WO2018212007A1 - Method for electrochemically producing germane - Google Patents
Method for electrochemically producing germane Download PDFInfo
- Publication number
- WO2018212007A1 WO2018212007A1 PCT/JP2018/017649 JP2018017649W WO2018212007A1 WO 2018212007 A1 WO2018212007 A1 WO 2018212007A1 JP 2018017649 W JP2018017649 W JP 2018017649W WO 2018212007 A1 WO2018212007 A1 WO 2018212007A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cathode
- geh
- germane
- electrolytic solution
- anode
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
Definitions
- the present invention relates to a method for producing germane electrochemically.
- germane As a raw material for producing the SiGe substrate, germane (GeH 4 ) is used, and it is expected that the amount of GeH 4 used will increase as the use of the SiGe substrate increases.
- Patent Document 1 describes that GeH 4 can be produced electrochemically with high current efficiency by using a Cu alloy or Sn alloy as a cathode. ing.
- Non-Patent Document 1 discloses that as a result of screening Pt, Zn, Ti, graphite, Cu, Ni, Cd, Pb, and Sn as cathodes used when electrochemically producing GeH 4 , Cd or Cu is present. It describes that it was optimal in terms of current efficiency and contamination.
- Non-Patent Document 2 As a result of investigating a plurality of cathodes as cathodes used when electrochemically producing GeH 4 , the hydrogenation rate was 99% or more when Hg was used as the cathode. It is disclosed.
- the conventional method for electrochemically producing GeH 4 as described in the above-mentioned document is, for example, that the cathode (bronze manufactured by McMaster-Carr) used in the example of Patent Document 1 is plated or coated.
- GeH 4 is industrially produced because it is difficult to apply a method such that an effective element exists only on the surface, and the toxicity of the cathode (Hg) used in Non-Patent Document 2 is high. It was unsuitable as a method.
- One embodiment of the present invention provides an industrially advantageous method for producing GeH 4 electrochemically.
- a configuration example of the present invention is as follows.
- a method for producing germane electrochemically by energizing an electrolytic solution containing a germanium compound in an electrochemical cell having a diaphragm, an anode and a cathode containing silver to generate germane at the cathode.
- the electrolytic solution is an electrolytic solution containing germanium dioxide and an ionic substance.
- the ionic substance is potassium hydroxide or sodium hydroxide.
- GeH 4 can be produced electrochemically in an industrially advantageous manner, particularly with high current efficiency.
- FIG. 1 is a schematic diagram of the apparatus used in the examples.
- An electrochemical method for producing GeH 4 according to an embodiment of the present invention includes a germanium compound in an electrochemical cell having a diaphragm, an anode, and a cathode including silver.
- the electrolytic solution is energized to generate GeH 4 at the cathode to produce GeH 4 electrochemically.
- GeH 4 can be produced electrochemically with an industrially advantageous method, particularly with high current efficiency. Therefore, by using GeH 4 obtained by this method, the SiGe substrate can be produced industrially advantageously.
- Such industrial reactions include, for example, reactions on a scale such that the electrolyte capacity is 500 to 2500 L, the number of cells is 30 to 150, and the current used is 100 to 300 A.
- GeH 4 can be produced with a current efficiency of preferably 10 to 90%, more preferably 12 to 40%.
- the said current efficiency can be specifically measured by the method as described in the following Example.
- the electrochemical cell is not particularly limited as long as it has a diaphragm, an anode, and the cathode, and a conventionally known cell can be used.
- Specific examples of the cell include a cell in which an anode chamber including an anode and a cathode chamber including a cathode are separated using a diaphragm.
- the cathode is not particularly limited as long as it contains Ag.
- the cathode may be an electrode made of metal Ag, an electrode made of an Ag-based alloy containing Ag as a main component, or an electrode plated or coated with metal Ag or an Ag alloy.
- Examples of the plated or coated electrode include an electrode obtained by plating or coating a metal Ag or an Ag alloy on a substrate such as Ni.
- metal Ag is expensive, it is preferably an electrode plated or coated with metal Ag or an Ag alloy from the viewpoint of cost.
- the shape of the cathode is not particularly limited, and may be any of a plate shape, a column shape, a hollow shape, and the like. Further, the size, surface area, etc. of the cathode are not particularly limited.
- the anode is not particularly limited, and an anode conventionally used in electrochemical production of GeH 4 may be used.
- An electrode made of a conductive metal such as Ni and Pt, and the conductive metal may be used.
- An electrode made of an alloy containing the main component is preferable, and an electrode made of Ni is preferable from the viewpoint of cost.
- the anode may be an electrode plated or coated with the conductive metal or an alloy containing the metal, as with the cathode.
- the shape, size, surface area, etc. of the anode are not particularly limited as in the case of the cathode.
- the diaphragm is not particularly limited, and a diaphragm that has been conventionally used in electrochemical cells and that can separate the anode chamber and the cathode chamber may be used.
- various electrolyte membranes and porous membranes can be used.
- the electrolyte membrane include polymer electrolyte membranes such as ion exchange solid polymer electrolyte membranes, specifically NAFION (registered trademark) 115, 117, NRE-212 (manufactured by Sigma-Aldrich).
- the porous film porous ceramics such as porous glass, porous alumina and porous titania, porous polymers such as porous polyethylene and porous propylene, and the like can be used.
- the electrochemical cell is divided into an anode chamber and a cathode chamber by the diaphragm, the O 2 gas generated at the anode and the GeH 4 generated at the cathode are not mixed, and the respective electrode chambers are mixed. It can be taken out from an independent outlet.
- O 2 gas and GeH 4 are mixed, the O 2 gas and GeH 4 react with each other and the yield of GeH 4 tends to decrease.
- GeH 4 is produced from an electrolytic solution containing a germanium compound.
- the electrolytic solution is preferably an aqueous solution.
- GeO 2 is preferable.
- concentration be saturated with respect to the solvent, preferably water.
- the electrolytic solution preferably contains an ionic substance in order to improve the conductivity of the electrolytic solution and promote the solubility of GeO 2 in water.
- an ionic substance a conventionally known ionic substance used in electrochemistry can be used, but KOH or NaOH is preferable from the viewpoint of excellent effects. Among these, KOH is preferable because KOH aqueous solution is more excellent in conductivity than NaOH aqueous solution.
- the concentration of KOH in the electrolytic solution is preferably 1 to 8 mol / L, more preferably 2 to 5 mol / L.
- concentration of KOH is within the above range, an electrolytic solution having a high GeO 2 concentration can be easily obtained, and GeH 4 can be efficiently produced with high current efficiency.
- concentration of KOH is less than the lower limit of the above range, the conductivity of the electrolyte solution tends to be low, a high voltage may be required for the production of GeH 4 , and the dissolved amount of GeO 2 in water Tends to decrease, and the reaction efficiency may decrease.
- concentration of KOH exceeds the upper limit of the above range, a material having high corrosion resistance tends to be required as the material of the electrode or cell, which may increase the cost of the apparatus.
- the magnitude of the current per unit area (current density) of the cathode when producing GeH 4 (when the current is applied) is excellent in the reaction rate, and can produce GeH 4 with high current efficiency. Therefore, it is preferably 30 to 500 mA / cm 2 , more preferably 50 to 400 mA / cm 2 .
- the current density is in the above range, the amount of hydrogen gas generated by electrolysis of water can be appropriately controlled without reducing the generation rate of GeH 4 per unit time and the reaction efficiency.
- the reaction temperature in (when generating the GeH 4) for producing a GeH 4 is excellent in reaction rate, in terms of such can be produced GeH 4 at a low cost, preferably 5 ⁇ 100 ° C., more preferably 10 to 40 ° C.
- the power consumption for heating the cell can be appropriately controlled without reducing the reaction efficiency.
- the reaction atmosphere (the gas phase portions of the anode chamber and the cathode chamber) when producing GeH 4 is not particularly limited, but is preferably an inert gas atmosphere, and nitrogen gas is preferable as the inert gas.
- the electrolytic solution in the electrochemical cell may remain stationary, may be stirred, or may be separately circulated by providing another liquid tank.
- the other liquid tank is provided and circulated, the change in the concentration of the reaction solution becomes relatively small, the current efficiency can be stabilized, and the GeO 2 concentration on the electrode surface is kept high, and the reaction rate is increased. Improvement can be expected. For this reason, it is preferable to circulate the said electrolyte solution in an electrochemical cell.
- ⁇ GeH 4 production equipment> This method is not particularly limited as long as the electrochemical cell is used.
- a power source measuring means (FT-IR, pressure gauge (PI), integrating meter, etc.),
- An apparatus having a conventionally known member such as a nitrogen gas (N 2 ) supply path, a mass flow controller (MFC), or an exhaust path can be used.
- N 2 nitrogen gas
- MFC mass flow controller
- Example 1 A vinyl chloride electrochemical cell having the anode chamber and the cathode chamber separated by a diaphragm as shown in FIG. 1 was prepared using the following materials.
- Cathode 0.5 cm ⁇ 0.5 cm ⁇ 0.5 mm thick Ag plate
- Anode 2 cm ⁇ 2 cm ⁇ 0.5 mm thick Ni plate
- Diaphragm Nafion (registered trademark) NRE-212 (manufactured by Sigma Aldrich) )
- Electrolyte solution Liquid obtained by dissolving GeO 2 at a concentration of 90 g / L in a 4 mol / L KOH aqueous solution.
- Electrolyte solution introduced into the cathode chamber 100 mL ⁇
- Amount of electrolyte introduced into the anode chamber 100 mL Standard electrode: A silver-silver chloride electrode is installed at the cathode
- the current efficiency is calculated from the amount of GeH 4 generated between 0 and 10 minutes after the current is applied and the applied current amount based on the following formula, and the current efficiency is the current efficiency for a reaction time of 10 minutes. It was. The results are shown in Table 1.
- Current efficiency (%) [Electric amount (C / min) ⁇ 10 (min) ⁇ 100] corresponding to generation of GeH 4 in the generation amount (mmol / min) / 100 Total applied electric amount (C / min) ⁇ 10 (min)]
- Example 1 The reaction was carried out under the same conditions as in Example 1 except that a 0.5 cm ⁇ 0.5 cm ⁇ 0.5 mm thick Cu plate was used as the cathode and the applied current was changed to ⁇ 85 mA for 10 minutes. The results are shown in Table 1.
- Example 2 The reaction was performed under the same conditions as in Example 1 except that a Cd plate having a size of 0.5 cm ⁇ 0.5 cm ⁇ thickness 0.5 mm was used as the cathode and the applied current was changed to ⁇ 55 mA for 10 minutes. The results are shown in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
該SiGe基板を作製する際の原料として、ゲルマン(GeH4)が使用されており、SiGe基板の使用の増加に伴い、GeH4の使用量も増加すると予想される。 Conventionally, high speed and low power consumption of semiconductor devices have been achieved by miniaturization of the devices, but strained silicon such as SiGe substrates has attracted attention as a technology for further speeding up and low power consumption. ing.
As a raw material for producing the SiGe substrate, germane (GeH 4 ) is used, and it is expected that the amount of GeH 4 used will increase as the use of the SiGe substrate increases.
本発明の構成例は以下の通りである。 As a result of intensive studies to solve the above problems, the present inventor found that the above problems can be solved by the following production method and the like, and has completed the present invention.
A configuration example of the present invention is as follows.
[3] 前記イオン性物質が、水酸化カリウムまたは水酸化ナトリウムである、[2]に記載の製造方法。
[4] 前記イオン性物質が水酸化カリウムであり、前記電解液中の水酸化カリウムの濃度が1~8mol/Lである、[2]または[3]に記載の製造方法。 [2] The manufacturing method according to [1], wherein the electrolytic solution is an electrolytic solution containing germanium dioxide and an ionic substance.
[3] The production method according to [2], wherein the ionic substance is potassium hydroxide or sodium hydroxide.
[4] The production method according to [2] or [3], wherein the ionic substance is potassium hydroxide, and the concentration of potassium hydroxide in the electrolytic solution is 1 to 8 mol / L.
[6] 前記ゲルマンを発生させる際の反応温度が5~100℃である、[1]~[5]のいずれかに記載の製造方法。 [5] The production method according to any one of [1] to [4], wherein the current density of the cathode during the energization is 30 to 500 mA / cm 2 .
[6] The production method according to any one of [1] to [5], wherein a reaction temperature for generating the germane is 5 to 100 ° C.
本発明の一実施形態に係る電気化学的にGeH4を製造する方法(以下「本方法」ともいう。)は、隔膜、陽極および銀を含む陰極を有する電気化学セル中で、ゲルマニウム化合物を含む電解液に通電して、陰極においてGeH4を発生させて、電気化学的にGeH4を製造する。
本方法によれば、工業的に有利な方法、特に高い電流効率でGeH4を電気化学的に製造することができる。従って、本方法で得られたGeH4を用いることで、SiGe基板を工業的に有利に製造することもできる。 «Electrochemical method for producing a GeH 4»
An electrochemical method for producing GeH 4 according to an embodiment of the present invention (hereinafter also referred to as “the present method”) includes a germanium compound in an electrochemical cell having a diaphragm, an anode, and a cathode including silver. The electrolytic solution is energized to generate GeH 4 at the cathode to produce GeH 4 electrochemically.
According to this method, GeH 4 can be produced electrochemically with an industrially advantageous method, particularly with high current efficiency. Therefore, by using GeH 4 obtained by this method, the SiGe substrate can be produced industrially advantageously.
なお、前記電流効率は、具体的には、下記実施例に記載の方法で測定することができる。 According to this method, GeH 4 can be produced with a current efficiency of preferably 10 to 90%, more preferably 12 to 40%.
In addition, the said current efficiency can be specifically measured by the method as described in the following Example.
前記電気化学セルとしては、隔膜、陽極および前記陰極を有すれば特に制限されず、従来公知のセルを用いることができる。
該セルとしては、具体的には、陽極を含む陽極室と、陰極を含む陰極室とを隔膜を用いて隔てたセル等が挙げられる。 <Electrochemical cell>
The electrochemical cell is not particularly limited as long as it has a diaphragm, an anode, and the cathode, and a conventionally known cell can be used.
Specific examples of the cell include a cell in which an anode chamber including an anode and a cathode chamber including a cathode are separated using a diaphragm.
前記陰極は、Agを含めば特に制限されない。
該陰極は、金属Agからなる電極やAgを主成分とするAg基合金からなる電極であってもよいし、金属AgまたはAg合金をメッキまたはコーティングした電極であってもよい。
前記メッキまたはコーティングした電極としては、Ni等の基材に金属AgまたはAg合金をメッキまたはコーティングした電極等が挙げられる。
これらの中でも、金属Agは高価であるため、コストの面からは、金属AgまたはAg合金をメッキまたはコーティングした電極であることが好ましい。 <Cathode>
The cathode is not particularly limited as long as it contains Ag.
The cathode may be an electrode made of metal Ag, an electrode made of an Ag-based alloy containing Ag as a main component, or an electrode plated or coated with metal Ag or an Ag alloy.
Examples of the plated or coated electrode include an electrode obtained by plating or coating a metal Ag or an Ag alloy on a substrate such as Ni.
Among these, since metal Ag is expensive, it is preferably an electrode plated or coated with metal Ag or an Ag alloy from the viewpoint of cost.
また、前記陰極の大きさ、表面積等も特に制限されない。 The shape of the cathode is not particularly limited, and may be any of a plate shape, a column shape, a hollow shape, and the like.
Further, the size, surface area, etc. of the cathode are not particularly limited.
前記陽極としては、特に制限されず、電気化学的にGeH4を製造する際に従来用いられてきた陽極を用いればよいが、NiおよびPt等の導電性金属からなる電極、該導電性金属を主成分とする合金からなる電極等が好ましく、コストの面から、Niからなる電極が好ましい。
また、前記陽極は、陰極と同様に、前記導電性金属または該金属を含む合金をメッキまたはコーティングした電極を使用してもよい。
前記陽極の形状、大きさ、表面積等も、前記陰極と同様に特に制限されない。 <Anode>
The anode is not particularly limited, and an anode conventionally used in electrochemical production of GeH 4 may be used. An electrode made of a conductive metal such as Ni and Pt, and the conductive metal may be used. An electrode made of an alloy containing the main component is preferable, and an electrode made of Ni is preferable from the viewpoint of cost.
The anode may be an electrode plated or coated with the conductive metal or an alloy containing the metal, as with the cathode.
The shape, size, surface area, etc. of the anode are not particularly limited as in the case of the cathode.
前記隔膜としては、特に制限されず、電気化学セルに従来用いられてきた、陽極室と陰極室とを隔てることが可能な隔膜を用いればよい。
このような隔膜としては、種々の電解質膜や多孔質膜を用いることができる。
電解質膜としては、高分子電解質膜、例えばイオン交換固体高分子電解質膜、具体的には、NAFION(登録商標)115、117、NRE-212(シグマアルドリッチ社製)等が挙げられる。
多孔質膜としては、多孔質ガラス、多孔質アルミナ、多孔質チタニア等の多孔質セラミックス、多孔質ポリエチレン、多孔質プロピレン等の多孔質ポリマー等を用いることができる。 <Diaphragm>
The diaphragm is not particularly limited, and a diaphragm that has been conventionally used in electrochemical cells and that can separate the anode chamber and the cathode chamber may be used.
As such a diaphragm, various electrolyte membranes and porous membranes can be used.
Examples of the electrolyte membrane include polymer electrolyte membranes such as ion exchange solid polymer electrolyte membranes, specifically NAFION (registered trademark) 115, 117, NRE-212 (manufactured by Sigma-Aldrich).
As the porous film, porous ceramics such as porous glass, porous alumina and porous titania, porous polymers such as porous polyethylene and porous propylene, and the like can be used.
O2ガスとGeH4とが混合すると、O2ガスとGeH4とが反応して、GeH4の収率が低下する傾向にある。 In one embodiment of the present invention, since the electrochemical cell is divided into an anode chamber and a cathode chamber by the diaphragm, the O 2 gas generated at the anode and the GeH 4 generated at the cathode are not mixed, and the respective electrode chambers are mixed. It can be taken out from an independent outlet.
When O 2 gas and GeH 4 are mixed, the O 2 gas and GeH 4 react with each other and the yield of GeH 4 tends to decrease.
本方法では、ゲルマニウム化合物を含む電解液からGeH4を製造する。
該電解液は、好ましくは水溶液である。 <Electrolytic solution containing germanium compound>
In this method, GeH 4 is produced from an electrolytic solution containing a germanium compound.
The electrolytic solution is preferably an aqueous solution.
前記電解液中のGeO2の濃度は、高い方が反応速度が速くなり、効率的にGeH4を合成できるため、溶媒、好ましくは水に対する飽和濃度にすることが好ましい。 As the germanium compound, GeO 2 is preferable.
The higher the concentration of GeO 2 in the electrolytic solution, the faster the reaction rate and the efficient synthesis of GeH 4 , so it is preferable that the concentration be saturated with respect to the solvent, preferably water.
該イオン性物質としては、電気化学に用いられる従来公知のイオン性物質を用いることができるが、前記効果に優れる等の点から、KOHまたはNaOHが好ましい。これらの中でも、KOH水溶液は、NaOH水溶液に比べより導電性に優れるため、KOHが好ましい。 The electrolytic solution preferably contains an ionic substance in order to improve the conductivity of the electrolytic solution and promote the solubility of GeO 2 in water.
As the ionic substance, a conventionally known ionic substance used in electrochemistry can be used, but KOH or NaOH is preferable from the viewpoint of excellent effects. Among these, KOH is preferable because KOH aqueous solution is more excellent in conductivity than NaOH aqueous solution.
KOHの濃度が前記範囲にあると、GeO2濃度の高い電解液を容易に得ることができ、高い電流効率でGeH4を効率的に製造することができる。
KOHの濃度が前記範囲の下限未満であると、電解液の導電性が低くなる傾向にあり、GeH4の製造に高電圧が必要になる場合があり、また、GeO2の水への溶解量が低下する傾向にあり、反応効率が低下する場合がある。一方、KOHの濃度が前記範囲の上限を超えると、電極やセルの材質として耐食性の高い材質が必要になる傾向にあり、装置のコストが高くなる場合がある。 The concentration of KOH in the electrolytic solution is preferably 1 to 8 mol / L, more preferably 2 to 5 mol / L.
When the concentration of KOH is within the above range, an electrolytic solution having a high GeO 2 concentration can be easily obtained, and GeH 4 can be efficiently produced with high current efficiency.
If the concentration of KOH is less than the lower limit of the above range, the conductivity of the electrolyte solution tends to be low, a high voltage may be required for the production of GeH 4 , and the dissolved amount of GeO 2 in water Tends to decrease, and the reaction efficiency may decrease. On the other hand, if the concentration of KOH exceeds the upper limit of the above range, a material having high corrosion resistance tends to be required as the material of the electrode or cell, which may increase the cost of the apparatus.
本方法において、GeH4を製造する際(前記通電の際)の陰極の単位面積当たりの電流の大きさ(電流密度)は、反応速度に優れ、高い電流効率でGeH4を製造できる等の点から、好ましくは30~500mA/cm2、より好ましくは50~400mA/cm2である。
電流密度が前記範囲にあると、単位時間当たりのGeH4の発生速度や反応効率を低下させることなく、水の電気分解による水素ガスの発生量を適度に制御することもできる。 <Reaction conditions>
In this method, the magnitude of the current per unit area (current density) of the cathode when producing GeH 4 (when the current is applied) is excellent in the reaction rate, and can produce GeH 4 with high current efficiency. Therefore, it is preferably 30 to 500 mA / cm 2 , more preferably 50 to 400 mA / cm 2 .
When the current density is in the above range, the amount of hydrogen gas generated by electrolysis of water can be appropriately controlled without reducing the generation rate of GeH 4 per unit time and the reaction efficiency.
反応温度が前記範囲にあると、反応効率を低下させることなく、セルの加熱のための電力消費を適度に制御することもできる。 The reaction temperature in (when generating the GeH 4) for producing a GeH 4 is excellent in reaction rate, in terms of such can be produced GeH 4 at a low cost, preferably 5 ~ 100 ° C., more preferably 10 to 40 ° C.
When the reaction temperature is within the above range, the power consumption for heating the cell can be appropriately controlled without reducing the reaction efficiency.
前記他の液槽を設けて循環流通させた場合、反応液濃度の変化が相対的に小さくなり、電流効率の安定化が期待できるとともに、電極表面のGeO2濃度が高く保たれ、反応速度の向上が期待できる。このため、電気化学セル中の前記電解液は循環流通させることが好ましい。 In this method, the electrolytic solution in the electrochemical cell may remain stationary, may be stirred, or may be separately circulated by providing another liquid tank.
When the other liquid tank is provided and circulated, the change in the concentration of the reaction solution becomes relatively small, the current efficiency can be stabilized, and the GeO 2 concentration on the electrode surface is kept high, and the reaction rate is increased. Improvement can be expected. For this reason, it is preferable to circulate the said electrolyte solution in an electrochemical cell.
本方法では、前記電気化学セルを用いれば特に制限されないが、該セル以外に、例えば、図1に示すような、電源、測定手段(FT-IR、圧力計(PI)、積算計等)、窒素ガス(N2)供給路、マスフローコントローラー(MFC)、排気路など、従来公知の部材を有する装置を用いることができる。
また、図示しない、前述の循環流路等を有する装置を用いてもよい。 <GeH 4 production equipment>
This method is not particularly limited as long as the electrochemical cell is used. In addition to the cell, for example, as shown in FIG. 1, a power source, measuring means (FT-IR, pressure gauge (PI), integrating meter, etc.), An apparatus having a conventionally known member such as a nitrogen gas (N 2 ) supply path, a mass flow controller (MFC), or an exhaust path can be used.
Moreover, you may use the apparatus which has the above-mentioned circulation flow path etc. which is not illustrated.
以下の材料を用い、図1に示すような、隔膜で陽極室と陰極室とを隔てた塩化ビニル製電気化学セルを作製した。
・陰極:0.5cm×0.5cm×厚さ0.5mmのAg板
・陽極:2cm×2cm×厚さ0.5mmのNi板
・隔膜:ナフィオン(登録商標) NRE-212(シグマアルドリッチ社製)
・電解液:4mol/LのKOH水溶液に90g/Lの濃度でGeO2を溶解させた液体
・陰極室への電解液導入量:100mL
・陽極室への電解液導入量:100mL
・標準電極:銀-塩化銀電極を陰極に設置 [Example 1]
A vinyl chloride electrochemical cell having the anode chamber and the cathode chamber separated by a diaphragm as shown in FIG. 1 was prepared using the following materials.
Cathode: 0.5 cm × 0.5 cm × 0.5 mm thick Ag plate Anode: 2 cm × 2 cm × 0.5 mm thick Ni plate Diaphragm: Nafion (registered trademark) NRE-212 (manufactured by Sigma Aldrich) )
Electrolyte solution: Liquid obtained by dissolving GeO 2 at a concentration of 90 g / L in a 4 mol / L KOH aqueous solution. Electrolyte solution introduced into the cathode chamber: 100 mL
・ Amount of electrolyte introduced into the anode chamber: 100 mL
Standard electrode: A silver-silver chloride electrode is installed at the cathode
なお、電流を流す際に電気化学セルの温度をコントロールしなかったところ、反応温度は14℃であった。
陰極室の出口ガスを、積算計を用いて測定することで、反応により生じた出口ガス全量(GeH4および水素ガスを含むガス)を測定し、FT-IRを用いることで、出口ガス全量中のGeH4濃度を測定した。これらの測定結果から、GeH4の発生量を算出した。 After the gas phase portions of the anode chamber and the cathode chamber in the obtained electrochemical cell were purged with nitrogen gas (N 2 ), Hokuto Denko Corporation's Hz-5000 was used as a power source, and current was kept at −57 mA for 10 minutes. To produce GeH 4 electrochemically. The current density at this time was 99 mA / cm 2 .
When the temperature of the electrochemical cell was not controlled when the current was passed, the reaction temperature was 14 ° C.
The outlet gas of the cathode chamber, by measuring with integrating meter, the outlet gas total amount produced by the reaction (gas containing GeH 4 and hydrogen gas) was measured by using FT-IR, the outlet gas total amount of The GeH 4 concentration of was measured. From these measurement results, the amount of GeH 4 generated was calculated.
電流効率(%)=[前記発生量(mmol/min)のGeH4が発生するのに相当する電気量(C/min)×10(min)×100]/[印加した全電気量(C/min)×10(min)] The current efficiency is calculated from the amount of GeH 4 generated between 0 and 10 minutes after the current is applied and the applied current amount based on the following formula, and the current efficiency is the current efficiency for a reaction time of 10 minutes. It was. The results are shown in Table 1.
Current efficiency (%) = [Electric amount (C / min) × 10 (min) × 100] corresponding to generation of GeH 4 in the generation amount (mmol / min) / 100 Total applied electric amount (C / min) × 10 (min)]
陰極として0.5cm×0.5cm×厚さ0.5mmのCu板を使用し、印加する電流を-85mAで10分間に変更した以外は実施例1と同様の条件で反応を行った。結果を表1に示す。 [Comparative Example 1]
The reaction was carried out under the same conditions as in Example 1 except that a 0.5 cm × 0.5 cm × 0.5 mm thick Cu plate was used as the cathode and the applied current was changed to −85 mA for 10 minutes. The results are shown in Table 1.
陰極として0.5cm×0.5cm×厚さ0.5mmのCd板を使用し、印加する電流を-55mAで10分間に変更した以外は実施例1と同様の条件で反応を行った。結果を表1に示す。 [Comparative Example 2]
The reaction was performed under the same conditions as in Example 1 except that a Cd plate having a size of 0.5 cm × 0.5 cm × thickness 0.5 mm was used as the cathode and the applied current was changed to −55 mA for 10 minutes. The results are shown in Table 1.
Claims (6)
- 隔膜、陽極および銀を含む陰極を有する電気化学セル中で、ゲルマニウム化合物を含む電解液に通電して、陰極においてゲルマンを発生させて、電気化学的にゲルマンを製造する方法。 A method of producing germane electrochemically by energizing an electrolyte containing a germanium compound in an electrochemical cell having a diaphragm, an anode, and a cathode containing silver to generate germane at the cathode.
- 前記電解液が、二酸化ゲルマニウムとイオン性物質とを含む電解液である、請求項1に記載の製造方法。 The manufacturing method according to claim 1, wherein the electrolytic solution is an electrolytic solution containing germanium dioxide and an ionic substance.
- 前記イオン性物質が、水酸化カリウムまたは水酸化ナトリウムである、請求項2に記載の製造方法。 The production method according to claim 2, wherein the ionic substance is potassium hydroxide or sodium hydroxide.
- 前記イオン性物質が水酸化カリウムであり、前記電解液中の水酸化カリウムの濃度が1~8mol/Lである、請求項2または3に記載の製造方法。 The production method according to claim 2 or 3, wherein the ionic substance is potassium hydroxide and the concentration of potassium hydroxide in the electrolyte is 1 to 8 mol / L.
- 前記通電の際の陰極の電流密度が30~500mA/cm2である、請求項1~4のいずれか1項に記載の製造方法。 The production method according to any one of claims 1 to 4, wherein a current density of the cathode during the energization is 30 to 500 mA / cm 2 .
- 前記ゲルマンを発生させる際の反応温度が5~100℃である、請求項1~5のいずれか1項に記載の製造方法。 The production method according to any one of claims 1 to 5, wherein a reaction temperature for generating the germane is 5 to 100 ° C.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020197034666A KR20190140026A (en) | 2017-05-19 | 2018-05-07 | How to make germane electrochemically |
CN201880031311.0A CN110621810A (en) | 2017-05-19 | 2018-05-07 | Method for electrochemically producing germane |
JP2019519183A JP7110185B2 (en) | 2017-05-19 | 2018-05-07 | Method for producing germane electrochemically |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017099787 | 2017-05-19 | ||
JP2017-099787 | 2017-05-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018212007A1 true WO2018212007A1 (en) | 2018-11-22 |
Family
ID=64274277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/017649 WO2018212007A1 (en) | 2017-05-19 | 2018-05-07 | Method for electrochemically producing germane |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7110185B2 (en) |
KR (1) | KR20190140026A (en) |
CN (1) | CN110621810A (en) |
TW (1) | TWI743360B (en) |
WO (1) | WO2018212007A1 (en) |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU1732697A1 (en) * | 1990-01-19 | 1995-10-27 | Институт химии высокочистых веществ АН СССР | Method of synthesis of germanium hydride |
US5925232A (en) | 1995-12-06 | 1999-07-20 | Electron Tranfer Technologies | Method and apparatus for constant composition delivery of hydride gases for semiconductor processing |
JP2001028342A (en) * | 1999-07-15 | 2001-01-30 | Hitachi Ltd | Thin-film forming method and liquid crystalline display |
RU2203983C2 (en) * | 2001-03-13 | 2003-05-10 | Государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" | Process of electrochemical winning of hydrogen arsenide |
RU2230830C1 (en) | 2003-07-08 | 2004-06-20 | Общество с ограниченной ответственностью "Фирма "ХОРСТ" | High-purity germanium hydride preparation method |
US8021536B2 (en) | 2006-04-13 | 2011-09-20 | Air Products And Chemical, Inc. | Method and apparatus for achieving maximum yield in the electrolytic preparation of group IV and V hydrides |
US8399349B2 (en) * | 2006-04-18 | 2013-03-19 | Air Products And Chemicals, Inc. | Materials and methods of forming controlled void |
CN100558941C (en) * | 2007-12-03 | 2009-11-11 | 浙江树人大学 | Binode electro-chemistry hydride generator |
US8361303B2 (en) * | 2010-09-02 | 2013-01-29 | Air Products And Chemicals, Inc. | Electrodes for electrolytic germane process |
CN102249188B (en) * | 2011-05-21 | 2012-12-26 | 南京中锗科技股份有限公司 | Preparation method of germane gas |
US9228267B1 (en) * | 2011-11-07 | 2016-01-05 | Ardica Technologies, Inc. | Use of fluidized-bed electrode reactors for alane production |
CN102560589B (en) * | 2012-03-08 | 2015-05-13 | 厦门大学 | Method for preparing Ge-Sb-Te ternary phase-change material film |
CN102912374B (en) * | 2012-10-24 | 2015-04-22 | 中国科学院大连化学物理研究所 | Electrochemical reduction CO2 electrolytic tank using bipolar membrane as diaphragm and application of electrochemical reduction CO2 electrolytic tank |
CN103160347A (en) * | 2012-12-11 | 2013-06-19 | 云南亿星之光新能源科技开发有限公司 | Synthetic method of synthetic hydrogen fuels |
-
2018
- 2018-05-07 CN CN201880031311.0A patent/CN110621810A/en active Pending
- 2018-05-07 WO PCT/JP2018/017649 patent/WO2018212007A1/en active Application Filing
- 2018-05-07 JP JP2019519183A patent/JP7110185B2/en active Active
- 2018-05-07 KR KR1020197034666A patent/KR20190140026A/en not_active Application Discontinuation
- 2018-05-16 TW TW107116522A patent/TWI743360B/en active
Non-Patent Citations (2)
Title |
---|
BOLEA, E. ET AL.: "Electrochemical hydride generation for the simultaneous determination of hydride forming elements by inductively coupled plasma-atomic emission spectrometry", SPECTROCHIMICA ACTA PART B: ATOMIC SPECTROSCOPY, vol. 59, no. 4, 30 April 2004 (2004-04-30), pages 505 - 513, XP055561809 * |
TURYGIN, V. V. ET AL.: "Electrochemical Preparation of Germane", INORGANIC MATERIALS, vol. 44, no. 10, October 2008 (2008-10-01), pages 1081 - 1085, XP055561805 * |
Also Published As
Publication number | Publication date |
---|---|
TWI743360B (en) | 2021-10-21 |
KR20190140026A (en) | 2019-12-18 |
CN110621810A (en) | 2019-12-27 |
JP7110185B2 (en) | 2022-08-01 |
JPWO2018212007A1 (en) | 2020-03-26 |
TW201900931A (en) | 2019-01-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Lim et al. | Electrochemically deposited Sn catalysts with dense tips on a gas diffusion electrode for electrochemical CO 2 reduction | |
CN101634035B (en) | Electrochemical method and electrochemical device for synergistically generating ozone and hydrogen peroxide in neutral medium | |
US20220056602A1 (en) | Method for Converting Carbon Dioxide (CO2) into CO by an Electrolysis Reaction | |
WO2014042781A2 (en) | Process and high surface area electrodes for the electrochemical reduction of carbon dioxide | |
CN102666932A (en) | Negative electrode, electrolytic cell for electrolysis of alkali metal chloride, and method for producing negative electrode | |
US20180010255A1 (en) | Methanol generation device, method for generating methanol, and electrode for generating methanol | |
JP6221067B2 (en) | Formic acid production apparatus and method | |
KR20120024499A (en) | Electrodes for electrolytic germane process | |
WO2018212007A1 (en) | Method for electrochemically producing germane | |
JP7030115B2 (en) | How to electrochemically produce Germanic | |
JP7030114B2 (en) | How to electrochemically produce Germanic | |
JP2015224392A (en) | Oxygen-consuming electrode and method for its production | |
CA2503244C (en) | One-step electrosynthesis of borohydride | |
US20150096898A1 (en) | Methanol generation device, method for generating methanol, and electrode for generating methanol | |
JP7327422B2 (en) | Electrode for reduction reaction | |
KR101257921B1 (en) | Electrolytic hydrogen-generating electrode and method for producing the same | |
JP2574678B2 (en) | Equipment for producing aqueous solution containing peroxide | |
WO2024162841A1 (en) | Electrolyte solution and a method of manufacturing thereof | |
WO2024162842A1 (en) | A method of generating hydrogen and oxygen from a liquid feed stream | |
CZ304861B6 (en) | Electrolytic cell for preparing hydrogen | |
JP2017115223A (en) | Manufacturing method of l-cysteine mineral acid salt | |
KR20150034171A (en) | Undivided electrolytic cell and use of the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18802407 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019519183 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197034666 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18802407 Country of ref document: EP Kind code of ref document: A1 |