Study on boron and fluorine-doped C3N4 as a solid activator for cyclohexane oxidation with H2O2 catalyzed by 8-quinolinolato ironIII complexes under visible light irradiation
Study on boron and fluorine-doped C3N4 as a solid activator for cyclohexane oxidation with H2O2 catalyzed by 8-quinolinolato ironIII complexes under visible light irradiation
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硼氟掺杂C3N4作为可见光照射下8-羟基喹啉铁(III)配合物催化H2O2环己烷氧化反应固体活化剂的研究
DOI：
10.1016/j.apcata.2019.117342
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发表时间：
2020-01-25
影响因子：
5.5
通讯作者：
Li, Youji
中科院分区：
文献类型：
--
作者：
Tang, Senpei;Fu, Zaihui;Li, Youji
该论文公开了硼氟掺杂碳氮化物（C3N4BF）作为固体活化剂，可以有效加速相对惰性的5,7-二氯-8-羟基喹啉铁配合物（Fe-III(Q(b))(3)）在可见光照射下光催化乙腈（MeCN）中的过氧化氢（H2O2）将环己烷氧化为环己醇和环己酮。实现了25.87%的环己烷转化率，几乎是没有它的两倍，并且明显高于使用普通C3N4作为活化剂或在热催化下获得的结果。此外，它对 Fe-III(Qb)(3) 光催化的这种活化作用也在 H2O2 涉及的其他底物（如甲苯、乙苯、苯甲醇和硫代苯甲醚）的氧化中观察到。 UV-vis和PL光谱、光电流瞬态测量和理论计算支持C3N4，尤其是C3N4 BF可以与Fe-III(Qb)(3)形成强的pi-pi堆积相互作用，从而诱导Fe-III(Qb)(3)的弱结构畸变，并通过捕获活化剂的光生电子增强其光还原活化。因此，Fe-III(Q(b))(3)与C3N4/特别是C3N4 BF的协同催化作用可以显着加速上述热氧化/尤其是光氧化。
This paper discloses that boron and fluorine-doped carbon nitride (C3N4BF), as a solid activator, can efficiently accelerate the relatively inert 5,7-dichloro-8-quinolinolato ironm complex (Fe-III(Q(b))(3)) to photo-catalyze the oxidation of cyclohexane to cyclohexanol and cyclohexanone by hydrogen peroxide (H2O2) in acetonitrile (MeCN) under visible light irradiation and achieve 25.87 % cyclohexane conversion, which is almost twice as high as without it and obviously higher than the results obtained using ordinary C3N4 as an activator or under thermo-catalysis. Furthermore, its such activation effect on Fe-III(Qb)(3) photocatalysis is also observed in the H2O2-involved oxidation of other substrates such as toluene, ethylbenzene, benzyl alcohol and thioanisole. UV-vis and PL spectra, photocurrent transient measurements and theoretical calculations support that C3N4 and especially C3N4 BF can form strong pi-pi stacking interactions with Fe-III(Qb)(3), thus inducing a weakly structural distortion of Fe-III(Qb)(3) and enhancing its photo-reductive activation via capturing the photo-generated electrons of the activator. As a result, the synergistic catalytic effect of Fe-III(Q(b))(3)with C3N4/especillly C3N4 BF can significantly accelerate the above thermo-/especially photo-oxidations.