JP6254565B2 - 二酸化炭素を電気化学的に転換するための新規触媒混合物及び電気化学的装置 - Google Patents
二酸化炭素を電気化学的に転換するための新規触媒混合物及び電気化学的装置 Download PDFInfo
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- JP6254565B2 JP6254565B2 JP2015232576A JP2015232576A JP6254565B2 JP 6254565 B2 JP6254565 B2 JP 6254565B2 JP 2015232576 A JP2015232576 A JP 2015232576A JP 2015232576 A JP2015232576 A JP 2015232576A JP 6254565 B2 JP6254565 B2 JP 6254565B2
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Images
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Description
本明細書において用語「CO2の電気化学的転換」は、電気化学的プロセスの任意の工程で、二酸化炭素、炭酸塩、又は重炭酸塩が別の化学物質に転換されるプロセスを意味する。
(a)化学反応を加速すること、又は
(b)プロセスで実質的に消費されることなく、反応の過電圧を低下させること。
化学反応を加速すること、又は
プロセス中で実質的に消費されることなく、反応の過電圧を低下させること。
標準的な3電極電気化学セルに、反応Rに一般的に使用されている電解質を満たす。一般的な電解質には、0.1Mの硫酸があり、又は0.1MのKOH水溶液も使用することができる。
活性金属を、3電極電気化学セルと適切な対電極に取り付ける。
数回のCVサイクルを実行して、活性金属を洗浄する。
電解質中の可逆水素電極(RHE)電位を測定する。
反応Rの反応物をセルに充填し、反応Rに関連するピークの電位に注意しながら、反応RのCVを測定する。
V1=RHEと反応に関連するピークの開始電位の差を計算する。
V1A=RHEと反応に関連するピークの最大電位の差を計算する。
0.0001〜99.9999%の物質Sを電解質に加える。
助触媒を用いる反応におけるRHEを測定する。
反応Rに関連するピークの電位に注意しながら、反応RのCVを再度測定する。
V2=RHEと反応に関連するピークの開始電位の差を計算する。
V2A=RHEと反応に関連するピークの最大電位の差を計算する。
CO2の電気化学的転換の過電圧を低下させ、かつ反応の選択性(電流効率)を向上させるために、白金と1−エチル−3−メチルイミダゾリウムテトラフルオロボラート(EMIM−BF4)とを含む活性元素−助触媒混合物を使用する。
この例は、水の添加がCO形成速度を上昇させることを示す。この実験は、例1に記載のセルと手順を用いたが、以下の例外を含む:例1で使用した99.9999%のEMIM−BF4の代わりに、98.55%のEMIM−BF4と0.45%の水とを含む溶液を使用し、電位は、RHEに対して−0.6Vで10又は30分間維持し、次に電位を50mV/秒でプラスに上げた。図10にその結果を示す。1.2Vと5Vとの間のピークに注意されたい。これはCO形成に関連するピークであり、例1のものよりはるかに大きい。すなわち水の添加は、おそらく反応物として作用することによりCO形成を加速させた。
CO2に、パラジウムとヨウ化コリンを含む活性元素−助触媒混合物を使用することは、水中でのCO2の電気化学的転換のための過電圧を低下させる。
CO2のギ酸への電気化学的転換に関する過電圧を低下させるために、パラジウムと塩化コリンを含む活性元素−助触媒混合物を使用する。
CO2からCOへの電気化学的転換に関する過電圧を低下させるために、ニッケルと塩化コリンを含む活性元素−助触媒混合物を使用する。
活性元素(金)−助触媒混合物がCO2センサーに有用であることを証明する。
この例は、一酸化炭素の定常状態での製造を示す。
[1]
少なくとも1種の触媒活性元素、及び少なくとも1種の助触媒を含む、触媒。
[2]
CO 2 を、CO 2 との反応による1種以上の生成物に電気的に転換する、[1]に記載の触媒。
[3]
前記触媒活性元素は、V、Cr、Mn、Fe、Co、Ni、Cu、Sn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Ir、Pt、Au、Hg、Al、Si、C、In、Sn、Tl、Pb、Bi、Sb、Te、U、Sm、Tb、La、Ce、及びNdの1種以上を含む、[1]に記載の触媒。
[4]
前記生成物は、以下の少なくとも1種を含む、[2]に記載の触媒:CO、OH − 、HCO − 、H 2 CO、(HCO 2 ) − 、H 2 CO 2 、CH 3 OH、CH 4 、C 2 H 4 、CH 3 CH 2 OH、CH 3 COO − 、CH 3 COOH、C 2 H 6 、O 2 、H 2 、(COOH) 2 、及び(COO − ) 2 。
[5]
前記反応生成物は、H 2 CO 2 を含む、[4]に記載の触媒。
[6]
前記触媒活性元素は、Pt、Pd、Au、Ag、Ni、Fe、Co、Ru、及びRhの少なくとも1種を含む、[1]に記載の触媒。
[7]
前記助触媒は、有機カチオン及び有機アニオンの少なくとも1種を含む、[1]〜[6]のいずれか一項に記載の触媒。
[8]
前記助触媒は、約0.0000062重量%〜99.999重量%の濃度を有する、[1]に記載の触媒。
[9]
前記助触媒は、ホスフィン類、イミダゾニウム類、ピリジニウム類、ピロリジニウム類、ホスホニウム類、スルホニウム類、プロリナート類、及びメチオニナート類の少なくとも1種を含む、[1]に記載の触媒。
[10]
前記助触媒は、コリン類を含む、[1]に記載の触媒。
[11]
前記助触媒は、1−エチル−3−メチルイミダゾニウムカチオン類を含む、[1]に記載の触媒。
[12]
前記助触媒は、トリフルオロボラートアニオン類を含む、[1]に記載の触媒。
[13]
前記助触媒は、溶媒、電解質、又は添加物である、[1]に記載の触媒。
[14]
[1]に記載の触媒を含む、CO 2 センサー。
[15]
[1]に記載の触媒を含む、燃料電池。
[16]
以下の工程を含む、化学反応生成物の製造方法:
反応物の存在下で触媒活性元素と助触媒とを組み合わせる工程;及び
反応を進行させて反応生成物を製造する工程。
[17]
前記反応に電気エネルギーを適用して、前記反応物から反応生成物への電気化学的転換を達成する工程をさらに含む、[16]に記載の方法。
[18]
前記触媒活性元素は、V、Cr、Mn、Fe、Co、Ni、Cu、Sn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Ir、Pt、Au、Hg、Al、Si、C、In、Sn、Tl、Pb、Bi、Sb、Te、U、Sm、Tb、La、Ce、及びNdよりなる群から選択される、[16]に記載の方法。
[19]
前記触媒活性元素は、Pb、Hg、Tl、In、Cd、Bi、Zr、Cr、Sn、W、Pd、及びRuよりなる群から選択される、[18]に記載の方法。
[20]
前記助触媒は、有機カチオン及び有機アニオンの少なくとも1つを含む、[16]に記載の方法。
[21]
前記助触媒は、ホスフィン類、イミダゾニウム類、ピリジニウム類、ピロリジニウム類、ホスホニウム類、スルホニウム類、プロリナート類、メチオニナート類、コリン類、塩化コリン、臭化コリン、ヨウ化コリンからなる群より選択される、[16]に記載の方法。
[22]
前記反応物はCO 2 である、[16]に記載の方法。
[23]
前記反応生成物は、CO、OH − 、HCO − 、H 2 CO、(HCO 2 ) − 、H 2 CO 2 、CH 3 OH、CH 4 、C 2 H 4 、CH 3 CH 2 OH、CH 3 COO − 、CH 3 COOH、C 2 H 6 、O 2 、H 2 、(COOH) 2 、(COO − ) 2 、Cl 2 、Br 2 、I 2 、NaOH、KOH、NaClO、NaClO 3 、KClO 3 、及びCF 3 COOHの少なくとも1種である、請求項16に記載の方法。
[24]
前記反応生成物はギ酸(H 2 CO 2 )である、[23]に記載の方法。
Claims (10)
- 少なくとも0.45%の水;二酸化炭素(CO2)を1種以上の反応生成物に転換する少なくとも1種の触媒活性元素;及びそれとは別個の成分として少なくとも1種の助触媒を含む、CO2を電気化学的に還元するための触媒混合物であって、
前記触媒活性元素は、V、Cr、Mn、Fe、Co、Ni、Cu、Sn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Ir、Pt、Au、Hg、Al、Si、In、Tl、Pb、Bi、Sb、Te、U、Sm、Tb、La、Ce、及びNdの1種以上を含み、
前記助触媒は、有機分子又は有機分子の混合物であり
前記助触媒は、ホスフィン、イミダゾリウム(ただし、芳香環の水素原子部分に結合する窒素原子を含むイミダゾリウムを除く)、ピリジニウム(ただし、芳香環の水素原子部分に結合する窒素原子を含むピリジニウムを除く)、ピロリジニウム、ホスホニウム、スルホニウム、プロリナート、メチオニナート、プロピルイソキノリニウム、チウロニウム及びコリンの少なくとも1種を含む、
触媒混合物、
ここで、ある物質Sが、触媒活性元素Mにより触媒される反応Rの助触媒であるかどうかは、以下を含む試験で決定する:
作用電極、対電極、及び参照電極を含む3電極電気化学セルに、反応Rを行うのに適切な電解質Eを満たすこと:
前記触媒活性元素Mを、前記作用電極に保持させ、かつ前記対電極を取付けること;
前記参照電極を用いて、電解質E中の可逆水素電極(RHE)電位を測定すること;
反応Rの反応物を前記セルに充填すること;
反応Rについてのサイクリックボルタンメトリーを測定して、反応Rに関連するピークの電位を特定すること;
RHEと反応Rに関連するピークの開始電位の差V1を計算すること;
RHEと反応Rに関連するピークの最大電位の差V1Aを計算すること;
0.0001〜99.9999重量%の前記物質Sを前記電解質Eに加えること;
RHE電位を、前記物質Sを加えた電解質E中で測定すること;
前記物質Sを加えた状態で、反応Rのサイクリックボルタンメトリーを再度測定すること;
RHEと反応Rに関連するピークの開始電位の差V2を計算すること;
RHEと反応Rに関連するピークの最大電位の差V2Aを計算すること;
0.0001〜99.9999%の物質Sの任意の濃度で、V2<V1又はV2A<V1Aかどうかを決定すること、
複数の濃度でV2<V1又はV2A<V1Aである場合、物質Sが、反応Rの助触媒である。 - 電気エネルギーを適用した場合に、過電圧の低下(V1−V2)を少なくとも0.5Vとして、CO2を、反応Rの少なくとも1種の反応生成物に電気化学的に転換することができる、請求項1に記載の触媒混合物、ただし、反応Rは光電気化学反応ではない。
- 前記少なくとも1種の反応生成物は、以下の少なくとも1種を含む、請求項2に記載の触媒混合物:CO、HCO−、(HCO 2 ) − 、H2CO2、CH4、C2H4、CH3CH2OH、CH3COO−、CH3COOH、C2H6、(COOH)2、及び(COO−)2。
- 前記助触媒が、次の式のイミダゾリウム、ピリジニウム、プロピルイソキノリニウム及びチウロニウムからなる群より選択される有機カチオンを含む、請求項1に記載の触媒混合物:
- 前記助触媒は、1−エチル−3−メチルイミダゾニウムカチオン及びコリンの少なくとも1つを含み、かつ前記助触媒がビス(トリフルオロメチルスルホニル)イミドアニオンを含有しない、請求項1に記載の触媒混合物。
- 請求項1〜5のいずれか一項に記載の触媒混合物を含み、前記触媒活性元素が、前記助触媒と接触して電極の少なくとも一部を構成する、電気化学セル、CO2センサー、又は燃料電池である電気化学的装置。
- 以下の工程を含む、化学反応生成物の製造方法:
CO2の存在下で、請求項1〜5のいずれか一項に記載の触媒活性元素及び助触媒を組み合わせる工程、ここで前記触媒活性元素は、電気化学セルのカソードの少なくとも一部を構成し、かつ前記助触媒が触媒活性元素を構成しない;及び
電気エネルギーを加えて、CO2を電気化学的に前記反応生成物に転換する工程。 - 以下の工程を含む、化学反応生成物を製造するための電気化学的方法:
請求項1に記載の少なくとも1つの触媒活性元素を含む、少なくとも1つの電極を有する電気化学的装置を与える工程;
CO2の存在下で、前記触媒活性元素を、請求項1に記載の前記助触媒と組み合わせる工程;及び
前記少なくとも1つの電極に電気エネルギーを加えて、反応Rを行って、前記CO2を電気化学的に前記反応生成物に転換する工程、ただし、反応Rは光電気化学反応ではない。 - アノード及びカソードを含む、電気化学的装置であって、
前記カソードが、カソード電位を有し、かつV、Cr、Mn、Fe、Co、Ni、Cu、Sn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Ir、Pt、Au、Hg、Al、Si、C、In、Tl、Pb、Bi、Sb、Te、U、Sm、Tb、La、Ce、及びNdからなる群より選択される少なくとも1つの触媒活性元素を含み、かつ
前記カソードは、少なくとも0.45%の水、二酸化炭素(CO2)及び助触媒を含む電解質と接触し、前記助触媒は、1−エチル−3−メチルイミダゾニウムカチオン、コリン、塩化コリン、臭化コリン、及びヨウ化コリンの少なくとも1種を含み、
電気エネルギーを適用して、前記アノードと前記カソードとの間に電位差を与えた際に、前記カソード電位が、標準水素電極(SHE)に対して−0.9V以上の場合に、この電気化学的装置は、CO2の少なくとも一部を、反応生成物に転換し、この転換は、光電気化学反応ではなく、
前記反応生成物が、CO、HCO−、H2CO、(HCO2)−、H2CO2、CH4、C2H4、CH3CH2OH、CH3COO−、CH3COOH、C2H6、(COOH)2、及び(COO−)2からなる群より選択される、電気化学的装置。 - 前記カソード電位が標準水素電極(SHE)に対して−0.6V以下の場合に、CO2の少なくとも一部を反応生成物に転換させることができる、請求項9に記載の装置。
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JP2013525088A (ja) | 2013-06-20 |
EP2553147A1 (en) | 2013-02-06 |
WO2011120021A1 (en) | 2011-09-29 |
CA2794105C (en) | 2018-07-10 |
US20110237830A1 (en) | 2011-09-29 |
US10023967B2 (en) | 2018-07-17 |
AU2011230545B2 (en) | 2016-02-11 |
AU2011230545A1 (en) | 2012-10-11 |
CN102892929B (zh) | 2016-09-14 |
CA2794105A1 (en) | 2011-09-29 |
JP2016041427A (ja) | 2016-03-31 |
KR101721287B1 (ko) | 2017-03-29 |
KR20130060185A (ko) | 2013-06-07 |
EP2553147B1 (en) | 2022-05-18 |
AU2011230545C1 (en) | 2016-06-09 |
US20150122640A1 (en) | 2015-05-07 |
CN102892929A (zh) | 2013-01-23 |
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