CN104743529A - Synthesis method of tungsten nitride with high catalytic performance - Google Patents

Synthesis method of tungsten nitride with high catalytic performance Download PDF

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CN104743529A
CN104743529A CN201510128005.7A CN201510128005A CN104743529A CN 104743529 A CN104743529 A CN 104743529A CN 201510128005 A CN201510128005 A CN 201510128005A CN 104743529 A CN104743529 A CN 104743529A
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tungsten nitride
powder
preparation
catalytic performance
high catalytic
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CN104743529B (en
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秦明礼
陈鹏起
陈铮
刘烨
鲁慧峰
王炫力
吴昊阳
贾宝瑞
曲选辉
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University of Science and Technology Beijing USTB
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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

A kind of synthetic method of high catalytic performance tungsten nitride
Technical field
The invention belongs to powder metallurgy preparing technical field, specifically provide a kind of preparation method of nanocrystalline tungsten nitride powder.
Background technology
Refractory metals tungsten is not only as there being outstanding performance during simple substance, and its compound oxidation tungsten, tungsten sulfide, tungsten nitride also all have to be applied very widely.Wherein tungsten nitride is a kind of new catalytic material, the performance more superior than sulfide catalyst is had in hydrogenating desulfurization, hydrodenitrification, not only can avoid the sulphur pollution brought because of commercial catalysts prevulcanized, also there is very high selectivity to the hydrogenolysis of heteroatomic ring, can hydrogen consumption in reduction process greatly, there is larger industrial significance.These processes use precious metal as catalyzer traditionally.Therefore, nitride is used to replace the hope of precious metal promotion people to study synthesis and the katalysis of this type of catalyzer.
Meanwhile, current research shows, when material reaches nano-scale time, its optics, calorifics, electricity, magnetics, mechanics and even chemical property also just correspondingly occur to change very significantly, have the unexistent high-performance of general material.Equally, time tungsten nitride grain-size reaches Nano grade, its catalytic performance also improves a lot.On the other hand because purple tungsten has the highest Lacking oxygen defect in the oxide compound of tungsten, surfactivity is high, so be widely used at present preparing ultrafine tungsten powder, Wimet WC etc.Therefore prepare nanocrystalline tungsten nitride by preferentially preparing purple tungsten, then obtain through subsequent nitridation.
At present, the preparation method of nano level tungsten nitride mainly prepares Tungsten oxide 99.999 presoma by sol-gel method, spray pyrolysis, rotary kiln calcination method etc., and then passes into nitrogenize in ammonia.Liu Bing sends out, and (University Of Nanchang's journal: industry science version, 2006,28 (3): 235-238.) are raw material with ammonium metawolframate, adopt the method that then mist projection granulating is calcined, and preparation median size is 0.64 μm of WO 3precursor powder, then the particle nitrogenize under pure ammonia condition filtering out about 100nm.Although the method can prepare the tungsten nitride powder being less than 100nm, powder process rate is very low.Chen (Journal of Solid State Chemistry, 2011,184 (2): 455-462.) by wolframic acid and octylame mix and blend 24h, then passes into ammonia after reaction in 48 hours, calcining preparation WN under 650 ~ 800 DEG C of conditions.The WN that the method is prepared is corynebacterium, and crystal grain is tiny, but preparation time is oversize, and preparation cost is higher.Therefore, exploitation newly a kind of preparation method with high catalytic performance tungsten nitride is needed.
Summary of the invention
The object of the present invention is to provide a kind of novel method preparing nano silicon nitride tungsten, solve preparation time oversize, and the problem that preparation cost is higher.
The present invention directly adopts tungstate ammonium metawolframate to be raw material, has the feature of short route, low cost, and the size of the tungsten nitride prepared is controlled, and catalytic performance is excellent.
Processing step of the present invention is as follows:
1, raw material: the raw material adopted has ammonium metawolframate, ammonium nitrate, auxiliary and ethylenediamine tetraacetic acid (EDTA);
2, solution preparation: selected raw material is water-soluble according to certain proportioning, mixes;
3, precursor power: aqueous solution heating step (2) obtained, along with the volatilization of the aqueous solution, solution is bubbling after generation is concentrated, releases a large amount of gas, vigorous oxidation reduction reaction occurs within tens seconds, generates precursor powder.
4, the preparation of tungsten nitride: precursor step (3) obtained is at 650 DEG C ~ 900 DEG C temperature, and calcine in ammonia atmosphere, the time is 1 ~ 2 hour, obtains the nano silicon nitride tungsten powder of pure, porosity and size tunable.
Wherein in step (2), the mol ratio in ammonium nitrate and tungsten source is 12 ~ 36; The mol ratio in auxiliary and tungsten source is 5 ~ 15; Ethylenediamine tetraacetic acid (EDTA) and tungsten source mol ratio are 0.5 ~ 1.
Advantage of the present invention is:
1, directly tungstate ammonium metawolframate is adopted to be raw material, short route, low cost, simple process, quick, be applicable to large-scale production;
2, by controlling kind and the proportioning of raw material, the reaction process of precursor power can be controlled, controls particle diameter, the pore texture of presoma;
3, produce a large amount of gas in reaction process of the present invention, effectively control the contact of reactant and oxygen in reaction process, to the purple tungsten powder important role of generation presoma;
4, precursor powder reactive behavior is high, can reduce thermal treatment temp, and improve thermal treatment rate;
5, can by the nitriding temperature of ammonia, control obtain granularity, the pore texture of tungsten nitride.Thus reach the object improving catalytic performance.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of tungsten nitride powder;
Fig. 2 is tungsten nitride powder scanning electron microscopic observation photo (wherein a is x2,000, b is x9,000 times).
Embodiment
Embodiment 1
Ammonium metawolframate ((NH is taken according to stoichiometry 4) 6h 2w 12o 40) 0.01mol, ammonium nitrate (NH 4nO 3) 0.24mol, urea (CO (NH 2) 2) 0.072mol, ethylenediamine tetraacetic acid (EDTA) (EDTA) 0.005mol.Raw material powder is dissolved in appropriate deionized water for stirring to completely dissolve after, constant temperature 200 DEG C heating, reacts after solution evaporate to dryness and obtains precursor tungsten oxide powder.By precursor 650 DEG C of nitrogenize in ammonia, be incubated and within 2 hours, obtain the tungsten nitride that diameter is 30 ~ 80nm.
Embodiment 2
Ammonium metawolframate ((NH is taken according to stoichiometry 4) 6h 2w 12o 40) 0.01mol, ammonium nitrate (NH 4nO 3) 0.24mol, urea (CO (NH 2) 2) 0.072mol, ethylenediamine tetraacetic acid (EDTA) (EDTA) 0.005mol.Raw material powder is dissolved in appropriate deionized water for stirring to completely dissolve after, constant temperature 200 DEG C heating, reacts after solution evaporate to dryness and obtains precursor tungsten oxide powder.By precursor 750 DEG C of nitrogenize in ammonia, be incubated and within 2 hours, obtain the tungsten nitride that diameter is 30 ~ 100nm.
Embodiment 3
Ammonium metawolframate ((NH is taken according to stoichiometry 4) 6h 2w 12o 40) 0.01mol, ammonium nitrate (NH 4nO 3) 0.3mol, citric acid (C 6h 8o 7) 0.072mol, ethylenediamine tetraacetic acid (EDTA) (EDTA) 0.005mol.Raw material powder is dissolved in appropriate deionized water for stirring to completely dissolve after, constant temperature 200 DEG C heating, reacts after solution evaporate to dryness and obtains precursor Tungsten oxide 99.999 foam.By precursor 900 DEG C of nitrogenize in ammonia, be incubated and within 1 hour, obtain the tungsten nitride that diameter is 50 ~ 100nm.
Embodiment 4
Ammonium metawolframate ((NH is taken according to stoichiometry 4) 6h 2w 12o 40) 0.01mol, ammonium nitrate (NH 4nO 3) 0.24mol, citric acid (CO (NH 2) 2) 0.1mol, ethylenediamine tetraacetic acid (EDTA) (EDTA) 0.005mol.Raw material powder is dissolved in appropriate deionized water for stirring to completely dissolve after, constant temperature 200 DEG C heating, reacts after solution evaporate to dryness and obtains precursor tungsten oxide powder.By precursor 650 DEG C of nitrogenize in ammonia, be incubated and within 2 hours, obtain the tungsten nitride that diameter is 50 ~ 80nm.
Embodiment 5
Ammonium metawolframate ((NH is taken according to stoichiometry 4) 6h 2w 12o 40) 0.01mol, ammonium nitrate (NH 4nO 3) 0.24mol, glycine (C 2h 5nO 2) 0.072mol, ethylenediamine tetraacetic acid (EDTA) (EDTA) 0.005mol.Raw material powder is dissolved in appropriate deionized water for stirring to completely dissolve after, constant temperature 200 DEG C heating, reacts after solution evaporate to dryness and obtains precursor tungsten oxide powder.By precursor 750 DEG C of nitrogenize in ammonia, be incubated and within 2 hours, obtain the tungsten nitride that diameter is 50 ~ 100nm.

Claims (4)

1. a synthetic method for high catalytic performance tungsten nitride, is characterized in that having following steps:
(1) raw material: with ammonium metawolframate, ammonium nitrate, auxiliary and ethylenediamine tetraacetic acid (EDTA) for raw material;
(2) solution preparation: selected raw material is water-soluble according to certain proportioning, mixes; Ammonium nitrate and ammonium metawolframate mol ratio are 12 ~ 36; The mol ratio of auxiliary and ammonium metawolframate is 5 ~ 15; Ethylenediamine tetraacetic acid (EDTA) and ammonium metawolframate mol ratio are 0.5 ~ 1;
(3) precursor power: the aqueous solution heating that step (2) is obtained, along with the volatilization of the aqueous solution, solution is bubbling after generation is concentrated, releases a large amount of gas, in seconds there is vigorous oxidation reduction reaction, form a kind of presoma powder of porous;
(4) preparation of tungsten nitride: the precursor nitrogenize under ammonia atmosphere step (3) obtained, obtains the nano silicon nitride tungsten powder of pure, porosity and size tunable.
2. the synthetic method of a kind of high catalytic performance tungsten nitride according to claim 1, is characterized in that the auxiliary in step (1) is urea, glycine, oxysuccinic acid, thiocarbamide, citric acid at least one wherein.
3. the preparation method of a kind of high catalytic performance tungsten nitride according to claim 1, is characterized in that in step (4), nitriding temperature is 650 DEG C ~ 900 DEG C under ammonia atmosphere.
4. the preparation method of a kind of high catalytic performance tungsten nitride according to claim 1, is characterized in that the time of nitrogenize under ammonia atmosphere in step (4) is 1 ~ 2h.
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN107915212A (en) * 2016-10-08 2018-04-17 中国科学院大连化学物理研究所 Caterpillar shape WN nano materials that lamella stacks and preparation method thereof
CN109675598A (en) * 2019-03-04 2019-04-26 合肥工业大学 A kind of preparation method of the nickel tungsten carbide composite nano-powder as elctro-catalyst
CN109678157A (en) * 2019-03-04 2019-04-26 合肥工业大学 A kind of preparation method of high catalytic activity nanometer tungsten carbide
CN110228797A (en) * 2018-07-25 2019-09-13 北京科技大学 A kind of method that low cost prepares two-dimentional molybdenum nitride or tungsten nitride nanometer sheet
CN110368970A (en) * 2019-08-26 2019-10-25 合肥工业大学 A kind of preparation method of the activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst
CN112938910A (en) * 2021-04-16 2021-06-11 中国检验检疫科学研究院 Synthetic method and application of lamellar tungsten nitride nano material
CN113755879A (en) * 2021-09-06 2021-12-07 隆基绿能科技股份有限公司 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

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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
CN101786610A (en) * 2010-03-19 2010-07-28 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

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CN1470327A (en) * 2002-07-24 2004-01-28 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
CN101786610A (en) * 2010-03-19 2010-07-28 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

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915212A (en) * 2016-10-08 2018-04-17 中国科学院大连化学物理研究所 Caterpillar shape WN nano materials that lamella stacks and preparation method thereof
CN110228797A (en) * 2018-07-25 2019-09-13 北京科技大学 A kind of method that low cost prepares two-dimentional molybdenum nitride or tungsten nitride nanometer sheet
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
CN109675598A (en) * 2019-03-04 2019-04-26 合肥工业大学 A kind of preparation method of the nickel tungsten carbide composite nano-powder as elctro-catalyst
CN109678157A (en) * 2019-03-04 2019-04-26 合肥工业大学 A kind of preparation method of high catalytic activity nanometer tungsten carbide
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
CN110368970A (en) * 2019-08-26 2019-10-25 合肥工业大学 A kind of preparation method of the activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst
CN112938910A (en) * 2021-04-16 2021-06-11 中国检验检疫科学研究院 Synthetic method and application of lamellar tungsten nitride nano material
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
CN113755879A (en) * 2021-09-06 2021-12-07 隆基绿能科技股份有限公司 Delta-phase tungsten nitride electrode material and preparation method and application thereof
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

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