JP4630995B2 - Photocatalytic performance evaluation method by pulse photoexcitation surface hole content measurement - Google Patents
Photocatalytic performance evaluation method by pulse photoexcitation surface hole content measurement Download PDFInfo
- Publication number
- JP4630995B2 JP4630995B2 JP2000213772A JP2000213772A JP4630995B2 JP 4630995 B2 JP4630995 B2 JP 4630995B2 JP 2000213772 A JP2000213772 A JP 2000213772A JP 2000213772 A JP2000213772 A JP 2000213772A JP 4630995 B2 JP4630995 B2 JP 4630995B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- photocatalytic
- pulse
- light
- insulating sheet
- 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.)
- Expired - Fee Related
Links
- 230000001699 photocatalysis Effects 0.000 title claims description 24
- 238000005259 measurement Methods 0.000 title claims description 9
- 238000011156 evaluation Methods 0.000 title claims description 8
- 230000001443 photoexcitation Effects 0.000 title description 2
- 239000010409 thin film Substances 0.000 claims description 22
- 230000005284 excitation Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 2
- 238000000034 method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 239000005041 Mylar™ Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Images
Landscapes
- Analysing Materials By The Use Of Radiation (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は光触媒性能評価法に関するものであり、入射光として波長可変パルス光を用いることにより、瞬時に使用予定環境下での触媒性能を見積もることができ、さらに複雑な機構を持つ光触媒反応の劣化原因の解明にも役立つものである。
【０００２】
【従来の技術】
物質の光触媒性能を評価する場合、光触媒物質の持つバンドギャップ以上の光を照射しながら表面に塗布した油や、色素または反応ガスの分解量を時系列で観測する手法が取られるが、いずれも光触媒反応が微弱であるため、その触媒性能を観測するには長い時間（数十分以上）を必要とした。
【０００３】
また、光触媒性能の優劣を決定する原因は非常に複雑であり、物質表面に関して言えば反応表面積、表面酸化電位、結晶構造等であるが、これらを評価する手法はすでに確立しているのに対して、光触媒反応を起こすのに最も重要な役割を果たす正孔の表面への挙動を観測する手法は確立されていない。そのため、その物質のどの特性が触媒性能の優劣を決定しているのか不明瞭であった。
【０００４】
【発明が解決しようとする課題】
本発明は、光触媒物質にパルス光を入射し、表面に励起された正孔数をカウントすることで、その光触媒性能を瞬時に測定する手法を提供するものである。
【０００５】
【課題を解決するための手段】
本発明のパルス光励起表面正孔量測定による光触媒性能評価法は、光触媒薄膜の表面に透明な絶縁シートをかぶせ、それらを２枚の透明電極ではさみ、パルスレーザーを入射することで表面に励起された正孔数をデジタルオシロスコープで瞬時に観測することを特徴とする。入射パルスレーザーの波長を可変させることにより、その物質の光触媒性能の入射波長依存性も見積もることができる。
【０００６】
又、本発明のパルス光励起表面正孔量測定による光触媒性能評価法を行う装置は、光触媒薄膜、その片側に設けられた絶縁シート、絶縁シートを介して設けられた一方の透明電極、及び絶縁シートの反対側に設けられた他方の透明電極から構成される積層体を設置し、その積層体の絶縁シート側の透明電極に外部抵抗及びディジタルオシロスコープを結合し、他側の透明電極を接地することにより電気回路を構成し、同期信号発信器から同期信号をパルスレーザ及びディジタルオシロスコープに付与し、発生したパルスレーザーにより薄膜表面に励起された電荷を外部抵抗を通して放電すると同時にその抵抗値を電圧としてディジタルオシロスコープ上に表示し、得られた表示値を下記式１に付与してその際の量子効率を算出することにより、光触媒性能を評価する装置である。
【０００７】
【発明の実施の形態】
図１は本発明のパルス光励起表面正孔量測定回路のブロック図を示す説明図である。光触媒薄膜試料の表面にマイラーシート（絶縁シート）をかぶせ、透明導電膜が蒸着されたネサガラス（透明電極）で薄膜試料及びマイラーシートをはさむ。透明電極の光照射側端子は外部抵抗Ｒを通して接地し、透明電極の反対側はそのまま接地する。
【０００８】
励起光としてパルスレーザーを透明電極を通して薄膜試料に入射し、薄膜試料中に電子−正孔対分離が生じ薄膜試料表面に電荷が励起されると、密着しているマイラーシート（絶縁シート）に電荷が蓄えられる。貯えられた電荷は外部抵抗Ｒ［Ω］を通じて放電される。このＲでの放電電圧ｖを、入射光パルスと同期されたディジタルオシロスコープで時間軸（ｔ）測定を行う。マイラーシート（絶縁シート）、及び薄膜試料の合成容量をＣ［Ｆ］、表面に励起された総電荷量をΔｑ［Ｃ］とｓると、ｖは次式で表される。
【０００９】
【式１】
即ち、回路の合成容量Ｃ及び抵抗値Ｒが既知であれば光触媒薄膜表面に励起される総電荷量を求めることができ、同時にレーザーパルスのパワーを観測しておけば、入射フォトンに対して何個の正孔が光触媒反応に寄与でき得るか（量子効率）を求めることが可能となる。また、入射パルスの波長を変化させそれぞれの量子効率を求めておけば、実際に使用される環境下での光触媒性能を短時間で見積もることができる。以下本発明を実施例に基づいて説明する。
【００１１】
【実施例】
（実施例１）
光触媒薄膜試料としてレーザーアブレーション法で単結晶サファイア基板（１０ｍｍ×１０ｍｍ×０．５ｍｍｔ）上に製膜した二酸化チタン（ＴｉＯ2）薄膜を2枚用意した。製膜法はパルスレーザーデポジション法を用いた。製膜条件はいずれも、１パルス当たりのエネルギーを１００ｍＪ、繰り返し周波数１０ＨｚのＹＡＧレーザー（波長５３２ｎｍ）、基板温度４６０℃で３時間堆積させもので、酸素分圧のみ、試料Ａ：３０ｍＴｏｒｒと試料Ｂ：３５ｍＴｏｒｒとわずかに変化させた。両者をＸ線回折法により評価を行った結果、両サンプルともＴｉＯ2ルチル構造が優先的に成長していることが確認された他は違いは発見されなかった。
【００１２】
このようにして得られた２つのサンプル（試料Ａ及び試料Ｂ）に対して、パルス光励起表面正孔量測定を行った。入射光パルスとして、窒素レーザー（波長３３７ｎｍ、１パルス当たりのエネルギー５０μＪ、パルス幅５×１０-9ｓｅｃ）を用い、外部抵抗Ｒは１Ｍ［Ω］を使用した。測定結果を図２に示す。
【００１３】
図２は、本発明のパルス光励起表面正孔量測定法を用いて、酸化チタン薄膜に入射光として窒素レーザー（波長３３７ｎｍ、１パルス当たりのエネルギー５０μＪ、パルス幅５×１０-9ｓｅｃ）を照射した際の図１における抵抗Ｒ（＝１ＭΩ）での放電電圧波形である。本発明の測定波形より（１）式を用いて、表面に励起された総電荷量をΔｑ［Ｃ］を算出する。
【００１４】
この測定波形を式（１）を用いてフィッティング（（１）式の関数と測定波形が一致するようにパラメータΔｑを導き出す）を行い表面に移動した総電荷量Δｑ［Ｃ］を比較すると、試料Ａは試料Ｂより（この波長において）表面へ約１．３倍の正孔輸送能力を持っており、より高い光触媒性能を保持していることが推測される。
【００１５】
（実施例２）
実施例１で使用した２つの試料の実際の光触媒性能を評価するために、薄膜表面に有機色素（メチレンブルー溶液、濃度１ｍｍｏ１／ｌ）を塗布し、ＵＶ光（波長<４００ｎｍ）を照射しながら表面の色素の分解を吸光度変化として一定時間おきに観測した（真空理工株式会社製 光触媒評価チェッカーＰＣＣ−１を使用）。約２０分間のＵＶ照射後両者の分解量に違いが現れ始め、試料Ａが試料Ｂより光触媒性能が高いことが確認され、実施例１の結果を支持するものとなった。
【００１６】
なお今回は、実施例１において入射波長として３３７ｎｍを使用したが、波長を変化させ各々の波長における電荷輸送能力を測定しておけば、実際の利用環境下（自然光、室内蛍光灯など）での触媒性能を短時間で見積もることが可能である。
【００１７】
【発明の効果】
本発明は、これまで評価が困難であった“表面への正孔の移動し易さ”という光触媒性能の優劣を決定する新指標を導入することが可能となり、高活性光触媒の設計に役立つ。また、瞬時に光触媒性能を評価することができる、という本発明に特有の顕著な効果を生ずるものである。
【図面の簡単な説明】
【図１】図１は、本発明のパルス光励起表面正孔量測定回路のブロック図を示す説明図である。
【図２】図２は、本発明のパルス光励起表面正孔量測定結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocatalyst performance evaluation method, and by using wavelength-tunable pulsed light as incident light, it is possible to instantaneously estimate the catalyst performance under the intended use environment, and to further degrade the photocatalytic reaction having a complicated mechanism. It is also useful for elucidating the cause.
[0002]
[Prior art]
When evaluating the photocatalytic performance of a substance, a method of observing the amount of oil, pigment, or reactive gas decomposed in time series while irradiating light beyond the band gap of the photocatalytic substance is used. Since the photocatalytic reaction is weak, it took a long time (several tens of minutes) to observe the catalyst performance.
[0003]
In addition, the reasons for determining the superiority or inferiority of the photocatalytic performance are very complex. Regarding the surface of the material, the reaction surface area, surface oxidation potential, crystal structure, etc., while methods for evaluating these have already been established. Thus, a method for observing the behavior of holes, which plays the most important role in causing a photocatalytic reaction, to the surface has not been established. Therefore, it was unclear which characteristics of the material determined the superiority or inferiority of the catalyst performance.
[0004]
[Problems to be solved by the invention]
The present invention provides a technique for instantaneously measuring the photocatalytic performance of a photocatalytic substance by entering pulsed light and counting the number of holes excited on the surface.
[0005]
[Means for Solving the Problems]
The photocatalytic performance evaluation method by measuring the amount of holes on the surface of the photoexcited surface of the present invention is such that a transparent insulating sheet is placed on the surface of the photocatalytic thin film, sandwiched between two transparent electrodes, and excited by the pulse laser. It is characterized by instantaneously observing the number of holes with a digital oscilloscope. By varying the wavelength of the incident pulse laser, the dependence of the photocatalytic performance of the substance on the incident wavelength can also be estimated.
[0006]
In addition, the apparatus for performing the photocatalytic performance evaluation method by measuring the amount of surface hole of pulsed light excitation according to the present invention includes a photocatalytic thin film, an insulating sheet provided on one side thereof, one transparent electrode provided via the insulating sheet, and an insulating sheet A laminate composed of the other transparent electrode provided on the opposite side of the laminate is installed, an external resistor and a digital oscilloscope are connected to the transparent electrode on the insulating sheet side of the laminate, and the transparent electrode on the other side is grounded An electric circuit is constructed by applying a synchronizing signal from a synchronizing signal generator to a pulse laser and a digital oscilloscope, and the electric charge excited on the surface of the thin film by the generated pulse laser is discharged through an external resistor, and at the same time, the resistance value is digitalized as a voltage. By displaying on an oscilloscope and assigning the obtained display value to the following equation 1 to calculate the quantum efficiency at that time A device for evaluating the photocatalytic performance.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is an explanatory diagram showing a block diagram of a pulsed light excitation surface hole quantity measuring circuit of the present invention. A mylar sheet (insulating sheet) is placed on the surface of the photocatalytic thin film sample, and the thin film sample and the mylar sheet are sandwiched with nesa glass (transparent electrode) on which a transparent conductive film is deposited. The light irradiation side terminal of the transparent electrode is grounded through the external resistor R, and the opposite side of the transparent electrode is grounded as it is.
[0008]
When a pulse laser is incident on the thin film sample through the transparent electrode as excitation light and electron-hole pair separation occurs in the thin film sample and the charge is excited on the surface of the thin film sample, the charge is applied to the closely contacted mylar sheet (insulating sheet). Is stored. The stored charge is discharged through the external resistance R [Ω]. The discharge voltage v at R is measured on the time axis (t) with a digital oscilloscope synchronized with the incident light pulse. Assuming that the combined capacity of the Mylar sheet (insulating sheet) and the thin film sample is C [F] and the total charge excited on the surface is Δq [C], v is expressed by the following equation.
[0009]
[Formula 1]
That is, if the combined capacitance C and resistance value R of the circuit are known, the total amount of charge excited on the surface of the photocatalytic thin film can be obtained. At the same time, if the power of the laser pulse is observed, what is the amount of incident photons? It is possible to determine whether the number of holes can contribute to the photocatalytic reaction (quantum efficiency). Further, if the quantum efficiency is obtained by changing the wavelength of the incident pulse, it is possible to estimate the photocatalytic performance in an environment where it is actually used in a short time. Hereinafter, the present invention will be described based on examples.
[0011]
【Example】
Example 1
Two titanium dioxide (TiO 2 ) thin films formed on a single crystal sapphire substrate (10 mm × 10 mm × 0.5 mmt) by a laser ablation method were prepared as photocatalytic thin film samples. The film forming method was a pulse laser deposition method. The film forming conditions are as follows: a YAG laser (wavelength of 532 nm) with an energy per pulse of 100 mJ and a repetition frequency of 10 Hz, and a substrate temperature of 460 ° C., deposited for 3 hours. Only oxygen partial pressure, sample A: 30 mTorr and sample B : Slightly changed to 35 mTorr. As a result of evaluating both by the X-ray diffraction method, no difference was found except that both samples confirmed that the TiO 2 rutile structure was preferentially grown.
[0012]
The two samples (sample A and sample B) thus obtained were subjected to pulsed photoexcitation surface hole amount measurement. As the incident light pulse, a nitrogen laser (wavelength 337 nm, energy per pulse 50 μJ, pulse width 5 × 10 −9 sec) was used, and the external resistance R was 1 M [Ω]. The measurement results are shown in FIG.
[0013]
FIG. 2 shows that the titanium oxide thin film is irradiated with a nitrogen laser (wavelength 337 nm, energy per pulse 50 μJ, pulse width 5 × 10 −9 sec) as incident light on the titanium oxide thin film by using the pulsed light excitation surface hole quantity measurement method of the present invention. 2 is a discharge voltage waveform at a resistance R (= 1 MΩ) in FIG. From the measurement waveform of the present invention, using equation (1), Δq [C] is calculated from the total amount of charges excited on the surface.
[0014]
When this measurement waveform is fitted using Equation (1) (parameter Δq is derived so that the function of Equation (1) matches the measurement waveform) and the total charge amount Δq [C] moved to the surface is compared, It is surmised that A has a hole transport capability about 1.3 times that of sample B (at this wavelength) to the surface and retains higher photocatalytic performance.
[0015]
(Example 2)
In order to evaluate the actual photocatalytic performance of the two samples used in Example 1, an organic dye (methylene blue solution, concentration 1 mmol / l) was applied to the surface of the thin film, and the surface was irradiated with UV light (wavelength <400 nm). Was observed at regular intervals as a change in absorbance (using a photocatalyst evaluation checker PCC-1 manufactured by Vacuum Riko Co., Ltd.). After the UV irradiation for about 20 minutes, a difference began to appear between the two, and it was confirmed that Sample A had higher photocatalytic performance than Sample B, which supported the results of Example 1.
[0016]
In this example, 337 nm was used as the incident wavelength in Example 1. However, if the charge transport capability at each wavelength is measured by changing the wavelength, the actual use environment (natural light, indoor fluorescent lamp, etc.) can be used. It is possible to estimate the catalyst performance in a short time.
[0017]
【The invention's effect】
The present invention makes it possible to introduce a new index for determining the superiority or inferiority of photocatalytic performance such as “ease of movement of holes to the surface”, which has been difficult to evaluate, and is useful for designing highly active photocatalysts. Moreover, the remarkable effect peculiar to this invention that the photocatalyst performance can be evaluated instantaneously is produced.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram showing a block diagram of a pulsed light excitation surface hole quantity measurement circuit of the present invention.
FIG. 2 is a graph showing the measurement results of the pulsed light excitation surface hole amount of the present invention.
Claims (3)
絶縁シートを被せた薄膜を挟むための１対の透明電極；A pair of transparent electrodes for sandwiching a thin film covered with an insulating sheet;
薄膜表面に励起光を入射するためのパルスレーザー源；A pulsed laser source to make the excitation light incident on the thin film surface
薄膜からの放電電圧を測定するためのオシロスコープ；及びAn oscilloscope for measuring the discharge voltage from the thin film; and
前記パルスレーザー源と前記オシロスコープとを同期させるための同期手段；Synchronization means for synchronizing the pulsed laser source and the oscilloscope;
を具備する、光触媒性能評価装置。A photocatalyst performance evaluation device comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213772A JP4630995B2 (en) | 2000-07-14 | 2000-07-14 | Photocatalytic performance evaluation method by pulse photoexcitation surface hole content measurement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213772A JP4630995B2 (en) | 2000-07-14 | 2000-07-14 | Photocatalytic performance evaluation method by pulse photoexcitation surface hole content measurement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002031612A JP2002031612A (en) | 2002-01-31 |
| JP4630995B2 true JP4630995B2 (en) | 2011-02-09 |
Family
ID=18709469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000213772A Expired - Fee Related JP4630995B2 (en) | 2000-07-14 | 2000-07-14 | Photocatalytic performance evaluation method by pulse photoexcitation surface hole content measurement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4630995B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4599547B2 (en) * | 2001-09-28 | 2010-12-15 | 独立行政法人 日本原子力研究開発機構 | Two-layer photocatalytic titanium oxide film and method for producing the same |
| KR20040043895A (en) * | 2002-11-20 | 2004-05-27 | 주식회사 유진텍 이십일 | Apparatus for measuring photocatalytic activity and method using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11258206A (en) * | 1998-03-16 | 1999-09-24 | Ebara Corp | Method and device for evaluating photocatalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3247857B2 (en) * | 1997-09-09 | 2002-01-21 | 宇部日東化成株式会社 | Method and apparatus for measuring photocatalytic activity |
| JP2001183321A (en) * | 1999-12-28 | 2001-07-06 | Research Institute Of Innovative Technology For The Earth | Method for evaluating photocatalytic film |
-
2000
- 2000-07-14 JP JP2000213772A patent/JP4630995B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11258206A (en) * | 1998-03-16 | 1999-09-24 | Ebara Corp | Method and device for evaluating photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002031612A (en) | 2002-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tsuji et al. | Electrocatalytic activity of amorphous RuO2 electrode for oxygen evolution in an aqueous solution | |
| Chidsey et al. | Micrometer-spaced platinum interdigitated array electrode: fabrication, theory, and initial use | |
| Heimer et al. | Direct time-resolved infrared measurement of electron injection in dye-sensitized titanium dioxide films | |
| Leung et al. | Extending surface-enhanced Raman spectroscopy to transition-metal surfaces: carbon monoxide adsorption and electrooxidation on platinum-and palladium-coated gold electrodes | |
| Tadjeddine et al. | Vibrational spectroscopy of the electrochemical interface by visible-infrared sum-frequency generation | |
| US7141859B2 (en) | Porous gas sensors and method of preparation thereof | |
| Nakade et al. | Enhancement of electron transport in nano-porous TiO2 electrodes by dye adsorption | |
| JP2504897B2 (en) | How to use electronic components containing fullerenes | |
| Lomoth et al. | Redox‐Switchable Direction of Photoinduced Electron Transfer in an Ru (bpy) 32+–Viologen Dyad | |
| Yu et al. | In-situ spectroscopic studies of electrochromic hydrated nickel oxide films | |
| EP2154520A1 (en) | Gas sensor, gas measuring system using the gas sensor, and gas detection module for the gas measuring system | |
| Iwai et al. | Ultrafast interfacial charge separation processes from the singlet and triplet MLCT states of Ru (bpy) 2 (dcbpy) adsorbed on nanocrystalline SnO2 under negative applied bias | |
| Gomes et al. | Ethanol electro-oxidation over Pt (h k l): Comparative study on the reaction intermediates probed by FTIR and SFG spectroscopies | |
| Fawcett et al. | Kinetics and thermodynamics of the electroreduction of buckminsterfullerene in benzonitrile | |
| JP4630995B2 (en) | Photocatalytic performance evaluation method by pulse photoexcitation surface hole content measurement | |
| Bozzini et al. | In situ spectroelectrochemical measurements during the electro-oxidation of ethanol on WC-supported Pt-black, based on sum-frequency generation spectroscopy | |
| Hernández-Balaguera et al. | The dominant role of memory-based capacitive hysteretic currents in operation of photovoltaic perovskites | |
| Sato et al. | The effect of CdS on the charge separation and recombination dynamics in PbS/CdS double-layered quantum dot sensitized solar cells | |
| Katsuta et al. | Electrical properties of rutile (TiO2) thin film | |
| Yoshimura et al. | Light emission from tracking discharges on organic insulation | |
| JP2002257812A (en) | Method for evaluating performance of semiconductor photocatalyst by complementary measurement of pulse laser light-excited surface carrier | |
| Goossens et al. | A photoelectrochemical impedance spectroscopic study of passive metals | |
| Balog et al. | The effect of trap states on the optoelectronic properties of nanoporous nickel oxide | |
| Jennings et al. | In situ spectroelectrochemical studies of the fluorescence of 5-substituted indole trimer films | |
| Nakabayashi et al. | Surface state assisted electron tunneling through a space charge layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20060223 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070713 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100716 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100824 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100916 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101015 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131126 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |