Effects of TMPDO and 4-NOH-TMPD on H2O2/HTS Catalytic System for Free Radicals Generation and Its Application†

doi:10.7503/cjcu20170668

Abstract

Abstract:

EPR technique was used to investigate the formation and variation of free radicals on the catalyst and in the liquid phase after adsorption of 2,2,6,6-tetramethyl-piperdin-4-one(TMPDO) and 2,2,6,6-tetramethyl-piperdin-4-one oxime(4-NOH-TMPD) over hollow titanium silicalite(HTS) zeolite in the presence of H₂O₂. The results showed that the EPR signal of HO· in the HTS/H₂O₂ system was significantly decreased after 4-NOH-TMPD adsorbed on HTS, while the signal intensity of · free radical increased by 28 times and that of TiOO^-· increased by more than double. Moreover, Simifonia software simulation indicated that the free radicals of TiOO^-·(η²)…4-NOH-TMPD were formed in the HTS/H₂O₂/4-NOH-TMPD system, and the stabilization of the double-site adsorption of 4-NOH-TMPD in HTS/H₂O₂ to TiOOH was the fundamental cause for the above changes. Furthermore, it was found that as 4-NOH-TMPD added into the HTS/H₂O₂ system, the signal of free radicals on the catalyst almost disappeared while two new free radicals were formed due to the interaction between acetone oxime in liquid phase and Ti—OO^-· or · free radicals, giving HTS/H₂O₂/4-NOH-TMP system with the catalytic activity for the oxidative coupling of acetone oxime to form 2,3-dimethyl-2,3-dinitrobutane(DMNB).

Key words: Electron paramagnetic resonance(EPR), Hollow titanium silicalite(HTS), 2,2,6,6-Tetrame-thyl-piperdin-4-one oxime(4-NOH-TMPD), Acetone oxime

CLC Number:

O643.31

TrendMD:

CHEN Jie, ZHAO Yingxian, ZHANG Yongming, ZHANG Shengjian, YAN Shan, ZHAO Hong, LI Xianming, YING Liyan. Effects of TMPDO and 4-NOH-TMPD on H₂O₂/HTS Catalytic System for Free Radicals Generation and Its Application^†[J]. Chem. J. Chinese Universities, 2018, 39(3): 497.

Figures/Tables 15

Scheme 1 Structures of surface active sites in TS-1/H2O2 system

Fig.1 Solution EPR spectra of experiment(A) and simulation(B)(A) a. HTS/H2O2/4-NOH-TMPD; b. HTS/H2O2/TMPDO; c. HTS/H2O2; d. 0.08 mol/L DMPO. (B) Reaction condition: a. 0.1 g HTS+10.0 g H2O2+0.1 g 4-NOH-TMPD; b. 0.1 g HTS+10.0 g H2O2+0.1 g TMPDO; c. 0.1 g HTS+10.0 g H2O2; 70 ℃, 1 h.

Table 1 Intensities of HO· and · in different systems

System	Intensity of HO·(Gain)	Intensity of ·(Gain)
HTS/H₂O₂	1.5×10⁶	2.5×10⁵
HTS/H₂O₂/TMPDO		5.0×10⁶
HTS/H₂O₂/4-NOH-TMPD		7.0×10⁶

Scheme 2 Formation of TiOO·(η2)…4-NOH-TMPD by interaction of TiOOH(η2)…4-NOH-TMPD with HO·

Scheme 3 Formation of HOO· by interaction of TiOOH(η2)…4-NOH-TMPD with H2O2

Fig.2 EPR spectra of HTS in different systemsa. HTS/H2O2; b. HTS/H2O2/4-NOH-TMPD; c. HTS/H2O2/4-NOH-TMPD/acetone oxime. Reaction condition: a. 0.1 g HTS+10.0 g H2O2; b. 0.1 g HTS+10.0 g H2O2+0.1 g NOH-TMPD; c. 0.1 g HTS+10.0 g H2O2+0.1 g NOH-TMPD, 2 g acetone oxime. 70 ℃, 1 h.

Fig.3 EPR spectra for experiment(a) and simula- tion(b) of HTS in HTS/H2O2 system

Fig.4 EPR spectra for experiment(a) and simulation(b) of HTS in HTS/H2O2/4-NOH-TMPD system

Table 2 EPR parameters of Ti—OO-· in different systems

Systems	g_x	g_y	g_z₁(A)	g_z₂(B)	g_z₃	g	Ref.
HTS/H₂O₂	2.00157	2.00805	2.02525	2.02089		2.01153	This work
TS/H₂O₂	2.0024	2.0085	2.0259	2.0230			[26]
TS/H₂O₂	2.0033	2.0095	2.0269	2.0234			[24]
TS/H₂O₂(Water solvent)	2.0023	2.0090	2.0266	2.0236			[15]
TS/H₂O₂(CH₃OH solvent)	2.0023	2.0090	2.0260	2.0235	2.0220		[15]
HTS/4-NOH-TMPD/H₂O₂	1.98284	2.00524	2.02246			2.00963	This work

Fig.5 Relative EPR intensity of TiOO-· species (A and B) in HTS at different systemsa. HTS/H2O2(A); b. HTS/H2O2(B);c. HTS/4-NOH-TMPD/H2O2(A);d. HTS/4-NOH-TMPD/H2O2(B).

Fig.6 Solution EPR spectra of different systems after acetone ammoximationa. Fresh HTS, m(HTS):m(acetone oxime)=0.6, n(H2O2):n(acetone oxime)=4.0; b. fresh HTS, m(HTS):m(4-NOH-TMPD)=2.0, m(HTS):m(acetone oxime)=0.6, n(H2O2):n(acetone)=4.0; DMPO: 0.08 mol/L. Reaction conditions: n(NH3):n(H2O2)=1: 2, m(H2O2):m(acetone oxime)=1.0, 70 ℃, NH3 and H2O2 were dropped into reactor within 1 h, and reaction time was 15 min.

Scheme 4 Formation of DMNB though radical reactions

Fig.7 Solution EPR spectra of HTS/4-NOH-TMPD/H2O2 after acetone ammoximation a. Experiment spectrum; b. simulation spectrum; c. surplus spectrum.

Scheme 5 Formation of DMNB by the interaction of TiOO-·(η2)…4-NOH-TMPD with acetone oxime

Fig.8 Effect of TMPDO on the oxidation coupling reaction of acetone oxime catalyzed by HTSReaction conditions: 0.1 mol acetone oxime, 50.0 g H2O, n(H2O2):n(acetone oxime)=4.0, m(HTS):m(acetone oxime)=0.3, n(H2O2) :n(NH3) =4.0, dripping H2O2 and NH3 into the solution at fixed pH 10—11 and 90 ℃, keeping isothermal reaction for 2 h.

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Effects of TMPDO and 4-NOH-TMPD on H₂O₂/HTS Catalytic System for Free Radicals Generation and Its Application^†

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