电化学选择性氢化脱氯反应

1、关于电化学选择性氢化脱氯反应第一张，PPT共二十六页，创作于2022年6月目录1. 银、钯催化的电化学选择性氢化脱氯反应简介2. 多氯吡啶甲酸的电化学选择性氢化脱氯反应3. 其他多氯有机物的电化学选择性氢化脱氯反应4. 总结和展望Zhejiang University of Technology2第二张，PPT共二十六页，创作于2022年6月1.银、钯催化的电化学选择性氢化脱氯反应简介有机合成：合成部分氯代有机物作为药物中间体或原料药；要求:区域选择性脱氯。1.1. 主要用途及要求Zhejiang University of TechnologyRondinini S., et al. Ele

2、ctroreduction of Halogenated Organic Compounds, 2010, 279;Alonao F., et al. Chem. Rev., 2002, 102(11): 4009-4091.环境保护：降解环境中存在的高毒、难降解氯代有机物；要求：化学选择性脱氯。3第三张，PPT共二十六页，创作于2022年6月1.2.催化原理Isse A.A., et al. J. Phys. Chem. C, 2009, 113: 14983; Wang A., et al. J. Am. Chem. Soc.: 2010, 132: 9534. Dabo P., et a

3、l. Environ. Sci. Technol., 2000, 34: 1265; Chen G.,et al. J. Phys. Chem. B, 2006, 110: 4863.Fig. 1.1 The hydrodechlorination mechanism on silver electrodeFig. 1.2 The hydrodechlorination mechanism on palladium electrode4第四张，PPT共二十六页，创作于2022年6月2.多氯吡啶甲酸的电化学选择性氢化脱氯化工学报, 2010, 61: 699.Zhejiang Universit

4、y of Technology5第五张，PPT共二十六页，创作于2022年6月Fig. 2.1 CVs of 3,5,6-T (a) at four electrodes in a N2-saturated 0.25 M PBS at pH = 3, (b) at a Ag(r) electrode in a N2-saturated 0.5 M H2SO4 (pH = 0.2), a 0.5 M NaOH (pH = 13.3) aqueous solution, and 0.25 M PBS of three different pH values (3, 7, and 11); scan

5、 rate v = 50 mV s-1, T = 297 K.Electrochim. Acta, 2015, 151: 284;ZL 201410264884.1Zhejiang University of Technology2.1. 银催化Ag(p)Ag(r)pH = 3Ag(r)6第六张，PPT共二十六页，创作于2022年6月Table 2.1 Electrochemical reduction of 3.33 mM 3,5,6-T in a N2-saturated 0.5 M H2SO4 (pH = 0.2), a 0.5 M NaOH (pH = 13.3) aqueous so

6、lution, and 0.25 M PBS of three different pH values (3, 7, and 11) at 297 K on five cathodes.EntryCathodesIappa or EappaSolution pHFinal product distribution (%)Current efficiency (%)b3,5-D selectivity (%)c3,6-D selectivity (%) c3,5-D3,6-D3,5,6-T1Ni10 mA30098.20002Cu10 mA30098.50003Ag(p)1.0 mA32.50.

7、895.42.554.317.44GC1.0 mA30094.40005Ag(r)10 mA344.02.649.344.086.85.16Ag(r)-1.1 V13.30.437.896.27Ag(r)-1.1 V110.922.688.78Ag(r)-0.93 V735.415.347.235.467.029.09Ag(r)-0.73 V339.52.458.039.594.05.7010Ag(r)10 mA0.20098.7000a 2 Fmol-1 of 3,5,6-T were consumed in the all 10 electrolys

8、is experiments.b Current efficiency calculated with respect to the produced 3,5-D. c 3,5-D and 3,6-D selectivity calculated with respect to the converted 3,5,6-T.Zhejiang University of Technology7第七张，PPT共二十六页，创作于2022年6月Fig. 2.2 Product selectivity and carbon mass balance during the electrochemical r

9、eduction of 42.5 mM 3,5,6-T at 297 K. Catholye: 30 mL 0.25 M PBS at pH = 3. Cathode: Ag(r) mesh electrodes (2.5 cm3 cm).Zhejiang University of TechnologypH = 3 Ag(r)8第八张，PPT共二十六页，创作于2022年6月Zhejiang University of TechnologyFig. 2.3 Effects of pH on the selectivity for hydrodechlorination of TeCP on s

10、ilver cathodes. 9第九张，PPT共二十六页，创作于2022年6月Fig. 2.5 LSV of Ni foam, Ag mesh, Cu foam electrodes, and Pd/Ni foam, Pd/Ag mesh, Pd/Cu foam electrodes in a 0.5 M NaOH aqueous solution, v = 5 mV/s, with two concentrations of 3,6-D, Temperature: 25 .Fig. 2.4 SEM of Ni and Pd/Ni foam, Ag and Pd/Ag mesh, Cu an

11、d Pd/Cu foam.ZL 201510401434.7;ZL 201510401039.9.Zhejiang University of Technology2.2. 钯催化Pd/Ni foamNi foamAg meshCu foamPd/Ag meshPd/Cu foam10第十张，PPT共二十六页，创作于2022年6月EntryCatholyte pH Final product distribution (%)CE c (%)3,6-DPA3-ClPA6-ClPA11.25M NaOH14096.13.1087.220.25 M NaOH11.513.5088.710.6084.

12、030.5 M KH2PO4 + 0.3 M NaOH7.29.413.856.527.90.362.240.5 M KH2PO4 + 0.2 M NaOH4.46.647.336.450.5 M KH2PO4 + 0.2 M NaOH90.32.3081.76d 0.75 M H2SO4 + 20 % v/v Ethanol0086.9Table 2.2 Effect of electrolyte composition on the ECH dechlorination of 0.25 M 3,6-D.aa Cathode: a

13、Pd/Ni foam (Projected area: 26 cm2, Pd loading: 2.25 mg/cm2). c CE was calculated with t = 6 h.d 3,6-D was added into the catholyte in a divided fashion during the first hour of electrolysis due to its poor solubility.Zhejiang University of Technology11第十一张，PPT共二十六页，创作于2022年6月Fig. 2.6 Effect of pH o

14、n product selectivity and CE during the ECH dechlorination of 3,6-D. Cathode: a Pd/Ni foam; Catholyte: (A and A) 50 mL 1.25 M NaOH + 96 mM 3,6-D, and B (B ) 50 mL 0.75 M H2SO4 + 96 mM 3,6-D+ 20% v/v Ethanol; CE was calculated with t = 1, 2, 3, 4, 5 or 6.0 h.Zhejiang University of Technology1.25 M Na

15、OH 0.75 M H2SO4 12第十二张，PPT共二十六页，创作于2022年6月Scheme 1 Proposed mechanisms for the ECH dechlorination of 3,6-D.Zhejiang University of Technology13第十三张，PPT共二十六页，创作于2022年6月Fig. 2.7 Effects of cathode catalysts and pH on the selectivity for hydrodechlorination of TeCP.Zhejiang University of Technology14第十四

16、张，PPT共二十六页，创作于2022年6月3.其他多氯有机物电化学选择性氢化脱氯3.1.三氯甲基苯Fig. 3.1 CV of 5.0 mM benzenyltrichloride and benzyl chloride, in CH3CN + 0.1 mM TBAP on Ag electrode ( 2 mm), at 298K, v = 100 mV s-1, T = 20 . 物理化学学报, 2013, 29: 973.Zhejiang University of TechnologyAg electrodeAg electrode15第十五张，PPT共二十六页，创作于2022年6月E

17、ntryEappa(V)Final product distribution1-1.317% (5), 48% (4E), 35% (4Z)2-1.862% (10), 21% (11E), 17% (11Z)3b-1.292% (10), 8% (toluene)Table 3.1 Electroreduction of benzenyltrichloride at Ag mesh (2.53.0 cm2), in 40 mL catholyte (CH3CN + 0.1 mM TBAP + 5.0 mM benzenyltrichloride), at 20.a Applied poten

18、tial vs. Ag/Ag+.b In present of 1 M CH3COOHZhejiang University of Technology16第十六张，PPT共二十六页，创作于2022年6月3.2.氯乙酸Fig. 3.2 CVs of three electrodes in blank 0.5 M NaOH (1(blue), 2, 3(red) and in present of 50 mM TCAA (1(black, red and green) or 50 mM MCAA (2, 3(black), v = 50 mV s-1, T = 298 K.J. Electroa

19、n. Chem., 2012, 664: 39.Zhejiang University of TechnologyCCl3COOH (TCAA)CH2ClCOOH (MCAA)Ag(p)Ag(r)17第十七张，PPT共二十六页，创作于2022年6月Fig. 3.3 CVs of Ag(r) electrode in blank aqueous solutions + (1) 0.05 M TCAA, (2) 0.05 M DCAA, (3) 0.05 M MCAA, (4) nothing, at 50 mV s-1.Zhejiang University of Technology1-CCl

20、3COOH (TCAA)2-CHCl2COOH (DCAA)3-CH2ClCOOH (MCAA)4-blankpH = 2.2pH = 718第十八张，PPT共二十六页，创作于2022年6月Fig. 3.4 The reduction of TCAA (0.05 M) using Ag (r) electrode, at 298 K, in aqueous solutions of (1) 0.5 M H2SO4, (2) 0.5 M Na2SO4 and (3) 0.5 M NaOH.Fig. 3.5 Current efficiency for the reduction of 0.05

21、M TCAA, using Ag (r) electrode (2 cm 3 cm 0.1 cm), using applied current 110 mA, (1) 0.5 M H2SO4, (2) 0.5 M Na2SO4 and (3) 0.5 M NaOH. Zhejiang University of Technology19第十九张，PPT共二十六页，创作于2022年6月 Fig.3.6 SEM: (1) Ag(p) electrode, (2) Pd/Ag(p) electrode, (3) Ag(r) electrode, and (4) Pd/Ag electrode.3.

22、3. 2,4-二氯苯氧乙酸Electrochem.Commun., 2009, 11: 2133; Electrochim. Acta, 2013, 96: 90.Zhejiang University of TechnologyAg(p) electrodeAg(r) electrodePd/Ag(p) electrodePd/Ag(r) electrode20第二十张，PPT共二十六页，创作于2022年6月Fig. 3.7 CVs of five electrodes in blank 0.5M NaOH (a, b, c, d(black), f(black) and in presen

23、ce of 25 mM 2,4-D (d(red, green), e, f(red), = 50 mV s-1.Zhejiang University of Technology21第二十一张，PPT共二十六页，创作于2022年6月EntryCathodesFinal product distributionCurrentEfficiency (%)Current (mA)/time (h)1Pd/GC1.7% PAA, 98.3% 2,4-D1.650/22Pd/Ag(p)9.9% PAA, 49.6% ClPAA, 40.5% 2,4-D37.250/23Pd/Ag(r)-PdCl217

24、.7% PAA, 37.3% ClPAA, 45.0% 2,4-D77.925/24Pd/Ag(r)-PdCl237.4% PAA, 49.1% ClPAA, 13.5% 2,4-D66.450/25Pd/Ag(r)-PdCl225.3% PAA, 37.2% ClPAA, 35.5% 2,4-D31.475/26Pd/Ti6.8% PAA, 6.1% ClPAA, 87.1% 2,4-D21.125/27Pd/Ti5.7% PAA, 5.5% ClPAA, 88.8% 2,4-D9.150/28Pd/Ti4.5% PAA, 4.9% ClPAA, 90.6% 2,4-D5.075/29Pd/

25、Ag(r)-PdSO410.1% PAA, 46.5% ClPAA, 43.4% 2,4-D71.525/210Pd/Ag(r)-PdSO426.2% PAA, 48.1% ClPAA, 25.7% 2,4-D53.950/211Pd/Ag(r)-PdSO412.4% PAA, 32.3% ClPAA, 55.3% 2,4-D20.475/2Table 3.2 Electroreductions of 25 mM 2,4-D in 0.5 M NaOH, on four different electrodes (34 cm2). PAA:phenoxyacetic acid; ClPAA: 2-Cl and 4-Cl-phenoxyacetic acid; 2,4-D: 2,4-diCl-phenoxyacetic ac