CN1445536A - Method for synthesizing predecessor of tungsten trioxide and hydrogen sulfide gas sensor made from the predecessor - Google Patents
Method for synthesizing predecessor of tungsten trioxide and hydrogen sulfide gas sensor made from the predecessor Download PDFInfo
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- CN1445536A CN1445536A CN 02107410 CN02107410A CN1445536A CN 1445536 A CN1445536 A CN 1445536A CN 02107410 CN02107410 CN 02107410 CN 02107410 A CN02107410 A CN 02107410A CN 1445536 A CN1445536 A CN 1445536A
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- tungstic acid
- hydrogen sulfide
- gas sensor
- acid precursor
- sulfide gas
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Abstract
A process for synthesizing the precursor of WO3 includes such steps as dissolving soluble W compound in solvent, adding viscosity increaser, depositing on a substrate, and high-temp heat treating to decompose its organic component and obtain a uniform WO3 film. A hydrogen sulfide gas sensor prepared from said WO3 film has high sensitivity, better selectivity and high response speed.
Description
Technical field
The invention relates to a kind of precursor synthetic method that is used for the sensing material of gas sensor, be particularly to a kind of synthetic method of tungstic acid precursor and with its these hydrogen sulfide gas sensor of making.
Background technology
As everyone knows, sulfuretted hydrogen (H
2S) be a kind of pollutant common in the course of industrialization, its main source is petro chemical industry and gas industry, and other for example Leather Factory, paper mill, dyestuff factory, Electroplate Factory, refuse incinerator and sewage treatment plant etc.
Sulfuretted hydrogen is a kind of colourless gas, and has rotten egg foul smell, and its toxicity is very strong, and permissible concentration is 10ppm in air, and blast bound scope is 4.3%-46.0%.Hydrogen sulfide gas belongs to the neural poison of chemical, stimulation and stanch air for the harm of human body, can destroy red blood cell, 0.1ppm the time can cause olfactory stimulation, during several ppm, human body will feel to have the fetid odour of strong dislike, but,, do not have meaning so detect high-concentration hydrogen sulfide with sense of smell because high-concentration hydrogen sulfide has the effect that suppresses olfactory nerve as long as just can not hear blink.When concentration of hydrogen sulfide just has serious pungency and asphyxiating greater than 500ppm, to the health influence greatly, except that forfeiture sensation immediately, and may cause death.The standard of being announced according to Taiwan board of workers of Executive Yuan is 10ppm (Threshold LimitedValue in the maximum permissible concentration of 8 hourly averages of workplace sulfuretted hydrogen; TLV), therefore, how the hydrogen sulfide gas of trace in the air is done detection by quantitative, become relevant operation place urgent problem.
At present the gas sensor of semi-conductor type is widely used, and that this gas sensor has is simple in structure, processing procedure is simple and easy, material usage reaches advantages such as cost of manufacture is cheap less.This semi-conductor type gas sensor is to utilize gas to carry out adsorption reaction on the sensing material surface, and when sense gasses molecule or atomic adsorption during on the sensing material surface, the sensing material surface can absorb or emit unnecessary electronics.And the free electron density on sensing material surface is changed, therefore cause the variation of sensing material resistance value, and decide the concentration of gas according to its resistance change.Wherein used sensing material is metal oxide mostly, and these metal oxides all have semi-conductive characteristic.General metal oxide commonly used has SnO
2, WO
3, ZnO, TiO
2And Fe
2O
3, the aerial crystal boundary of these sensing materials (Grain Boundary) energy barrier is higher, and electronics is difficult for passing through, so resistance is very high.But when it is exposed to reducibility gas (Reducing Gas), for example H
2S, CO, CH
4, NO
x, SO
2, H
2, NH
3During Deng gas, its crystal boundary energy barrier can reduce, and can allow electronics pass through easily, so resistance or conductivity can produce variation clearly, and changes along with the concentration of gas, and this also is the principle that it is mainly used to sense gasses.
The employed sensing material of semi-conductor type gas sensor must just have enough energy and tested gas reaction mostly under the situation of high temperature; And producing tangible sensitivity, its operating temperature is greatly between 200-400 ℃.
The relevant patent of traditional these hydrogen sulfide gas sensor has Jap.P. 6-18467 number, US PatentNo.4822465, US Patent No.4197089 and US Patent No.5321146 etc.
Wherein Jap.P. is for 6-18467 number to disclose with ammonium tungstate (Ammonium Paratungstate) { (NH
4)
10W
12O
415H
2O} is an original material, obtains tungsten trioxide powder after heat treated, this powder of sintering under 600 ℃ of conditions again, and become sensing material.Its major defect is:
Because above-mentioned sensing material has that structural strength is poor, between powder and the powder or shortcoming such as the bond power between powder and the base material is weak, therefore the soundness of whole sensing component is not good.
US Patent No.4822465 is to use radio frequency sputter (RF Sputtering) for method the sensing material tungsten oxide to be deposited on the substrate, the common homogeneity of this method is not good, especially generally there is alloy to exist in the sensing material, be that the target itself that sputter is used is a kind of potpourri, so its alloy possibility skewness of the sensor of making, and make the consistance between sensor and the sensor not good.
Again, US Patent No.4197089 then drops in the wolframic acid amine aqueous solution on the base material, carries out thermal decomposition subsequently and makes it form the sensing film of one deck tungstic acid at substrate surface.Though the made sensor of the method for this patent can obtain preferable selectivity, this practice is comparatively coarse, and whole processing procedure is difficult for grasping for the microtexture of sensing film, so performances such as the sensitivity of this sensor and selectivity also just are difficult for prediction.
US Patent No.5 321146 is to use Na (OW (OOCR)
2)
2Be to make the raw material of tungstic acid, be attached to this raw material deposition on the substrate with methods such as rotary coating, dip coated or spraying coatings after, carry out that thermal decomposition makes at substrate surface formation one deck tungstic acid sensing film.But the used method of this patent need use than costliness or toxicity is stronger or not tractable chemicals, not only increases cost, also increases the difficulty on making.Moreover, for synthetic this raw material Na (OW (OOCR)
2)
2, reaction must be carried out in the drying box of isolating, and operation is inconvenience rather, and in addition, in the entire synthesis process, drying box needs inert gas, and needs the vacuum equipment extraction product, also increases make numerous and diverse.And the raw material Na of above-mentioned use (OW (OOCR)
2)
2In sodium be very inflammable dangerous goods, so the employed chemicals of this patent will increase the danger of making.
Summary of the invention
Fundamental purpose of the present invention provides a kind of precursor synthetic method that is used for the sensing material tungstic acid of these hydrogen sulfide gas sensor; the synthetic of this precursor can be synthesized in atmosphere; need not make the medicine and the solvent of apparatus danger; also need not use complicated utensil; course of reaction is also comparatively simple, reaches to reduce production costs and the purpose useful to the protection of environment.
Another object of the present invention provides the these hydrogen sulfide gas sensor that tungstic acid precursor that a kind of the present invention of utilization synthesizes is made, utilize screen painting, rotary coating, vacuum splashing and plating or fabrication techniques such as dipping, molten gel on substrate by the tungstic acid that this precursor produced, reach the acquisition processing procedure and simplify with production is easy in a large number; And have high sensitivity and a good optionally purpose of these hydrogen sulfide gas sensor.
The object of the present invention is achieved like this: a kind of synthetic method of tungstic acid precursor, and it comprises that the tungsten compound that dissolves a solubility is in a solvent; And the viscosity of regulating this solution in above-mentioned solution adding tackifier.
In the synthetic method of above-mentioned tungstic acid precursor, this tungsten compound is a kind of group that water miscible tungsten chloride, tungsten bromide, tungsten oxchloride, bromine tungsten oxide, wolframic acid etc. are formed that is selected from.These tackifier are for being selected from the group that glycerine, polyvinyl alcohol (PVA), cellulose etc. are formed, and wherein this solvent is to be selected from the group that alcohol, water or glycerine etc. are formed.
In said method, after the viscosity furnishing of tungsten oxide precursor is fit to be rotated the viscosity of coating or screen painting, this tungsten oxide precursor deposition is coated on the substrate, then carried out high-temperature heat treatment organic principle is decomposed, can obtain the layer of even WO 3 film.Yet in the above-mentioned steps, the mode of deposition coating tungsten oxide precursor is not limited to screen painting or rotary coating, can also dip coated or modes such as spraying coating or vacuum splashing and plating carry out.
The present invention also provides the tungstic acid precursor that utilizes the present invention to make to form these hydrogen sulfide gas sensor through the following steps, one ceramic substrate at first is provided, printed electrode and electric resistance heater at this substrate, another side then printed electrode and with rotary coating or screen painting deposition this tungstic acid precursor of coating and a catalyst layer on this substrate, carry out wiring and encapsulation afterwards, and obtain a these hydrogen sulfide gas sensor.
The these hydrogen sulfide gas sensor that gets according to the present invention, it comprises: a substrate; A pair of top electrode is positioned at a side of this substrate; A pair of bottom electrode is positioned at the opposite side of this substrate; One electric resistance heater is between this bottom electrode and connect two bottom electrodes; The tungstic acid layer, between this top electrode, wherein this tungstic acid is through thermal decomposition and sintering and get by this tungstic acid precursor of the present invention; One catalyst layer is positioned on this tungstic acid layer; And most Communication signal wires, in order to external top electrode and bottom electrode.
The material that is applicable to catalyst layer of the present invention is mainly gold (Au) and palladium (Pd) metallic element, but in order to cooperate the processing procedure needs, then with organic gold misfit thing and organic metal palladium misfit thing for it, these organic misfit things can obtain the gold and the palladium of metallic state after thermal treatment and decomposing.This substrate is not limited to potsherd, also can use silicon, glass sheet, plastic sheet etc.As for this electric resistance heater for being selected from RuO
2, material such as W, Pt, Ni.This electrode is then for being selected from metal materials such as Au, Pt, Ag/Pd, Ni.
According to the synthetic method of tungstic acid precursor of the present invention, can in atmosphere, synthesize, need not make the medicine and the solvent of apparatus danger; not only processing procedure is simple, also need not use complicated utensil, therefore for whole processing procedure; can reduce production costs, also quite helpful to the protection of environment.
Describe in detail below in conjunction with the preferred embodiment conjunction with figs..
Description of drawings
Fig. 1 is the schematic top plan view of these hydrogen sulfide gas sensor of the present invention.
Fig. 2 is the schematic side view of these hydrogen sulfide gas sensor of the present invention.
Fig. 3 is the elevational schematic view of these hydrogen sulfide gas sensor of the present invention.
Fig. 4 is the curve map of sensitivity test of the present invention.
Fig. 5 is the curve map of reaction response time of the present invention.
Fig. 6 is the curve map of the reaction response time of comparative example of the present invention.
Fig. 7 is the curve map of resistance of the present invention and concentration relationship.
Fig. 8 is the curve map of voltage of the present invention and concentration relationship.
Fig. 9 is the curve map of repeatability of the present invention.
Embodiment
The synthetic method of precursor of sensing material tungstic acid that preparation of the present invention is used for these hydrogen sulfide gas sensor is as follows:
10ml alcohol is placed in the vial of 20ml, adds 1.0g tungsten chloride (Tungtenhexachloride, WCl
6), a magnetic stirring bar to be put into this vial, and this vial is placed on the rotating spoon, rotation is stirred and is made its dissolving.Polyvinyl alcohol (PVA) (PVA) with total amount 1.0g slowly adds wherein again, and continues to stir until whole dissolvings.
Second kind of synthetic method of precursor of sensing material tungstic acid that preparation of the present invention is used for these hydrogen sulfide gas sensor is as follows:
With 2.5g wolframic acid (Tungsticacid, H
2WO
4) be placed in 20ml vial in, add till glycerine (Glycerol) is 10ml to cumulative volume.A magnetic stirring bar is put into this vial, and this vial is placed on the rotation agitating heating device, make its stirring and dissolving gradually.
Embodiment 3:
Preparation of the present invention is used for the catalyst of these hydrogen sulfide gas sensor, and synthetic method is as follows:
In the vial of 20ml, add the 0.4g organic misfit thing of gold (Organic-Au) and organic misfit thing of 0.2g Metal Palladium (Organic-Pd) and 10ml ortho-xylene (O-xylene), a magnetic stirring bar is put into this vial, and this vial is placed on the rotating spoon stirring and dissolving.
Embodiment 4:
The method that the precursor that utilizes tungstic acid of the present invention prepares these hydrogen sulfide gas sensor is as follows:
Consult Fig. 1-shown in Figure 3, get a ceramic substrate 10, below this reaches above substrate 10, print a pair of top electrode 20 and bottom electrode 50 with screen painting (Screen printing) earlier, afterwards, (between bottom electrode) prints an electric resistance heater 40 with screen painting below this substrate 10.Precursor with the sensing materials of embodiment 1 or 2 preparations deposits 20 of top electrodes that are coated on this substrate 10 with screen painting or rotary coating (Spin coating) mode afterwards, and thermal decomposition and sinter tungstic acid sensing material layer 30 under high-temperature.Afterwards with the catalyst material of embodiment 3 with the rotary coating mode deposit be coated on this tungstic acid sensing material layer above, and under high-temperature, carry out thermal decomposition and form a catalyst layer 30A.Carry out wiring and encapsulation with the Communication signal wire 60 that connects each electrode afterwards, and obtain these hydrogen sulfide gas sensor of the present invention.
Then, these hydrogen sulfide gas sensor of the present invention is carried out the test of relation, selectivity and repeatability of relation, change in voltage and the concentration of sensitivity, reaction response time, resistance variations and concentration, and be comparative example with tradition hydrogen sulfide sensor commodity of the same type, carry out sensitivity and the comparison of reacting response time, its result is as follows:
Sensitivity (Sensitivity) is meant the sensitivity level of general sensor to test gas, sensitivity be with following equation ((Ra-Rg)/Rg) get: wherein Ra be sensor in airborne resistance, Rg is the resistance of sensor in test gas.The sensitivity test of present embodiment is to carry out under 250 ℃.By the resistance material (RuO that is positioned on the sensor base plate
2) well heater that forms provides desired reaction temperature.
Fig. 4 shows the gas sensor that makes according to present embodiment for the performance performance of detecting sulfuretted hydrogen, wherein ◆ the gas sensor of representing the present invention to make, and the existing hydrogen sulfide sensor commodity of the same type of ■ representative.
The gas sensor that makes of the present invention has good detecting ability to the hydrogen sulfide gas of low concentration (dozens of ppb) as seen from Figure 4, and at 1ppmH
2During S, sensitivity can reach 6 times, when 10ppm (TLV) more up to 34 times.In the general merchandise, be limited under the sensing of the these hydrogen sulfide gas sensor of semi-conductor type about most ppm at present, such sensing performance also is not suitable for environment or the monitoring of industrial safety.Because the TLV value of sulfuretted hydrogen is 10ppm, therefore with the consideration of environment or industrial safety, these hydrogen sulfide gas sensor must can disengage alert news under far below the situation of this TLV value.Therefore according to the made these hydrogen sulfide gas sensor of tungstic acid precursor of the present invention, use, obvious effects is arranged for the monitoring of industrial safety or environmental protection.
Consult shown in Figure 5ly, the reaction response time of gas sensor (Response Time) generally is with T
90And T
20Represent.T
90Be meant that sensor output signal in test gas arrives the required time of stationary value 90%, and T
20After removing test gas, its output signal is got back to the required time of the former value of reading 20%.
The output voltage of the these hydrogen sulfide gas sensor that the present invention is made presents a definite value stably in pure air, when bestowing the hydrogen sulfide gas of a 10ppm, its output voltage values reached a new stationary value in 90 seconds, and when removing hydrogen sulfide gas, its output voltage returns to the numerical value that originally was in the pure air again rapidly.T wherein
90With T
20Be respectively 20 seconds and 9 seconds.These performances surmount the employed existing hydrogen sulfide sensor commodity of the same type of comparative example, consult shown in Figure 6, T wherein
90With T
20Be respectively 50 seconds and 30 seconds.
Consult Fig. 7-shown in Figure 8, selectivity (Selectivity) is meant the ability of sensor discrimination test gas, and other gas composition is to the influence and the interference cases of sensor.This characteristic is one of important performance of gas sensor, the gas sensor that selectivity is not good, and meeting produce electrical signal because of the existence of some interference gas and cause erroneous judgement, this situation to make gas sensor produce serious disappearance.
Consult shown in Fig. 7,8, show resistance variations and the relation of concentration and the relation of change in voltage and concentration of these hydrogen sulfide gas sensor of the present invention respectively.By finding out among the figure that the gas sensor that tungstic acid raw material of the present invention is made has good selectivity to sulfuretted hydrogen (*), to CO (), CH
4(△) and H
2(◇) wait the interference that gas caused very little.
Consult shown in Figure 9ly, repeatability (Reproducibility) is meant the repeatability of same sensor through its output valve of follow-on test.Consult shown in Figure 9ly, it is presented under 250 ℃, the test result in the hydrogen sulfide gas of 10ppm.By finding out among Fig. 9 that the gas sensor that tungstic acid precursor according to the present invention is made has good repeatability.
Though the present invention discloses as above with preferred embodiment, so it is not in order to limiting the present invention, anyly has the knack of this skill person, and without departing from the spirit and scope of the present invention, a little change and the retouching done all belongs within protection scope of the present invention.
Claims (10)
1, a kind of synthetic method of tungstic acid precursor, it is characterized in that: it comprises the steps:
(a) dissolving soluble tungsten compound forms solution in a solvent;
(b) in described solution, add tackifier, regulate the viscosity of this solution, make the tungstic acid precursor.
2, the synthetic method of tungstic acid precursor according to claim 1 is characterized in that: this soluble tungsten compound is to select wherein at least a from tungsten chloride, tungsten bromide, tungsten oxchloride, bromine tungsten oxide or wolframic acid.
3, the synthetic method of tungstic acid precursor according to claim 1 is characterized in that: these tackifier are to select from glycerine, polyvinyl alcohol (PVA) or cellulosic wherein at least a.
4, the synthetic method of tungstic acid precursor according to claim 1 is characterized in that: this solvent is to select wherein at least a from alcohol, water or glycerine.
5, the these hydrogen sulfide gas sensor made of one of them the synthetic tungstic acid precursor of method of a kind of claim 1-4, it is characterized in that: the both sides that it is included in substrate are respectively equipped with a pair of top electrode and a pair of bottom electrode; Electric resistance heater is between this bottom electrode and connect two bottom electrodes; The tungstic acid layer is between this top electrode; Catalyst layer is positioned on this tungstic acid layer; Most external these top electrodes of Communication signal wire and bottom electrode.
6, the these hydrogen sulfide gas sensor made of tungstic acid precursor according to claim 5 is characterized in that: this tungstic acid is through thermal decomposition and sintering and get by one of them tungstic acid precursor of claim 1-4.
7, the these hydrogen sulfide gas sensor made of tungstic acid precursor according to claim 5 is characterized in that: this upper and lower electrode is to select wherein at least a from Au, Pt, Ag/Pd or Ni metal material.
8, the these hydrogen sulfide gas sensor made of tungstic acid precursor according to claim 5, it is characterized in that: this electric resistance heater is to select from RuO
2, W, Pt or Ni wherein at least a.
9, the these hydrogen sulfide gas sensor made of tungstic acid precursor according to claim 5 is characterized in that: the material of this catalyst layer is to select wherein at least a from gold or palladium metal element.
10, the these hydrogen sulfide gas sensor made of tungstic acid precursor according to claim 5 is characterized in that: this substrate is to select wherein at least a from potsherd, silicon, glass sheet or plastic sheet material.
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|---|---|---|---|
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|---|---|---|---|
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| CN1210563C CN1210563C (en) | 2005-07-13 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412227C (en) * | 2006-07-25 | 2008-08-20 | 天津大学 | Magnetically controlled opposite target sputtering process of preparing gas-sensitive WO3 film sensor |
| CN100427939C (en) * | 2006-12-21 | 2008-10-22 | 天津大学 | Tungstic acid thin film air-sensitive sensor surface modifying method |
| CN101303322B (en) * | 2008-07-08 | 2011-07-27 | 清华大学 | Surface modification method of WO3 thick film gas-sensitive sensor |
| CN101236170B (en) * | 2007-09-13 | 2012-08-29 | 陈东初 | Integrated all-solid-state pH electrochemical sensor based on nanometer tungsten oxide and method for making same |
| CN101331080B (en) * | 2005-10-14 | 2012-12-26 | 意法半导体股份有限公司 | Substrate-level assembly for an integrated device, manufacturing process thereof and related integrated device |
| CN103852494A (en) * | 2014-03-07 | 2014-06-11 | 天津大学 | Method for preparing nitrogen dioxide gas sensor element with ultra-fast response characteristics |
| CN105056938A (en) * | 2015-08-27 | 2015-11-18 | 盐城工学院 | Method for improving photocatalytic activity of tungsten trioxide film |
| CN106415254A (en) * | 2014-05-23 | 2017-02-15 | 通用电气公司 | Fuse for detecting failure of gas trap |
| US10555091B2 (en) | 2017-09-15 | 2020-02-04 | Stmicroelectronics S.R.L. | Method for manufacturing a thin filtering membrane and an acoustic transducer device including the filtering membrane |
-
2002
- 2002-03-14 CN CN 02107410 patent/CN1210563C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101331080B (en) * | 2005-10-14 | 2012-12-26 | 意法半导体股份有限公司 | Substrate-level assembly for an integrated device, manufacturing process thereof and related integrated device |
| CN100412227C (en) * | 2006-07-25 | 2008-08-20 | 天津大学 | Magnetically controlled opposite target sputtering process of preparing gas-sensitive WO3 film sensor |
| CN100427939C (en) * | 2006-12-21 | 2008-10-22 | 天津大学 | Tungstic acid thin film air-sensitive sensor surface modifying method |
| CN101236170B (en) * | 2007-09-13 | 2012-08-29 | 陈东初 | Integrated all-solid-state pH electrochemical sensor based on nanometer tungsten oxide and method for making same |
| CN101303322B (en) * | 2008-07-08 | 2011-07-27 | 清华大学 | Surface modification method of WO3 thick film gas-sensitive sensor |
| CN103852494A (en) * | 2014-03-07 | 2014-06-11 | 天津大学 | Method for preparing nitrogen dioxide gas sensor element with ultra-fast response characteristics |
| CN106415254A (en) * | 2014-05-23 | 2017-02-15 | 通用电气公司 | Fuse for detecting failure of gas trap |
| CN105056938A (en) * | 2015-08-27 | 2015-11-18 | 盐城工学院 | Method for improving photocatalytic activity of tungsten trioxide film |
| US10555091B2 (en) | 2017-09-15 | 2020-02-04 | Stmicroelectronics S.R.L. | Method for manufacturing a thin filtering membrane and an acoustic transducer device including the filtering membrane |
| US11317219B2 (en) | 2017-09-15 | 2022-04-26 | Stmicroelectronics S.R.L. | Method for manufacturing a thin filtering membrane and an acoustic transducer device including the filtering membrane |
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