JP2020180338A - 二酸化炭素還元用電極及びその製造方法 - Google Patents
二酸化炭素還元用電極及びその製造方法 Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 230000009467 reduction Effects 0.000 title claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000010409 thin film Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000004020 conductor Substances 0.000 claims abstract description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 19
- 229920002873 Polyethylenimine Polymers 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 239000010408 film Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 description 48
- 239000008151 electrolyte solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000971 Silver steel Inorganic materials 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydroxide ions Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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Abstract
Description
前記還元用薄膜が、窒素がドープされ且つ銅を担持した酸化グラフェンからなる二酸化炭素還元用電極が提供される。
酸化グラフェンの粒子と酸化銅の粒子を含む混合液を前記基材の表面に供給する原材料供給工程と、
前記基材の表面に付着した前記混合液を乾燥させ、酸化銅を担持した酸化グラフェンからなる薄膜前駆体を得る乾燥工程と、
前記薄膜前駆体を窒素供給物質に接触させて酸化グラフェンに窒素をドープするドープ工程と、
酸化銅を銅に還元し、窒素がドープされ且つ銅を担持した酸化グラフェンからなる還元用薄膜を前記基材に形成する還元工程と、
を有する二酸化炭素還元用電極の製造方法が提供される。
2H2O → 4H+ + 4e + O2 …(1)
プロトンは、連通用円筒部12a、14aに設けられた電解質膜20内を伝導して第1槽12内に移動する。また、電子は、対極54の第3導電ワイヤ56、電圧印加器60、作用極30の第2導電ワイヤ34を介して作用極30に移動する。なお、式(1)に従って生成した酸素は、排出管50から排出される。
14…第2槽 20…電解質膜
22…導入管 24…排気管
26…第1電解液 30…作用極
40…基材 42…還元用薄膜
44…ポリエチレンイミン膜 50…排出管
52…第2電解液 54…対極
60…電圧印加器 70、80…配位体
Claims (7)
- 導電体からなる基材と、前記基材に形成されて二酸化炭素を還元する還元用薄膜とを備える二酸化炭素還元用電極において、
前記還元用薄膜が、窒素がドープされ且つ銅を担持した酸化グラフェンからなる二酸化炭素還元用電極。 - 請求項1記載の電極において、前記基材の表面の少なくとも一部がポリエチレンイミン膜で覆われた二酸化炭素還元用電極。
- 請求項1又は2記載の電極において、前記基材が金属メッシュである二酸化炭素還元用電極。
- 導電体からなる基材と、前記基材に形成されて二酸化炭素を還元する還元用薄膜とを備える二酸化炭素還元用電極の製造方法において、
酸化グラフェンの粒子と酸化銅の粒子を含む混合液を前記基材の表面に供給する原材料供給工程と、
前記基材の表面に付着した前記混合液を乾燥させ、酸化銅を担持した酸化グラフェンからなる薄膜前駆体を得る乾燥工程と、
前記薄膜前駆体を窒素供給物質に接触させて酸化グラフェンに窒素をドープするドープ工程と、
酸化銅を銅に還元し、窒素がドープされ且つ銅を担持した酸化グラフェンからなる還元用薄膜を前記基材に形成する還元工程と、
を有する二酸化炭素還元用電極の製造方法。 - 請求項4記載の製造方法において、前記原材料供給工程の前に、前記基材の表面にポリエチレンイミンを付着させる表面処理工程を行う二酸化炭素還元用電極の製造方法。
- 請求項4又は5記載の製造方法において、酸化銅の粒子にオレイルアミンを配位子として配位させる第1配位処理工程と、オレイルアミンからなる前記配位子を3−メルカプトプロピオン酸からなる配位子に置換する第2配位処理工程を行い、その後、3−メルカプトプロピオン酸からなる配位子が配位した酸化銅の粒子と、酸化グラフェンとの混合液を調製する調製工程を行う二酸化炭素還元用電極の製造方法。
- 請求項4〜6のいずれか1項に記載の製造方法において、前記基材として金属メッシュを用いる二酸化炭素還元用電極の製造方法。
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Citations (4)
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WO2013089026A1 (ja) * | 2011-12-12 | 2013-06-20 | パナソニック株式会社 | 炭素系材料、電極触媒、酸素還元電極触媒、ガス拡散電極、水溶液電解装置、並びに炭素系材料の製造方法 |
US20170342578A1 (en) * | 2014-11-11 | 2017-11-30 | William Marsh Rice University | A new class of electrocatalysts |
CN108330506A (zh) * | 2018-01-16 | 2018-07-27 | 嘉兴学院 | 纳米铜合金/氮掺杂类石墨烯复合催化剂及其制备方法 |
WO2019065258A1 (ja) * | 2017-09-27 | 2019-04-04 | 積水化学工業株式会社 | 二酸化炭素還元装置、及び多孔質電極 |
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WO2013089026A1 (ja) * | 2011-12-12 | 2013-06-20 | パナソニック株式会社 | 炭素系材料、電極触媒、酸素還元電極触媒、ガス拡散電極、水溶液電解装置、並びに炭素系材料の製造方法 |
US20170342578A1 (en) * | 2014-11-11 | 2017-11-30 | William Marsh Rice University | A new class of electrocatalysts |
WO2019065258A1 (ja) * | 2017-09-27 | 2019-04-04 | 積水化学工業株式会社 | 二酸化炭素還元装置、及び多孔質電極 |
CN108330506A (zh) * | 2018-01-16 | 2018-07-27 | 嘉兴学院 | 纳米铜合金/氮掺杂类石墨烯复合催化剂及其制备方法 |
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