In-situ Preparation of Sulfonated Carbonaceous Copper Oxide-zirconia Nanocomposite As a Novel and Recyclable Solid Acid Catalyst for Reduction of 4-nitrophenol

Overview

Journal Sci Rep

Specialty Science

Date 2023 Jun 22

PMID 37349346

Authors

Mostafa Farrag

Affiliations

Soon will be listed here.

Abstract

The missing-linker defects of UiO-66 were exploited to covalently anchor Cu nanoclusters (Cu/UiO-66). The molecular interactions between the metals and oxides as copper-zirconia interfaces in Cu/UiO-66 are essential for heterogeneous catalysis, leading to remarkable synergistic impacts on activity and selectivity. Homogeneously distributed carbonaceous mixed metal oxides (CuO/ZrO@C) nanocomposite was prepared via carbonization of the Cu/UiO-66 at 600 °C for 3 h in air. To enhance the acidity properties of the CuO/ZrO@C nanocomposite, a small amount of sulfuric acid was added and heated at 150 °C under an N atmosphere (CuO/ZrO-SOH@C). The synthesised Cu/UiO-66 and CuO/ZrO-SOH@C catalysts were used as novel catalysts in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The Cu/UiO-66 and CuO/ZrO-SOH@C catalysts displayed complete conversion of the 4-NP solution during (4 and 2 min) stirring at room temperature, respectively. These two catalysts exhibited a high reduction rate of 8.61 × 10 s, and 18.3 × 10 s, respectively. The X-ray photoelectron spectroscopic (XPS) analysis showed the charge of copper atoms in the Cu/UiO-66 catalyst was Cu/Cu and in the CuO/ZrO-SOH@C catalyst was Cu/Cu with nearly the same ratio (65/35). The particle size and the elemental composition of the CuO/ZrO-SOH@C catalyst were analysed by using high resolution transmission electron microscopy (HR-TEM), and energy-dispersive X-ray spectroscopy (EDS), and elemental mapping, respectively. The key point beyond the high catalytic activity and selectivity of the CuO/ZrO-SOH@C catalyst is both the carbon-metal oxides heterojunction structure that leads to good dispersion of the CuO and ZrO over the carbon sheets, and the high acidity properties that come from the combination between the Brønsted acid sites from sulfuric acid and Lewis acid sites from the UiO-66. The catalysts exhibited good recyclability efficiency without significant loss in activity, indicating their good potential for industrial applications.

References

Katz M, Brown Z, Colon Y, Siu P, Scheidt K, Snurr R . A facile synthesis of UiO-66, UiO-67 and their derivatives. Chem Commun (Camb). 2013; 49(82):9449-51. DOI: 10.1039/c3cc46105j. View

Farrag M, Ali G . Hydrogen generation of single alloy Pd/Pt quantum dots over CoO nanoparticles via the hydrolysis of sodium borohydride at room temperature. Sci Rep. 2022; 12(1):17040. PMC: 9553983. DOI: 10.1038/s41598-022-21064-z. View

Villabrille P, Vazquez P, Blanco M, Caceres C . Equilibrium adsorption of molybdosilicic acid solutions on carbon and silica: basic studies for the preparation of ecofriendly acidic catalysts. J Colloid Interface Sci. 2005; 251(1):151-9. DOI: 10.1006/jcis.2002.8391. View

Zhu Y, Zheng J, Ye J, Cui Y, Koh K, Kovarik L . Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO to methanol. Nat Commun. 2020; 11(1):5849. PMC: 7674450. DOI: 10.1038/s41467-020-19438-w. View

Farrag M, Tschurl M, Dass A, Heiz U . Infra-red spectroscopy of size selected Au25, Au38 and Au144 ligand protected gold clusters. Phys Chem Chem Phys. 2013; 15(30):12539-42. DOI: 10.1039/c3cp51406d. View

Abdel-Mageed A, Rungtaweevoranit B, Parlinska-Wojtan M, Pei X, Yaghi O, Behm R . Highly Active and Stable Single-Atom Cu Catalysts Supported by a Metal-Organic Framework. J Am Chem Soc. 2019; 141(13):5201-5210. DOI: 10.1021/jacs.8b11386. View

Zhang X, Wang N, Geng L, Fu J, Hu H, Zhang D . Facile synthesis of ultrafine cobalt oxides embedded into N-doped carbon with superior activity in hydrogenation of 4-nitrophenol. J Colloid Interface Sci. 2017; 512:844-852. DOI: 10.1016/j.jcis.2017.11.005. View

Ling S, Slater B . Dynamic acidity in defective UiO-66. Chem Sci. 2018; 7(7):4706-4712. PMC: 6016445. DOI: 10.1039/c5sc04953a. View

Liu H, Jiang T, Han B, Liang S, Zhou Y . Selective phenol hydrogenation to cyclohexanone over a dual supported Pd-Lewis acid catalyst. Science. 2009; 326(5957):1250-2. DOI: 10.1126/science.1179713. View

10.

Larm N, Thon J, Vazmitsel Y, Atwood J, Baker G . Borohydride stabilized gold-silver bimetallic nanocatalysts for highly efficient 4-nitrophenol reduction. Nanoscale Adv. 2022; 1(12):4665-4668. PMC: 9418733. DOI: 10.1039/c9na00645a. View

11.

Hashimi A, Nazhif Mohd Nohan M, Chin S, Zakaria S, Chia C . Rapid Catalytic Reduction of 4-Nitrophenol and Clock Reaction of Methylene Blue using Copper Nanowires. Nanomaterials (Basel). 2019; 9(7). PMC: 6669591. DOI: 10.3390/nano9070936. View

12.

Wu H, Chua Y, Krungleviciute V, Tyagi M, Chen P, Yildirim T . Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption. J Am Chem Soc. 2013; 135(28):10525-32. DOI: 10.1021/ja404514r. View

13.

Larmier K, Liao W, Tada S, Lam E, Verel R, Bansode A . CO -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface. Angew Chem Int Ed Engl. 2017; 56(9):2318-2323. DOI: 10.1002/anie.201610166. View

14.

Xu W, Dong M, Di L, Zhang X . A Facile Method for Preparing UiO-66 Encapsulated Ru Catalyst and its Application in Plasma-Assisted CO Methanation. Nanomaterials (Basel). 2019; 9(10). PMC: 6835285. DOI: 10.3390/nano9101432. View

15.

Farrag M, Das M, Moody M, Samy El-Shall M . Ligand-Protected Ultrasmall Pd Nanoclusters Supported on Metal Oxide Surfaces for CO Oxidation: Does the Ligand Activate or Passivate the Pd Nanocatalyst?. Chemphyschem. 2020; 22(3):312-322. DOI: 10.1002/cphc.202000656. View

16.

Zhi L, Liu H, Xu Y, Hu D, Yao X, Liu J . Pyrolysis of metal-organic framework (CuBTC) decorated filter paper as a low-cost and highly active catalyst for the reduction of 4-nitrophenol. Dalton Trans. 2018; 47(43):15458-15464. DOI: 10.1039/c8dt03327g. View

17.

Ehsani A, Nejatbakhsh S, Soodmand A, Ebrahimi Farshchi M, Aghdasinia H . High-performance catalytic reduction of 4-nitrophenol to 4-aminophenol using M-BDC (M = Ag, Co, Cr, Mn, and Zr) metal-organic frameworks. Environ Res. 2023; 227:115736. DOI: 10.1016/j.envres.2023.115736. View