钴(Ⅱ)基分子配合物用于光催化二氧化碳还原
张继宏, 钟地长, 鲁统部

Co(Ⅱ)-Based Molecular Complexes for Photochemical CO2 Reduction
Jihong Zhang, Dichang Zhong, Tongbu Lu
表1 Co(Ⅱ)配合物分子催化剂光催化CO2还原
Table 1 Co(Ⅱ) complexes as molecular catalysts for photocatalytic CO2 reduction.
Entry CAT PS SD Solvent Light source Irradiation time (h) Product (TON) Quantum
yield (%)		 Selectivity (%) Refs.
1 C1
(80 μmol∙L−1)		 [Ru(bpy)3]2+ AH− H2O daylight lamp 18 CO(22) – 22 32
2 C2
(80 μmol∙L−1)		 [Ru(bpy)3]2+ AH− H2O daylight lamp 18 CO(9.6) – 32 32
3 C3
(80 μmol∙L−1)		 [Ru(bpy)3]2+ AH− H2O daylight lamp 18 CO (< 3) – < 1 32
4 C4
(1.7 mmol∙L−1)		 p-terphenyl TEOA CH3CN/MeOH Hg lamp
(λ > 290 nm)		 1 CO(10.2)
HCOO− (6.7)		 15(CO)
10(HCOO−)		 – 34
5 C4
(2.5 mmol∙L−1)		 phenazine TEA CH3CN/MeOH Hg lamp
(λ > 290 nm)		 1 HCOO− (5) 7(HCOO−) > 90 35
6 C5
(1.7 mmol∙L−1)		 p-terphenyl TEOA CH3CN/MeOH Hg lamp
(λ > 290 nm)		 1 CO(5.3)
HCOO−(3.5)		 – 51.6(CO)
34.4(HCOO−)		 36
7 C6
(1.7 mmol∙L−1)		 p-terphenyl TEOA CH3CN/MeOH Hg lamp
(λ > 290 nm)		 1 CO(1.0) – 44 36
8 C7
(1.7 mmol∙L−1)		 p-terphenyl TEOA CH3CN/MeOH Hg lamp
(λ > 290 nm)		 1 – – – 36
9 C8
(1.7 mmol∙L−1)		 p-terphenyl TEOA CH3CN/MeOH Hg lamp
(λ > 290 nm)		 1 CO(4.9)
HCOO−(2.5)		 – 58.5(CO)
30.4(HCOO−)		 37
10 C9
(1.7 mmol∙L−1)		 p-terphenyl TEOA CH3CN/MeOH Hg lamp
(λ > 290 nm)		 1 CO(2.7)
HCOO−(0.4)		 – 30.3(CO)
4.8(HCOO−)		 36
11 C10
(50 μmol∙L−1)		 fac-Ir(ppy)3 TEA CH3CN LED
(λ > 460 nm)		 22 CO(270) – 97 38
12 C11
(0.5 mmol∙L−1)		 [Ru(phen)3]2+ TEOA DMF Xe lamp,
IR-cut filter		 404 CO(8.3) – 31 39
13 C12
(0.5 mmol∙L−1)		 – TEOA DMF Xe lamp
(λ > 400 nm)		 > 25 CO(3) – – 40
14 C13
(0.5 mmol∙L−1)		 – TEOA DMF Xe lamp
(λ > 400 nm)		 > 25 CO(5) – – 40
15 C14
(5 μmol∙L−1)		 [Ru(bpy)3]2+ BIH CH3CN/TEOA LED
(λ = 460 nm)		 1.3 CO(2600) 2.8 98 41
16 C14
(5 μmol∙L−1)		 purpurin BIH DMF LED
(λ = 460 nm)		 11 CO(790) – 95 41
17 C15
(50 μmol∙L−1)		 [Ru(phen)3]2+ BIH/TEOA CH3CN LED
(λ = 460 nm)		 60 CO(221)
HCOO−(821)		 – 75.9(CO) 42
18 C15
(50 μmol∙L−1)		 [Ru(phen)3]2+ BIH CH3CN/PhOH LED
(λ = 460 nm)		 1 CO(829)
HCOO−(12)		 – 96(CO) 42
19 C16
(0.18 mmol∙L−1)		 [Ru(bpy)3]2+ TEA CH3CN/TTA Xe lamp
(λ > 410 nm)		 4 CO(3.4)
HCOO−(1.4)		 – 71.4(CO) 43
20 C17
(0.18 mmol∙L−1)		 [Ru(bpy)3]2+ TEA CH3CN/TTA Xe lamp
(λ > 410 nm)		 4 CO(5.1) – 38.9(CO) 43
21 C18
(10 μmol∙L−1)		 – TEA CH3CN Xe lamp
(λ > 320 nm)		 200 CO+
HCOO−(300)		 – – 44
22 C19
(50 μmol∙L−1)		 p-terphenyl TEA CH3CN Xe lamp
(λ > 320 nm)		 20 CO(62) – – 45
23 C20
(40 μmol∙L−1)		 p-terphenyl TEA CH3CN Xe lamp
(λ > 310 nm)		 6 CO(47.5) – – 46
24 C21
(42 μmol∙L−1)		 p-terphenyl TEA CH3CN Xe lamp
(λ > 310 nm)		 8 CO(50–100) – – 45
25 C22
(10 μmol∙L−1)		 [Ru(bpy)3]2+ AHˉ H2O Xe lamp
(λ > 400 nm)		 4 CO(926) – 82 47
26 C22
(5 μmol∙L−1)		 CuPS AHˉ H2O Xe lamp
(λ > 400 nm)		 4 CO(1085) – 90 49
27 C23
(5 μmol∙L−1)		 CuPS AHˉ H2O Xe lamp
(λ > 400 nm)		 4 CO(2680) – 77 49
28 C24
(5 μmol∙L−1)		 fac-Ir(ppy)3 TEA CH3CN LED
(λ = 460 nm)		 70 CO(953) – 85 50
29 C25
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA CH3CN/H2O LED
(λ = 450 nm)		 60 CO(56.9)
HCOO−(64.2)		 – 18.8(CO)
21.2(HCOOˉ)		 53
30 C26
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 60 CO(368) – 95 54
31 C27
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 15 – – – 54
32 C28
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 15 CO(13) – 65 54
33 C29
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 15 – – – 54
34 C30
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 12 CO(56) – 86 55
35 C30
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 48 CO(470) – 87 55
36 C31
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 12 CO(102) – 88 55
37 C31
(10 μmol∙L−1)		 fac-Ir(ppy)3 TEA DMF LED
(λ = 460 nm)		 48 CO(403) – 89 55
38 C32
(2 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(1179) 0.22 97 55
39 C33
(0.05 μmol∙L−1)		 [Ru(phen)3]2+ TEA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(11600) 97 60
40 C34
(0.05 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(1600) 0.007 85 60
41 C35
(0.05 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(12680) – 97 62
42 C36
(0.05 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(11280) – 98 62
43 C37
(0.05 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(1600) – 85 62
44 C38
(2.0 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 12 CO(790) 0.16 98 63
45 C39
(2.0 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 12 CO(1070) 0.22 98 63
46 C40
(2.0 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 12 CO(1330) 0.27 98 63
47 C41
(1.0 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 12 CO(950) 0.19 98 63
48 C42
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(16896) 0.04 98 64
49 C43
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O Blue LED 3 CO(7820) 0.28 87 68
50 C44
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O Blue LED 3 CO(8676) 0.31 83 68
51 C45
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O Blue LED 3 CO(14210) 0.51 95 68
52 C43
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O Blue LED 30 CO(46335)
CH4(2200)		 CO(0.17)
CH4(0.03)		 CO(90) CH4(4) 68
53 C44
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O Blue LED 30 CO(27311)
CH4(1766)		 CO(0.10)
CH4(0.03)		 CO(92) CH4(6) 68
54 C45
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O Blue LED 30 CO(5641)
CH4(648)		 CO(0.02)
CH4(0.01)		 CO(63) CH4(7) 68
55 C46
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(65000) 0.15 98 69
56 C47
(0.025 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(33792) 0.15 98 70
57 C47
(0.5 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O CO2/Ar = 1/9 LED
(λ = 450 nm)		 10 CO(600) – 95 70
58 C48
(0.5 μmol∙L−1)		 [Ru(phen)3]2+ TEOA CH3CN/H2O LED
(λ = 450 nm)		 10 CO(18656) – 97 70
59 C49
(30 μmol∙L−1)		 Ir(ppy)3 BIH DMA/TFE LED
(λ = 420 nm)		 4 CO(58.4)
COOH(55.7)		 – CO(33.2)
COOH(31.7)		 71