物理研究所 | Sheet-stacked caterpillar WN nano material and preparation method thereof |
| CN110228797B (en) * | 2018-07-25 | 2021-05-07 | 北京科技大学 | Method for preparing two-dimensional molybdenum nitride or tungsten nitride nanosheets at low cost |
| CN109675598B (en) * | 2019-03-04 | 2022-03-11 | 合肥工业大学 | Preparation method of nickel tungsten carbide nano composite powder used as electrocatalyst |
| CN109678157B (en) * | 2019-03-04 | 2022-05-10 | 合肥工业大学 | Preparation method of nano tungsten carbide with high catalytic activity |
| CN110368970B (en) * | 2019-08-26 | 2022-05-10 | 合肥工业大学 | Preparation method of activated carbon loaded tungsten carbide nano composite powder used as electrocatalyst |
| CN112938910B (en) * | 2021-04-16 | 2022-09-20 | 中国检验检疫科学研究院 | Synthetic method and application of lamellar tungsten nitride nano material |
| CN113755879B (en) * | 2021-09-06 | 2023-03-14 | 无锡隆基氢能科技有限公司 | Delta-phase tungsten nitride electrode material and preparation method and application thereof |
| CN117086321A (en) * | 2023-10-18 | 2023-11-21 | 国网甘肃省电力公司电力科学研究院 | Preparation method of superfine tungsten powder |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230251C (en) * | 2002-07-24 | 2005-12-07 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
| CN101016149A (en) * | 2006-09-29 | 2007-08-15 | 金堆城钼业集团有限公司 | Process for preparing nanometer nitride powder |
| CN101786610B (en) * | 2010-03-19 | 2012-01-04 | 郑州大学 | Preparation method of tungsten nitride nano powder |
| CN102019429A (en) * | 2011-01-04 | 2011-04-20 | 中国科学院上海硅酸盐研究所 | Preparation method of nano-tungsten powder |
-
2015
- 2015-03-23 CN CN201510128005.7A patent/CN104743529B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104743529A (en) | 2015-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104743529B (en) | Synthesis method of tungsten nitride with high catalytic performance | |
| Zhu et al. | Aqueous electrocatalytic N 2 reduction for ambient NH 3 synthesis: recent advances in catalyst development and performance improvement | |
| US10022709B2 (en) | Process for the production of non-sintered transition metal carbide and nitride nanoparticles | |
| Jiang et al. | Fabrication and photoactivities of spherical-shaped BiVO4 photocatalysts through solution combustion synthesis method | |
| Sahoo* et al. | Hydrothermal synthesis of single crystalline nano CeO2 and its structural, optical, and electronic characterization | |
| CN105366726B (en) | A kind of preparation method of the hollow sphere molybdenum bisuphide with stratiform shell structurre | |
| CN102574696A (en) | Composition comprising cerium oxide and zirconium oxide having a specific porosity, preparation method thereof and use of same in catalysis | |
| Yang et al. | Facile synthesis of cubical Co 3 O 4 supported Au nanocomposites with high activity for the reduction of 4-nitrophenol to 4-aminophenol | |
| CN113371682B (en) | Nano-micron spherical powder and preparation method and equipment thereof | |
| Du et al. | Synthesis of a hollow structured core–shell Au@ CeO 2–ZrO 2 nanocatalyst and its excellent catalytic performance | |
| CN102617139A (en) | Preparation method for strontium titanate lanthanum based powder material | |
| Liu et al. | Galvanic replacement synthesis of Ag x Au 1− x@ CeO 2 (0≤ x≤ 1) core@ shell nanospheres with greatly enhanced catalytic performance | |
| Yang et al. | Investigation of photocatalytic properties based on Fe and Ce Co-doped ZnO via hydrothermal method and first principles | |
| Zhu et al. | Room-temperature synthesis of cuprous oxide and its heterogeneous nanostructures for photocatalytic applications | |
| CN113413903A (en) | Preparation method and application of carbon-based transition metal monoatomic material | |
| CN104193397B (en) | Perovskite structure porous Ba 0.5sr 0.5co 0.8fe 0.2o 3-δmaterial and preparation method thereof | |
| CN103112883A (en) | Method for preparing superfine cuprous oxide powder | |
| JP5007667B2 (en) | Nickel oxide powder and method for producing the same | |
| Zhang et al. | Facile fabrication of VO2 (M) by thermolysis of ammonium metavanadate (NH4VO3) under sealed condition | |
| CN104843792B (en) | A kind of method of preparing the purple tungsten powder of nanometer needle-like | |
| CN107570724B (en) | The method that industrialization continuously prepares nano-tungsten powder | |
| CN107413361B (en) | Method for preparing non-noble metal tungsten carbide photocatalyst by hydrothermal method | |
| Liu et al. | Hierarchical hollow TiO 2@ CeO 2 nanocube heterostructures for photocatalytic detoxification of cyanide | |
| CN104419840B (en) | Anti-loaded nano porous gold/metal oxide composite and preparation method thereof | |
| CN102380408A (en) | Method for preparing nanometer sodium metatantalate photocatalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |