JP2016104897A - 光電極とその製造方法、およびそれを用いた光電気化学反応装置 - Google Patents
光電極とその製造方法、およびそれを用いた光電気化学反応装置 Download PDFInfo
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- JP2016104897A JP2016104897A JP2014243156A JP2014243156A JP2016104897A JP 2016104897 A JP2016104897 A JP 2016104897A JP 2014243156 A JP2014243156 A JP 2014243156A JP 2014243156 A JP2014243156 A JP 2014243156A JP 2016104897 A JP2016104897 A JP 2016104897A
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- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SLSPYQCCSCAKIB-UHFFFAOYSA-N bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F SLSPYQCCSCAKIB-UHFFFAOYSA-N 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- RAJISUUPOAJLEQ-UHFFFAOYSA-N chloromethanamine Chemical compound NCCl RAJISUUPOAJLEQ-UHFFFAOYSA-N 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
図1は第1の実施形態による光電極(photoelectrode)の製造工程を示す断面図である。図2は実施形態の光電極の製造工程で用いる触媒層の形成装置を示す図である。図1(a)に示すように、第1電極層110および第2電極層120と、これら電極層110、120間に設けられた光起電力層130とを備える積層体101を準備する。図1(b)に示すように、第1電極層110上に第1触媒層111を形成することによって、光電極102を作製する。ここでは図示を省略したが、第2電極層120上には必要に応じて第2触媒層が形成される。第1触媒層111は、図2に示す触媒層の形成装置1を用いて形成される。第1触媒層111の形成工程については、後に詳述する。
NO3 −+H2O+2e−→NO2 −+2OH− …(1)
Co2++2OH−→Co(OH)2 …(2)
次に、第2の実施形態による光電極の製造工程について説明する。図13(a)に示すように、第1電極層140および第2電極層150と、これら電極層140、150間に設けられた光起電力層160とを備える積層体103を準備する。図13(b)に示すように、第1電極層140上に第1触媒層141を形成することによって、光電極104を作製する。ここでは図示を省略したが、第2電極層150上には必要に応じて第2触媒層が形成される。第1触媒層141は、図2に示した触媒層の形成装置1を用いて形成される。第1触媒層141の形成工程については、後に詳述する。
次に、第1および第2の実施形態で作製した光電極102、104を用いた光電気化学反応装置について、図17を参照して説明する。ここでは、第1の実施形態で作製した光電極102を用いた光電気化学反応装置について主として述べるが、第2の実施形態で作製した光電極104を用いた場合においても、酸化反応と還元反応の生起電極が第1の実施形態とは反対となるだけで、基本的な構成は第1の実施形態で作製した光電極102を用いた光電気化学反応装置と同様である。
2H2O → 4H++O2+4e− …(3)
2CO2+4H++4e− → 2CO+2H2O …(4)
Claims (13)
- 光透過性電極を有する第1電極層と、金属電極を有する第2電極層と、前記第1電極層と前記第2電極層との間に設けられた光起電力層とを備える積層体を用意する工程と、
前記第1電極層上に形成される触媒層の少なくとも一部を構成する金属を含むイオンを含有する電解液に、前記積層体を浸漬する工程と、
前記電解液に浸漬された前記積層体に対して前記第2電極層から電流を導入し、前記第1電極層上に前記金属および前記金属を含む化合物からなる群より選ばれる少なくとも1つを電気化学的に析出させる工程と
を具備する光電極の製造方法。 - 前記電解液は、前記金属のイオン、前記金属の酸化物イオン、および前記金属の錯体イオンからなる群より選ばれる少なくとも1つの陽イオンと、無機酸イオンおよび水酸化物イオンからなる群より選ばれる少なくとも1つの陰イオンとを含有し、
前記積層体と対向するように前記電解液に浸漬された対極と前記積層体との間に、電源から電流を流すことにより、前記第1電極層上に前記金属、前記金属の水酸化物、および前記金属の酸化物からなる群より選ばれる少なくとも1つを析出させる、請求項1に記載の光電極の製造方法。 - 前記第1電極層は水を酸化する酸化電極であり、前記第2電極層は二酸化炭素および水の少なくとも一方を還元する還元電極であり、
前記触媒層は、前記金属として、マンガン、イリジウム、ニッケル、コバルト、鉄、スズ、インジウム、ルテニウム、ランタン、ストロンチウム、鉛、およびチタンからなる群より選ばれる少なくとも1つを含む金属酸化物を含有する、請求項1に記載の光電極の製造方法。 - 前記電解液は、前記金属のイオン、前記金属の酸化物イオン、および前記金属の錯体イオンからなる群より選ばれる少なくとも1つの陽イオンと、無機酸イオンからなる陰イオンとを含有し、
前記積層体と対向するように前記電解液に浸漬された対極と前記積層体との間に、電源から前記積層体の極性が負である電流を流すことにより、前記第1電極層上に前記金属の水酸化物および前記金属の酸化物から選ばれる少なくとも1つを析出させる、請求項3に記載の光電極の製造方法。 - 前記対極と前記積層体との間に流す電流により前記無機酸イオンを還元して水酸化物イオンを生成し、
前記陽イオンと前記水酸化物イオンにより前記第1電極層上に前記金属の水酸化物を析出させ、
前記第1電極層上に析出させた前記金属の水酸化物を加熱処理することにより、前記触媒層として前記金属の酸化物を生成する、請求項4に記載の光電極の製造方法。 - 前記無機酸イオンは、硝酸イオン、硫酸イオン、塩化物イオン、リン酸イオン、ホウ酸イオン、炭酸水素イオン、および炭酸イオンからなる群より選ばれる少なくとも1つである、請求項4または請求項5に記載の光電極の製造方法。
- 前記光起電力層は、前記第1電極層側に配置されたp型半導体層と、前記第2電極層側に配置されたn型半導体層と、前記p型半導体層と前記n型半導体層との間に配置されたi型半導体層を有するpin接合を少なくとも1つ備える、請求項3ないし請求項6のいずれか1項に記載の光電極の製造方法。
- 前記光起電力層は、前記第1電極層側に配置されたp型半導体層と、前記第2電極層側に配置されたn型半導体層とを有するpn接合を少なくとも1つ備える、請求項3ないし請求項6のいずれか1項に記載の光電極の製造方法。
- 前記第1電極層は二酸化炭素および水の少なくとも一方を還元する還元電極であり、前記第2電極層は水を酸化する酸化電極であり、
前記触媒層は、前記金属として、金、銀、銅、白金、パラジウム、ニッケル、亜鉛、カドミウム、インジウム、スズ、コバルト、鉄、および鉛からなる群より選ばれる少なくとも1つを含有する、請求項1に記載の光電極の製造方法。 - 請求項1ないし請求項9のいずれか1項に記載の光電極の製造方法により製造された光電極。
- 請求項10に記載の光電極と、
前記光電極が浸漬される電解液を収容する電解槽と
を具備する光電気化学反応装置。 - 前記光電極は、前記第1電極層および前記第2電極層の一方で水を酸化して酸素を生成し、前記第1電極層および前記第2電極層の他方で二酸化炭素を還元して炭素化合物を生成する、請求項11に記載の光電気化学反応装置。
- 第1電極層と、第2電極層と、前記第1電極層と前記第2電極層との間に設けられた光起電力層と、前記第1電極層上に形成された触媒層と、前記第2電極層に電気的に接続された配線部材とを備える光電極と、
前記光電極が浸漬される電解液を収容する電解槽とを具備し、
前記配線部材は前記電解槽の外部に導出されている光電気化学反応装置。
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PCT/JP2015/004039 WO2016088286A1 (ja) | 2014-12-01 | 2015-08-12 | 光電極とその製造方法、およびそれを用いた光電気化学反応装置 |
US15/414,395 US20170130343A1 (en) | 2014-12-01 | 2017-01-24 | Photoelectrode, method of manufacturing the same, and photoelectrochemical reaction device including the same |
US16/127,975 US20190010617A1 (en) | 2014-12-01 | 2018-09-11 | Photoelectrode, method of manufacturing the same, and photoelectrochemical reaction device including the same |
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JP2018154900A (ja) * | 2017-03-21 | 2018-10-04 | 株式会社東芝 | 電気化学反応装置と電気化学反応方法 |
JP2019065367A (ja) * | 2017-10-04 | 2019-04-25 | 株式会社豊田中央研究所 | 光エネルギー利用装置 |
KR20190063962A (ko) * | 2017-11-30 | 2019-06-10 | 한국생산기술연구원 | 슁글드 어레이 접합 방식을 이용한 광전기화학적 물분해용 고전압 광전극의 제조 방법 및 이에 따른 광전극 |
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