Page 12 - 《精细化工》2023年第4期
P. 12
g698g ㏳ࡃጒ FINE CHEMICALS す 40 ࢤ
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ౕ͚ᕔᝃⷞᕔϸ䉕͚喟 Ⅱ͚⮱ Cl чᄩ㜡יࡃݯᝃ⩢Ხ㙽㮭ȡₑ喑ຯ҂ើ
í
í
2H 2 O+2e ĺH 2 +2OH 喍HER喎 喍3喎 ݣ ClER喍ᝃ⁎⅜䚥⯽⩌喎Вࣷ倅 OER יࡃݯ
í
í
4OH ĺ2H 2 O+O 2 +4e 喍OER喎 喍4喎 䔶᠖ᕔᄦ⩢㼐⊤Ⅱݣ⅏᭫ᓄᰡͧ䛺㺮ȡᄦ OER ͚䬡
HER ᭜̭ᔘ䕌⮱ࣹ⩢ၽ䒙⼨䓴⼸喑๔็ Ҁڤᰶ≨ᕔ⮱㶕䲏䕇፥Όᰶݖλ ClER ͚䬡Ҁ喑व
[8]
HER יࡃݯ࠲᠙䓴⍎䛾ᆋ⅛ࡃ➖喍Mo 5 N 6 喎Ƞ⸤ࡃ 倅 OER 䔶᠖ᕔ⮱יࡃݯ䒰ͧఝ䯫 [18] ȡᣔݣ⩢㼐⣜
[9]
➖喍CoP/Co 2 P 喎Ƞࡃ➖喍Ni-Mo-S [10] 喎হᅯ⟣ࣹ ධ喍ຯ pH喎᭜⣝ OER 䔶᠖ᕔᰡͧキࢂᰶ᩵⮱
⅏⅔ࡃ➖喍LDH喎 [11] 喑㶕⣝ܧхᐯ⮱יࡃ≨ᕔȡ̻ ∂ȡDIONIGI ぶ [19] ܧ喑̻ OER Ⱕ℁喑ClER ౕ☚
HER Ⱕ℁喑⩞λ OER ᭜ 4 ⩢ၽࣺᏁ䓴⼸喑́ OÿO ߈႓̷᭜̺ݖ⮱喑ᒀ pH>7 ᬣ喑⩢Ѻጛ䮼Ɑ pH ⮱
䩛⮱ᒏ䰭ٸ䒰倅⮱ࡃ႓ࣺᏁ㘪ಿ喑ᄩ㜡 OER ࣺ ߍ㔹๔喑⁎⅜䚥⯽⩌হ OER 䬡⮱⩢Ѻጛ䓫ݝ
Ꮑ⮱ߕ߈႓ᒵ㑀ᚏ喑Ⱕᄦᱧ⤳Ό℁䒰ฺᱯȡₑ喑 ᰭ๔թ喍480 mV喎ȡहᬣ喑㔰㭾ݝ OER ౕ倅 pH
᱙᪴ᄳⱭ䛺आ䔝⩢㼐⊤Ⅱ OER יࡃݯȡౕ䓴ࣨ܍ У̸ᰡᰶݖ喑倅 pH ⮱ⷞᕔ⩢㼐䉕ᰡ䔯वλ⩢㼐⊤Ⅱȡ
Ꭱ͚喑ϧЙែڒγ๔䛼߈ᐭࣾ⩕λⅡ⩢㼐⮱倅᩵ ͧγԊⷞᕔ⊤Ⅱ⩢㼐䓴⼸͚ OER ⮱倅䔶᠖ᕔ喑䰭㺮
䲋䉢䛾ᆋ OER יࡃݯ喑ຯ䓴⍎䛾ᆋ⅔ࡃ➖ [12] Ƞ⅏ 倅≨ᕔ⮱ OER יࡃݯ喑Вౕ䒰ᄼ⮱䓴⩢Ѻ̸ӈ๔
⅔ࡃ➖ [13] Ƞ㓌ധ⅏⅔ࡃ➖ [14] Ƞ⅛ࡃ➖ [15] Ƞ⸤ࡃ➖ [16] ⩢≮ჳᏓ喑䖬ٺ⁎⅜䚥⯽⮱ᒏȡₑใ喑ᒀ pH>9
হ⵿ࡃ➖ [17] ȡѳ᭜喑܍ͻᰶ䔆ψיࡃݯ䘪गౕ⩢
ᬣ喑⩢㼐⋟͚чϔ⩌↶⋭喑ຯ Mg(OH) 2 ȠCa(OH) 2
㼐⌎Ⅱ͚䊤҉⩕喑ᄳڣ⩕λ๔㻱⩢㼐⌎Ⅱᄳч㐆 হ⊤Ⅱ͚ధᰶ⮱ڣЃ̺⏣ᕔధҀ喍ຯ㏳㣹হᓛ⩌➖喎
ᰶ䭽⮱⌎Ⅱ䉱⎽ፓᲒጕ๔ࢸ߈ȡ̻⌎ⅡⰥ℁喑⊤Ⅱ ᄳ㺳Ⰳ̭ψ≨ᕔѺ◦喑ϻ㔹䭺ѻיࡃݯ⮱יࡃᕔ㘪ȡ
᭜ౝ⤰̷䒰ͧ͝ჹ⮱䉱⎽喑ₑ⊤Ⅱ⮱⩢㼐ᰡͧ䛺 –
䮑䔶᠖ᕔ䬛䷅ใ喑⊤Ⅱ͚⮱ Cl जВⰡᣒ̻䔆ψ
㺮喑ᅑڣ᭜ᄦλ䲏͡⌎Ⅱⴚ㑧⮱ᬞౝࡧȡ⊤Ⅱ͚ 㑧ͼ⩢ၽ⮱䓴⍎䛾ᆋࣺᏁ喑ᄩ㜡יࡃݯ⮱㙽㮭喑ϻ
2+
2+
3+
+
+
ႅౕ⮱ Na ȠMg ȠCa ȠK হ B ぶ䭠⻨ၽ倅γ 㔹ᩦअיࡃݯ⮱㏱ [20] ȡₑ喑Cl ᑂࣾ⮱㙽㮭ч䔽
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⊤Ⅱ⮱ᄩ⩢ᕔ喑ₑ喑⩢㼐⊤Ⅱᬣᬍ䰭ाڣ͚⌨ߍ ⌽⏣㼐䓴⍎䛾ᆋധיࡃݯ喑ᄩ㜡יࡃݯ͚হיࡃ
䚥ᕔᝃⷞᕔ➖䉕В倅⏣⋟⩢ᄩ⢴ȡₑใ喑⩢㼐⊤ 㔽Ͳᕔअጛȡധλ䓴⍎䛾ᆋ⅛ࡃ➖ [21] Ƞ⸤ࡃ➖ [22] হ
Ⅱ䔅ͧ⊤Ⅱ⌎ࡃহ⯽⩌ϔӈ̭ज㘪ȡ ࡃ➖ [23] ⮱יࡃݯጟ㷘䃮ᬻڤᰶ㞜ສ⮱ᕔ㘪喑㘪์
᱙᪴仃ٵᄦⰛݺ⩢㼐⊤Ⅱ⮱ⵁ⾣㗹ᮜ䔈㵹γ䬽 ឬऄ⊤Ⅱ͚ Cl ⮱Ӣ㮭ȡओใ喑䔅जВ䕇䓴ౕיࡃݯ
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䔝喑䮼ऻᄦ䓾ᎡᲒ⩢㼐⊤Ⅱݣ⅏יࡃݯ䃫䃎হᕔ㘪 㶕䲏⊯㺳Ԋ៑ᅯ喑Გ㼐۠㙽㮭䬛䷅ȡKUANG ぶ [23]
⮱ᰭ䔈ᆂ䔈㵹γắ᠙হܳᲽ喑ᰭऻᄦ⩢㼐Ⅱיࡃ 䕇䓴ౕ NiS x F 㶕䲏̷⩌䪬 Fe(OH) 3 Გݣิ㔽 Cl 㙽㮭
–
ݯ䶳ഌ⮱ࣾᆂݺᮜ䔈㵹γᕨ㐀হᆂ᱈ȡ ⮱倅᩵ OER יࡃݯ喑ࣾ⣝ჹक़็࣌ၽ䚥⯽হⷠ䚥
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⯽⮱ᅯ⟣㐀ᲱजВᢿ⊤Ⅱ͚⮱ Cl 喑ϻ㔹倅γי
1 ⩢㼐⊤Ⅱ䲏͡⮱ᠾᝅ
ࡃݯ⮱㔽㮭ᕔȡ
⩢㼐⊤Ⅱᄦ OER 䭠Ხיࡃݯ⮱䔶᠖ᕔহ⽠Ⴧ 䓾ᎡᲒ喑⩢㼐⊤ⅡᲽ⅏⮱᩵⢴হ⽠Ⴧᕔ䘪ᓄݝ
–
ᕔܧγ㠈ݨ⮱㺮Ⅿȡ⩞λ⊤Ⅱ͚ႅౕ Cl 喑䭠Ხऄ γ̺倅喑ͧγᏁᄦⰛݺ⮱ᠾᝅ喑ⵁ⾣ϧঅጟ䃫
⩢㼐⋟ pH ⮱ᒞ৺喑ज㘪чࣾ⩌Ჽ⅜ࣺᏁ喍ClER喎 䃎䔶᠖ᕔহ⽠ჇᕔԞҠ⮱⩢㼐⊤Ⅱיࡃݯ喑࠲᠙䩝
ധ⅔ࡃ➖ [24] ȠLDH [25] Ƞ⸤䚥䧡 [26] Ƞ䓴⍎䛾ᆋव䛾 [27] Ƞ
ᝃ⁎⅜䚥⯽⮱⩌ȡ
[28]
䓴⍎䛾ᆋښ⅝ധ䛾ᆋ䚥⯽喍MHCMs喎 Ƞ⅛ࡃ➖ [21] Ƞ
䚥ᕔУ̸喟 [22] [23] [17]
í
0
í
2Cl īCl 2 +2e ȲE =1.36 V vs. SHE喍ᴴ۳⅏⩢Ხ喎ȳ ⸤ࡃ➖ Ƞࡃ➖ Ƞ⵿ࡃ➖ Ƞ䛾ᆋ䨞ᰶᱧᱽ
᫆ [29] 喑В̷יࡃݯጟ㷘䃮ᬻౕ⩢㼐⊤Ⅱ͚ڤᰶ䒰ສ
喍5喎
⮱ OER ࣷ HER 䔶᠖ᕔȡ䮑יࡃݯ≨ᕔ➖᱙䏘ᕔ
ⷞᕔУ̸喟
0
í
í
í
í
Cl +2OH īClO +H 2 O+2e ȲE =1.72 V vs. NHE喍̭ 㘪ใ喑Ჱᐧ̶㐡ܳᅯ็ႁ㏠ㆠ㐀ᲱȠԊ៑ᅯ㐀Ჱ
হ㶕䲏⋓⎬ᕔ㐀Ჱ᭜ᩦ䔈⩢㼐⊤Ⅱיࡃݯᕔ㘪⮱⤳
㝙⅏⩢Ხ喎ȳ 喍6喎
ᘠゃ⪒ȡ᱙᪴ᄳϻ䔆 3 ͗䲏㐩䔝⩢㼐⊤Ⅱיࡃݯ
ౕ䚥ᕔহⷞᕔ⣜ධ̸喑ClER হ⁎⅜䚥⯽⮱⩌
䃫䃎হᕔ㘪䲏⮱ᰭⵁ⾣䔈ᆂ喍ఫ 1喎ȡ
ࣺᏁᆋλ 2 ͗⩢ၽ࣯̻⮱ࣺᏁ喑㔹 OER ᭜ 4 ⩢ၽ࣯
̻⮱ࣺᏁȡₑ喑ϻߕ߈႓㻿ᏓᲒ䄡喑ClER হ⁎⅜ 2 ВࣺᏁᱧ⤳ͧᄩा⮱יࡃݯ䃫䃎⤳䃧
䚥⯽⮱⩌ᰡᰶݖ喑㔹ϻ☚߈႓㻿Ꮣⰸ喑OER ᰡᰶ
ݖȡ⩞λ ClER喍ᝃ⁎⅜䚥⯽⩌喎̻ OER ڤᰶ》 倅⽠ჇᕔȠ倅≨ᕔיࡃݯ⮱䃫䃎হवᲮ๔ౝ
ζᕔ喑⩢㼐⊤Ⅱ䰭㺮ᰡ倅⮱䓴⩢Ѻহ⊵㕄ᰡ็⮱㘪 Ӱ䔈γ⩢㼐⊤Ⅱ⮱ጕ๔䔈ₒহᎬ∈Ꮑ⩕ [30-31] ȡ䓴⍎
䛼ȡₑใ喑ౕ䚥ᕔУ̸ϔ⩌⮱ Cl 2 হౕⷞᕔУ 䛾ᆋহ䉢䛾ᆋ㘪์ӈ d 䒕䖀႑ᄦ⩢ၽ҉ͧϟᵥ䄂
̸⩌⮱⁎⅜䚥⯽ౕ⩢㼐⊤Ⅱ䓴⼸͚䒰䯫ั⤳喑⊤ ݯᝃӈ⾧ d 䒕䖀҉ͧϟ⩢䄂ݯ喑ౕⅡיࡃݯ͚ڤ
