CN102320601A - Multistage porous carbon-tungsten compound micro-nano powder and preparation method thereof - Google Patents

Multistage porous carbon-tungsten compound micro-nano powder and preparation method thereof Download PDF

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CN102320601A
CN102320601A CN2011102707507A CN201110270750A CN102320601A CN 102320601 A CN102320601 A CN 102320601A CN 2011102707507 A CN2011102707507 A CN 2011102707507A CN 201110270750 A CN201110270750 A CN 201110270750A CN 102320601 A CN102320601 A CN 102320601A
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nano powder
tungsten compound
multistage porous
compound micro
micro
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CN102320601B (en
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陈德良
张锐
翟海涛
张毅
尹莉
李涛
温合静
张光飞
陈倩
高佳冰
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Zhengzhou University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the field of nano-structured materials and advanced-functional materials and concretely relates to multistage porous carbon-tungsten compound micro-nano powder and a preparation method thereof. The carbon-tungsten compound micro-nano powder is in a multistage porous laminated structure, and a phase is WC, W2C, WC1-x or a mixture of the WC, the W2C and the WC1-x. When the carbon-tungsten compound micro-nano powder in the multistage porous laminated structure prepared by the method is used as an enhancing body for wear-resistant materials or cutting tools, the structure is favorable to increasing the bonding force of the enhancing body and a base material; when the carbon-tungsten compound micro-nano powder is used as a catalyst and a catalyst promoter, an easily-dispersed two-dimensional structure, the multistage porous structure and high specific surface area are more favorable to improving the catalytic performance of the catalyst; and in addition, a porous micro-nano sheet formed from nano particles has a larger volume and is favorable to being recycled.

Description

A kind of multistage porous carbon tungsten compound micro-nano powder and preparation method thereof
Technical field
The invention belongs to nano structural material and advanced function field of materials, be specifically related to a kind of multistage porous carbon tungsten compound micro-nano powder and preparation method thereof.
Background technology
Ultra-fine/nano hard alloy shows the HS that conventional material does not possess, H.T. owing to have nanometer or superfine crystal particle structure; Good performances such as high firmness and good wear resistance, heat-resisting erosion property; In materials processed, cutting tool material, aerospace and military project weapon aspect are widely used; Be one of wimet field main development tendency, tungsten carbide micro-nano powder is the important source material of ultra-fine cemented carbide.
Since Levy in 1973 and Boudart reported first WC have and surface catalysis performance like the precious metal such as Pt, the act as a fuel noble metal catalyst and the photochemical catalysis hydrolytic hydrogen production noble metal promoted agent equivalent material of battery of WC also receives much attention.Tungsten carbide micro-nano powder has high specific surface area, help improving its aspect catalysis performance and as the advantage of support of the catalyst.Have many reports about zero dimension and the micro-nano brilliant preparation of one dimension WC at present, but so far still not about having the report of the micro-nano crystalline substance of multistage vesicular structure carbide layers sheet.
Summary of the invention
The purpose of this invention is to provide a kind of multistage porous carbon tungsten compound micro-nano powder and preparation method thereof.
The present invention adopts following technical scheme:
A kind of multistage porous carbon tungsten compound micro-nano powder, this carbon tungsten compound micro-nano powder is multistage porous laminated structure, and thing is WC, W mutually 2C, WC 1-xPerhaps their mixture.
The apparent area of said laminated structure is the nm of (100-2000) nm * (100-2000), and apparent thickness is 5-100 nm; The specific surface area of laminated structure is 15-80 m 2/ g, void content are 10-30%.
The preparation method of multistage porous carbon tungsten compound micro-nano powder may further comprise the steps: with the wolframic acid base inorganic-organic lamellar compound that mixes is a precursor, in carbon-containing atmosphere, the reaction 1-30 h under 650-1000 ℃ obtains; Or with WO 3 xH 2O (0≤ x≤3) nanometer sheet is a precursor, earlier at NH 3Middle nitrogenize in carbon-containing atmosphere, is reacted 1-30 h down through 650-1000 ℃ and is obtained then.
Preparation process is: with the wolframic acid base inorganic-organic lamellar compound that mixes puts into Reaktionsofen, earlier logical shielding gas exhausted air feeds CO/CO again 2Mixed gas is warming up to 650-1000 ℃, and heat-up rate is 1-100 ℃/min, and insulation reaction 1-30 h makes multistage porous carbon tungsten compound micro-nano powder; Or with WO 3 xH 2O (0≤ x≤3) nanometer sheet is put into Reaktionsofen, and earlier logical shielding gas exhausted air feeds NH again 3Be warming up to 450-650 ℃, insulation 0.5-10h nitrogenize, feed CO/CO then 2Mixed gas is warming up to 650-1000 ℃, and heat-up rate is 1-100 ℃/min, and insulation reaction 1-30 h makes multistage porous carbon tungsten compound micro-nano powder.
When the thing of said carbon tungsten compound micro-nano powder is WC mutually, feed CO/CO 2Be warming up to 650-800 ℃ behind the mixed gas, insulation 5-15h makes multistage porous WC micro-nano powder.
The thing of said carbon tungsten compound micro-nano powder is W mutually 2During C, feed CO/CO 2Be warming up to 800-1000 ℃ behind the mixed gas, insulation 1-3h makes multistage porous W 2The C micro-nano powder.
The thing of said carbon tungsten compound micro-nano powder is WC mutually 1-xThe time, feed CO/CO 2Mixed gas is warming up to 650-780 ℃, and insulation 1-3h makes multistage porous WC 1-xMicro-nano powder.
CO/CO 2CO and CO in the mixed gas 2Volume ratio be 6-10:1.
Shielding gas is CO 2, N 2Or Ar.
Said Reaktionsofen is tubular type atmosphere furnace or box atmosphere furnace.
Wolframic acid base used among the present invention is inorganic-and organic lamellar compound that mixes is to be reactant, in non-polar solvent, to react and obtain with wolframic acid and organic amine; The mol ratio of W atom is 2 ~ 30 in organic amine and the wolframic acid; The volume ratio of non-polar solvent and organic amine is 2 ~ 30; Temperature of reaction is 10 ~ 40 ℃, and the reaction times is 10 ~ 120 h, products therefrom drying at room temperature after solid-liquid separation gets white powder wolframic acid base inorganic-organic lamellar compound that mixes; Wolframic acid is WO 3 xH 2O or H 2W 2O 7 xH 2O, 0≤ x≤3; Organic amine is straight chain alkyl amine CH 3(CH 2) n NH 2, 4≤ n≤18; Non-polar solvent is liquid alkane.
WO among the present invention 3 xH 2O (0≤ x≤3) nanometer sheet be with the wolframic acid base inorganic-organic lamellar compound that mixes is a precursor, reaction 10-120h makes under warp and the nitric acid room temperature, the volumetric molar concentration of nitric acid is 1-10mol/L, reaction finish after-filtration, washing leaching cake, dry H below 200 ℃ 2WO 4 xH 2O (0≤ x≤3) nanometer sheet is with H 2WO 4 xH 2The O nanometer sheet is calcined 0.5-10 h down at 200-800 ℃ and is made WO 3 xH 2O (0≤ x≤3) nanometer sheet.
The present invention with the wolframic acid base inorganic-organic lamellar compound or WO of mixing 3 xH 2O (0≤ x≤3) nanometer sheet is a presoma, at CO/CO 2In the mixed gas, made through the control temperature reaction that porous is multistage, the carbon tungsten compound micro-nano powder of laminated structure, thing is WC, W mutually 2C, WC 1-xPerhaps their mixture; The apparent area of its laminated structure is the nm of (100-2000) nm * (100-2000), and apparent thickness is 5-100 nm; The specific surface area of laminated structure is 15-80 m 2/ g, void content are 10-30%.
The wolframic acid base that the present invention adopted is inorganic-organic WO that mixes inorganic individual layer in the lamellar compound precursor 6Alternately arrange with organic amine, the carbon that the organic amine cracking generates in temperature-rise period is wrapped in the WC surface, has effectively stoped growing up of its crystal grain, and the space steric effect of banded precursor makes its transient structure still for banded, and good dispersion is not reunited.
The WO that the present invention adopted 3 xH 2O (0≤ x≤3) nanometer sheet good dispersibility, size homogeneous, the WO of two dimension 3Nanometer sheet is because space steric effect can keep good dispersion state, and difficult the reunion is because WO 3Density compare W 2N is little a lot, and in the process that generates tungsten nitride, the tungsten nitride that generates has earlier stoped monocrystalline WO 3The contraction of nanometer sheet, the W that makes generation 2The N product two-dimentional multistage W that littler nano particle is formed by connecting that serves as reasons 2The N micro nano structure; The multistage W of two dimension 2The N micro nano structure is at follow-up CO/CO 2Carburizing reagent takes place in the mixed gas form multistage porous carbon tungsten compound micro-nano powder.
The carbon tungsten compound micro-nano powder of the multistage porous that the present invention makes, laminated structure is when being used for high-abrasive material or cutting tool as the enhancing body, and this structure helps improving the bonding force that strengthens body and body material; As catalyzer and promotor the time; Be easy to the raising that dispersive two dimension laminated structure, multistage vesicular structure and high-specific surface area more help catalyst catalytic performance; In addition, micro-nano volume of porous of being made up of nano particle is bigger, helps recycling.
Among the present invention, be precursor to have sterically hindered sheet structure, at nitrogenize/carbonation reaction, it is constant basically that inflexible laminated structure skeleton keeps; On the other hand, thing phase change before and after answering, their density obviously increases, and the particle apparent volume is constant basically, therefore, forms multistage vesicular structure to reach the mediation of thing phase change and constant volume.
Description of drawings
Fig. 1 for embodiment 1 gained wolframic acid base inorganic-organic XRD figure spectrum that mixes lamellar compound;
Fig. 2 for embodiment 1 gained wolframic acid base inorganic-organic SEM photo that mixes lamellar compound;
Fig. 3 for embodiment 2 gained wolframic acid bases inorganic-organic XRD figure spectrum that mixes lamellar compound;
Fig. 4 for embodiment 2 gained wolframic acid bases inorganic-organic SEM photo that mixes lamellar compound;
Fig. 5 is the XRD figure spectrum of embodiment 3 gained samples;
Fig. 6 is the XRD figure spectrum of embodiment 4 gained samples;
Fig. 7 is the XRD figure spectrum of embodiment 5 gained samples;
Fig. 8 is the XRD figure spectrum of embodiment 6 gained samples;
Fig. 9 is the SEM photo of embodiment 6 gained samples;
Figure 10 is the XRD figure spectrum of embodiment 7 gained tungsten carbide micro-nano powders;
Figure 11 is the SEM photo of embodiment 7 gained tungsten carbide micro-nano powders;
Figure 12 is the FE-SEM photo of embodiment 7 gained tungsten carbide micro-nano powders;
Figure 13 is the XRD figure spectrum of embodiment 8 gained tungsten carbide micro-nano powders;
Figure 14 is the FE-SEM photo of embodiment 8 gained tungsten carbide micro-nano powders;
The HRTEM photo of Figure 15 embodiment 7 gained tungsten carbide micro-nano powders;
The TEM photo of Figure 16 embodiment 8 gained tungsten carbide micro-nano powders.
Embodiment
Embodiment 1
Take by weighing the 30ml NSC 9824, the 240ml normal heptane is put into 500 ml Erlenmeyer flasks, after the two is mixed, adds 9.09 g H 2WO 4, limit edged vigorous stirring begins to be yellow suspension liquid; Along with the prolongation of time, the color of suspension liquid is thin out gradually, becomes white at last; Stir 24 h, leave standstill 48 h, with white suspension liquid solid-liquid separation; With absolute ethanol washing solid phase 5 times, drying under reduced pressure 30 h under the room temperature, obtain 18.8 g wolframic acid bases inorganic-organic lamellar compound that mixes.Fig. 1 is its XRD figure spectrum, low diffraction angle (2 θ<20 °) the strong diffraction peak that occurs of zone can belong to and be (00 l) diffraction of crystal face, show that this product has typical two-dimensional layered structure.Fig. 2 can find out that for its SEM figure it is for being about 5 ~ 10 μ m, the zonal structure of generous about 0.5 μ m.
Embodiment 2
Take by weighing the 20ml NSC 9824, the 160ml normal heptane is put into 250 ml Erlenmeyer flasks, after the two is mixed, adds 3mL zero(ppm) water and 6.06 g H 2WO 4Uniform mixture, limit edged vigorous stirring begins to be yellow suspension liquid; Along with the prolongation of time, the color of suspension liquid is thin out gradually, becomes white at last; Stir 24 h, leave standstill 48 h, with white suspension liquid solid-liquid separation; With absolute ethanol washing solid phase 5 times, drying under reduced pressure 30 h under the room temperature, obtain 10.1 g wolframic acid bases inorganic-organic lamellar compound that mixes.Fig. 3 is its XRD figure spectrum, low diffraction angle (2 θ<20 °) the strong diffraction peak that occurs of zone can belong to and be (00 l) diffraction of crystal face, show that this product has typical two-dimensional layered structure.Fig. 4 can find out that for its SEM figure it is the sheet structure that the length of side is about 0.8 μ m.
Embodiment 3
Get 0.8g embodiment 1 gained wolframic acid base inorganic-organic lamellar compound that mixes places Al 2O 3On the ceramic plate, put it into boiler tube central authorities, feed CO earlier near thermocouple location 2Residual air in the 30min, purger feeds CO/CO then 2Mixed gas (CO and CO 2Volume ratio be 10:1), be warming up to 700 ℃ the insulation 3h, naturally cool to room temperature, obtain the black powder.Fig. 5 can find out that for its XRD figure spectrum the gained sample is six side's phase WC 1-x(JCPDS card No. 20-1316).
Embodiment 4
Get 0.8g embodiment 1 gained wolframic acid base inorganic-organic lamellar compound that mixes places Al 2O 3On the ceramic plate, put it into boiler tube central authorities, feed N earlier near thermocouple location 2Residual air in the 30min, purger feeds CO/CO then 2Mixed gas (CO and CO 2Volume ratio be 6:1), be warming up to 750 ℃ the insulation 5h, naturally cool to room temperature, obtain the black powder.Fig. 6 can find out that for its XRD figure spectrum the gained sample is six side's phase WC (JCPDS card No. 51-0939) and W 2The mixture of C (JCPDS card No. 35-0776).
Embodiment 5
Get 0.8g embodiment 2 gained wolframic acid bases inorganic-organic lamellar compound that mixes places Al 2O 3On the ceramic plate, put it into boiler tube central authorities, feed CO earlier near thermocouple location 2Residual air in the 30min, purger feeds CO/CO then 2Mixed gas (CO and CO 2Volume ratio be 10:1), be warming up to 750 ℃ the insulation 10h, naturally cool to room temperature, obtain the black powder.Fig. 7 can find out that for its XRD figure spectrum the gained sample is six side's phase WC (JCPDS card No. 51-0939), and the SEM photo shows that it is the very porous microsphere of uneven diameter 0.3-10um of size distribution.
Embodiment 6
Get 0.8g embodiment 1 gained wolframic acid base inorganic-organic lamellar compound that mixes places Al 2O 3On the ceramic plate, put it into boiler tube central authorities, feed N earlier near thermocouple location 2Residual air in the 30min, purger feeds CO/CO then 2Mixed gas (CO and CO 2Volume ratio be 10:1), be warming up to 850 ℃ the insulation 2h, naturally cool to room temperature.Fig. 8 is the XRD figure spectrum of gained sample, can find out that it is six side's phase W 2C (JCPDS card No. 35-0776).Fig. 9 is the SEM photo of gained sample, can find out that sample is multistage vesicular structure.
Embodiment 7
Get 0.8g embodiment 1 gained wolframic acid base inorganic-organic lamellar compound that mixes places Al 2O 3On the ceramic plate, put it into boiler tube central authorities near thermocouple location, feed Ar30min earlier, residual air in the purger feeds CO/CO then 2Mixed gas (CO and CO 2Volume ratio be 10:1), be warming up to 750 ℃ the insulation 10h, naturally cool to room temperature, obtain the black powder.Figure 10 can find out that for its XRD figure spectrum the gained sample is six side's phase WC (JCPDS card No. 51-0939), does not have the appearance of impurity peaks.Figure 11, Figure 12 and Figure 15 are respectively its SEM photo, FE-SEM photo and HRTEM photo; Can know and see; Product is by the multistage porous carbide layers sheet micro-nano powder of forming for the crystal grain of big or small 2-10 nanometer that has; Its apparent area is the nm of (100-2000) nm * (100-2000), and apparent thickness is 20-100 nm, specific surface area 78.90 m 2/ g, void content 24.71%.
Embodiment 8
Get 10g embodiment 2 gained wolframic acid bases inorganic-organic lamellar compound that mixes, slowly pour 500mL into, volumetric molar concentration is in the 1-10mol/L salpeter solution, limit edged vigorous stirring begins to be white suspension liquid; Along with the prolongation of time, the thin out gradually yellow of the color of suspension liquid becomes glassy yellow at last, stirs 48h; Leave standstill 24h, with yellow suspension liquid solid-liquid separation, with distilled water wash solid phase 5 times; Absolute ethanol washing solid phase 3 times, 120 ℃ of drying 10 h obtain 4.8 g glassy yellow solid H 2WO 4 xH 2O (0≤ x≤3) nanometer sheet is placed on 400 ℃ of calcining 2h in the crucible, obtains WO 3Nanometer sheet 4.7g.
Take by weighing 3.9gWO 3Nanometer sheet places Al 2O 3On the ceramic plate, put it into boiler tube central authorities, feed CO earlier near thermocouple location 2Residual air in the 30min, purger feeds NH then 3, being warming up to 650 ℃, insulation 2h feeds CO/CO again 2Mixed gas (CO and CO 2Volume ratio be 10:1) be warming up to 750 ℃, the insulation 10h, naturally cool to room temperature, obtain the black powder.Figure 13 can find out that for its XRD figure spectrum the gained sample is six side's phase WC (JCPDS card No. 51-0939), does not have the appearance of impurity peaks.Figure 14 is its SEM photo, can know and see that it is micro-nano of the wolfram varbide porous with multilevel hierarchy of the size homogeneous be made up of less nanometer sheet, and its apparent area is the nm of (100-500) nm * (100-500), and apparent thickness is 5-10 nm; Its BET specific surface area is 19.54 m 2/ g, void content are 15.37%; The TEM photo of Figure 16 shows that grain size of product is 20-30 nm.
Embodiment 9
Be with embodiment 6 differences, be warming up to 1000 ℃ of insulation 1h.
Embodiment 10
Be with embodiment 3 differences, be warming up to 780 ℃ of insulation 1h.
Embodiment 11
Be with embodiment 4 differences, be warming up to 650 ℃ of insulation 15h.
When heating up among the embodiment 3-11, heat-up rate is 25-80 ℃/min in the time of below 500 ℃, and heat-up rate is 5-25 ℃/min in the time of below 500 ℃.
Used instrument model among the present invention:
X-ray diffraction analysis (XRD): Beijing is general analyse general;
Sem (SEM): QUANTA-200 (Holland);
Field emission scanning electron microscope (FE-SEM): Nova-230 (FEI);
High resolution transmission electron microscopy (HRTEM): JEM-2100 (NEC).

Claims (10)

1. multistage porous carbon tungsten compound micro-nano powder, it is characterized in that: this carbon tungsten compound micro-nano powder is multistage porous laminated structure, and thing is WC, W mutually 2C, WC 1-xPerhaps their mixture.
2. multistage porous carbon tungsten compound micro-nano powder as claimed in claim 1 is characterized in that: the apparent area of said laminated structure is the nm of (100-2000) nm * (100-2000), and apparent thickness is 5-100 nm; The specific surface area of laminated structure is 15-80 m 2/ g, void content are 10-30%.
3. the preparation method of claim 1 or 2 described multistage porous carbon tungsten compound micro-nano powders; It is characterized in that may further comprise the steps: with the wolframic acid base inorganic-organic lamellar compound that mixes is a precursor; In carbon-containing atmosphere, the reaction 1-30 h under 650-1000 ℃ obtains; Or with WO 3 xH 2O (0≤ x≤3) nanometer sheet is a precursor, earlier at NH 3Middle nitrogenize in carbon-containing atmosphere, is reacted 1-30 h down through 650-1000 ℃ and is obtained then.
4. the preparation method of multistage porous carbon tungsten compound micro-nano powder as claimed in claim 3 is characterized in that: preparation process is: with the wolframic acid base inorganic-organic lamellar compound that mixes puts into Reaktionsofen, earlier logical shielding gas exhausted air feeds CO/CO again 2Mixed gas is warming up to 650-1000 ℃, and heat-up rate is 1-100 ℃/min, and insulation reaction 1-30 h makes multistage porous carbon tungsten compound micro-nano powder; Or with WO 3 xH 2O (0≤ x≤3) nanometer sheet is put into Reaktionsofen, and earlier logical shielding gas exhausted air feeds NH again 3Be warming up to 450-650 ℃, insulation 0.5-10h nitrogenize, feed CO/CO then 2Mixed gas is warming up to 650-1000 ℃, and heat-up rate is 1-100 ℃/min, and insulation reaction 1-30 h makes multistage porous carbon tungsten compound micro-nano powder.
5. the preparation method of multistage porous carbon tungsten compound micro-nano powder as claimed in claim 4 is characterized in that: when the thing of said carbon tungsten compound micro-nano powder is WC mutually, feed CO/CO 2Be warming up to 650-800 ℃ behind the mixed gas, insulation 5-15h makes multistage porous WC micro-nano powder.
6. the preparation method of multistage porous carbon tungsten compound micro-nano powder as claimed in claim 4 is characterized in that: the thing of said carbon tungsten compound micro-nano powder is W mutually 2During C, feed CO/CO 2Be warming up to 800-1000 ℃ behind the mixed gas, insulation 1-3h makes multistage porous W 2The C micro-nano powder.
7. the preparation method of multistage porous carbon tungsten compound micro-nano powder as claimed in claim 4 is characterized in that: the thing of said carbon tungsten compound micro-nano powder is WC mutually 1-xThe time, feed CO/CO 2Mixed gas is warming up to 650-780 ℃, and insulation 1-3h makes multistage porous WC 1-xMicro-nano powder.
8. the preparation method of multistage porous carbon tungsten compound micro-nano powder as claimed in claim 4 is characterized in that: CO/CO 2CO and CO in the mixed gas 2Volume ratio be 6-10:1.
9. like the preparation method of each described multistage porous carbon tungsten compound micro-nano powder of claim 3 to 8, it is characterized in that: shielding gas is CO 2, N 2Or Ar.
10. like the preparation method of each described multistage porous carbon tungsten compound micro-nano powder of claim 3 to 8, it is characterized in that: said Reaktionsofen is tubular type atmosphere furnace or box atmosphere furnace.
CN2011102707507A 2011-09-09 2011-09-14 Multistage porous carbon-tungsten compound micro-nano powder and preparation method thereof Expired - Fee Related CN102320601B (en)

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Cited By (5)

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CN106532070A (en) * 2016-09-28 2017-03-22 浙江工业大学 Preparation method of WN/WC with porous heterogeneous interface
CN108480655A (en) * 2018-04-10 2018-09-04 河南大学 A kind of carbon-supported metal tungsten nano particle
CN110562982A (en) * 2019-10-16 2019-12-13 陕西科技大学 Nano ditungsten carbide particles and preparation method and application thereof
CN113511684A (en) * 2020-04-10 2021-10-19 中国石油化工股份有限公司 WO3Nanosheet and preparation method thereof and gas sensor
CN115255378A (en) * 2022-06-27 2022-11-01 北京科技大学 Preparation method of porous tungsten material with multistage pore structure

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CN101780982A (en) * 2010-03-19 2010-07-21 郑州大学 Preparation method of tungsten carbide micro-nano powder

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106532070A (en) * 2016-09-28 2017-03-22 浙江工业大学 Preparation method of WN/WC with porous heterogeneous interface
CN108480655A (en) * 2018-04-10 2018-09-04 河南大学 A kind of carbon-supported metal tungsten nano particle
CN110562982A (en) * 2019-10-16 2019-12-13 陕西科技大学 Nano ditungsten carbide particles and preparation method and application thereof
CN113511684A (en) * 2020-04-10 2021-10-19 中国石油化工股份有限公司 WO3Nanosheet and preparation method thereof and gas sensor
CN113511684B (en) * 2020-04-10 2024-03-22 中国石油化工股份有限公司 WO 3 Nanosheets, preparation method thereof and gas sensor
CN115255378A (en) * 2022-06-27 2022-11-01 北京科技大学 Preparation method of porous tungsten material with multistage pore structure
CN115255378B (en) * 2022-06-27 2023-07-21 北京科技大学 Preparation method of porous tungsten material with multi-stage pore structure

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