Home

Citation: Xu Bo, Wu Yue. CATALYTIC ACTION OF MOLYBDOVANADOPHOSPHORIC ACIDS IN DIRECT HYDROXYLATION OF BENZENE——AN EXAMINATION OF THE MECHANISM OF H₂O₂ ACTIVATION[J]. Acta Physico-Chimica Sinica, ;1985, 1(03): 270-280. doi: 10.3866/PKU.WHXB19850312 shu

CATALYTIC ACTION OF MOLYBDOVANADOPHOSPHORIC ACIDS IN DIRECT HYDROXYLATION OF BENZENE——AN EXAMINATION OF THE MECHANISM OF H₂O₂ ACTIVATION

Xu Bo ,
Wu Yue

1.
Changchun Institute of Applied Chemistry; Chinese Academy of Sciences

Received Date: 20 November 1984
Available Online: 15 June 1985

The catalytic behavior of H_(3+n)PMo(12-n)V_nO_(40) (abbreviated to HPA-n hereafter) +H_2O_2 system in the direct hydroxylation of benzene is completely different from that of well-known Fenton reagent(Fe_(2+)+H_2O_2). The comparison experiments showed that the kinetics of the decomposition of H_2O_2 in HPA-n system generally gave Sshaped curves, which is different from that in Fenton system(Fig.2). The sensitivity of active species generated in the HPA_(-n)+H_2O_2 system toward benzene is far less than that generated in Fenton system, which parallels with the response to the concentration of H~+. Phenol is the only product in the HPA-n system. Data obtained from the hydroxylation experiments under different conditions and kinetic studies of the decomposition of H_2O_2 showed that, although the substituted number (n) of vanadium ion in heteropoly anion and the concentration of the catalyst had a great effect on the rate of the decomposition, they had little effect on the product yield (based on H_2O_2). On the other hand, the initial concentration of oxidant had little to do with the initial stage rate of decomposition, but affected the induced period and product yield to certain extent. Electronic spectra showed that during the decomposition of H_2O_2, two intermdiates might formed (Fig.9). Based on these facts, the mechanism of the activation of H_2O_2 and hydroxylation of benzene by molybdovanadophosphoric acid was suggested. It seems that the vanadium ion in hte heteroply anion might associated with H_2O_2 to form the transient “peracid like” species, followed by the transformation into side-on peroxo compound by auto catalytic process. The latter complex, which acted as an active species, played a major role in the activation of H_2O_2 and hydroxylation of benzene. The kinetic equation deduced from the suggested mechanism is as follows:
-(d[H_2O_2])/(dt)=k_1[I]+2k_4[H_2O_2]{[III][HPA]exp[HPA]k_3(t-τ)}{[HPA]+[III]exp[HPA]k_3(t-τ)}
[I] is the concentration of complex HPA·H_2O_2
...
1. [1]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂. Acta Physico-Chimica Sinica, 2025, 41(1): 100001-0. doi: 10.3866/PKU.WHXB202308032
2. [2]
  Mahmoud Sayed , Han Li , Chuanbiao Bie . Challenges and prospects of photocatalytic H₂O₂ production. Acta Physico-Chimica Sinica, 2025, 41(9): 100117-0. doi: 10.1016/j.actphy.2025.100117
3. [3]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
4. [4]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-0. doi: 10.3866/PKU.WHXB202312007
5. [5]
  Xiaofang Li , Zhigang Wang . 调节金助催化剂的d_z²占据轨道增强光催化合成H₂O₂. Acta Physico-Chimica Sinica, 2025, 41(7): 100080-0. doi: 10.1016/j.actphy.2025.100080
6. [6]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . Simultaneously Improving Inter-Plane Crystallization and Incorporating K Atoms in g-C₃N₄ Photocatalyst for Highly-Efficient H₂O₂ Photosynthesis. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-0. doi: 10.3866/PKU.WHXB202406005
7. [7]
  Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang . Recent Progress of Microstructure-Regulated g-C₃N₄ in Photocatalytic NO Conversion: The Pivotal Roles of Adsorption/Activation Sites. Acta Physico-Chimica Sinica, 2025, 41(5): 100039-0. doi: 10.1016/j.actphy.2024.100039
8. [8]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
9. [9]
  Yi Yang , Xin Zhou , Miaoli Gu , Bei Cheng , Zhen Wu , Jianjun Zhang . Femtosecond transient absorption spectroscopy investigation on ultrafast electron transfer in S-scheme ZnO/CdIn₂S₄ photocatalyst for H₂O₂ production and benzylamine oxidation. Acta Physico-Chimica Sinica, 2025, 41(6): 100064-0. doi: 10.1016/j.actphy.2025.100064
10. [10]
  Yu Wang , Haiyang Shi , Zihan Chen , Feng Chen , Ping Wang , Xuefei Wang . 具有富电子Pt^δ−壳层的空心AgPt@Pt核壳催化剂：提升光催化H₂O₂生成选择性与活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100081-0. doi: 10.1016/j.actphy.2025.100081
11. [11]
  Yang Xia , Kangyan Zhang , Heng Yang , Lijuan Shi , Qun Yi . Improving Photocatalytic H₂O₂ Production over iCOF/Bi₂O₃ S-Scheme Heterojunction in Pure Water via Dual Channel Pathways. Acta Physico-Chimica Sinica, 2024, 40(11): 2407012-0. doi: 10.3866/PKU.WHXB202407012
12. [12]
  Xueting Feng , Ziang Shang , Rong Qin , Yunhu Han . Advances in Single-Atom Catalysts for Electrocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2305005-0. doi: 10.3866/PKU.WHXB202305005
13. [13]
  Qi Wu , Changhua Wang , Yingying Li , Xintong Zhang . Enhanced photocatalytic synthesis of H₂O₂ by triplet electron transfer at g-C₃N₄@BN van der Waals heterojunction interface. Acta Physico-Chimica Sinica, 2025, 41(9): 100107-0. doi: 10.1016/j.actphy.2025.100107
14. [14]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 2408015-0. doi: 10.3866/PKU.WHXB202408015
15. [15]
  Xudong Liu , Huili Fan , Junping Xiao , Min Yang , Yan Li . Teaching Approaches to the A_E + A_N Mechanism of Electrophilic Addition Reactions between Olefins and Inorganic Acids in Organic Chemistry. University Chemistry, 2025, 40(7): 367-372. doi: 10.12461/PKU.DXHX202409041
16. [16]
  Xinyi Zhang , Kai Ren , Yanning Liu , Zhenyi Gu , Zhixiong Huang , Shuohang Zheng , Xiaotong Wang , Jinzhi Guo , Igor V. Zatovsky , Junming Cao , Xinglong Wu . Progress on Entropy Production Engineering for Electrochemical Catalysis. Acta Physico-Chimica Sinica, 2024, 40(7): 2307057-0. doi: 10.3866/PKU.WHXB202307057
17. [17]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(Ⅵ) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-0. doi: 10.3866/PKU.WHXB202309020
18. [18]
  Yongqing Xu , Yuyao Yang , Mengna Wu , Xiaoxiao Yang , Xuan Bie , Shiyu Zhang , Qinghai Li , Yanguo Zhang , Chenwei Zhang , Robert E. Przekop , Bogna Sztorch , Dariusz Brzakalski , Hui Zhou . Review on Using Molybdenum Carbides for the Thermal Catalysis of CO₂ Hydrogenation to Produce High-Value-Added Chemicals and Fuels. Acta Physico-Chimica Sinica, 2024, 40(4): 2304003-0. doi: 10.3866/PKU.WHXB202304003
19. [19]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . Molten Intermediate Transportation-Oriented Synthesis of Amino-Rich g-C₃N₄ Nanosheets for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-0. doi: 10.3866/PKU.WHXB202406021
20. [20]
  Weikang Wang , Yadong Wu , Jianjun Zhang , Kai Meng , Jinhe Li , Lele Wang , Qinqin Liu . Green H₂O₂ synthesis via melamine-foam supported S-scheme Cd_0.5Zn_0.5In₂S₄/S-doped carbon nitride heterojunction: synergistic interfacial charge transfer and local photothermal effect. Acta Physico-Chimica Sinica, 2025, 41(8): 100093-0. doi: 10.1016/j.actphy.2025.100093

Get Citation

PDF

XML

Metrics

PDF Downloads(1541)
Abstract views(2440)
HTML views(75)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Address：Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888

DownLoad: Full-Size Img PowerPoint

Return

CATALYTIC ACTION OF MOLYBDOVANADOPHOSPHORIC ACIDS IN DIRECT HYDROXYLATION OF BENZENE——AN EXAMINATION OF THE MECHANISM OF H2O2 ACTIVATION

Metrics

通讯作者: 陈斌, bchen63@163.com

CATALYTIC ACTION OF MOLYBDOVANADOPHOSPHORIC ACIDS IN DIRECT HYDROXYLATION OF BENZENE——AN EXAMINATION OF THE MECHANISM OF H₂O₂ ACTIVATION