1. School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan 523808, China; 2. Dongguan Key Laboratory of Emerging Contaminants, Dongguan 523808, China; 3. School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, China
Abstract：This paper reported the preparation of HNTs@CeO2-Au@Co3O4 core-shell hollow tubular composite catalyst for the reductive degradation of aqueous p-nitrophenol (4-NP) and dye (MB, MO) pollutants. The microstructure and physicochemical properties of the catalyst were characterized by the means of TEM, SEM, EDS, XRD, N2 adsorption-desorption, XPS, etc. The results showed that CeO2 and Co3O4 were used as internal and external active layers to well disperse and immobilize Au nanoparticles (NPs), which were constructed upon halloysite nanotubes (HNTs) via interfacial reaction. The formed core-shell composite catalyst (HNTs@CeO2-Au@Co3O4) was based on the HNTs carrier encapsulated by the CeO2/Co3O4 laminated structure with Au NPs. The catalyst can reduce over 96% of 4-NP, MB and MO pollutants within 3.5, 8 and 3min respectively, in which the corresponding first-order kinetic rate constant (0.856, 0.370, 1.337min-1) and turnover frequency (10.99, 1.90, 2.80min-1) were significantly superior to the control materials including HNTs-Au@Co3O4, HNTs@CeO2-Au and HNTs@CeO2@Co3O4. Besides, HNTs@CeO2-Au@Co3O4 catalyst maintained high reduction conversion of 4-NP, MB and MO pollutants and good structural integrity after 6 consecutive uses. The unique CeO2/Co3O4 laminated structural feature and synergistic enhancement effect of composite components effectively promoted the construction of the high-performance catalytic system, greatly improved the catalytic activity and stability of Au NPs, which endowed the HNTs@CeO2-Au@Co3O4 catalyst with remarkable catalytic capability and recycling performance.
Aslam S, Subhan F, Liu Z, et al.Magnetic Fe3O4@MIL-100(Fe) core-shells decorated with gold nanoparticles for enhanced catalytic reduction of 4-nitrophenol and degradation of azo dye[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2023,660:130904.
[2]
Das R, Sypu V S, Paumo H K, et al.Silver decorated magnetic nanocomposite (Fe3O4@PPy-MAA/Ag) as highly active catalyst towards reduction of 4-nitrophenol and toxic organic dyes [J].Applied Catalysis B:Environmental, 2019,244:546-558.
[3]
Aslam S, Subhan F, Yan Z, et al.Fabrication of gold nanoparticles within hierarchically ZSM-5-based micro-/mesostructures (MMZ) with enhanced stability for catalytic reduction of p-nitrophenol and methylene blue [J].Separation and Purification Technology, 2021, 254:117645.
[4]
Aslam S, Subhan F, Waqas M, et al.Cu nanoparticles confined within ZSM-5derived mesoporous silica (MZ) with enhanced stability for catalytic hydrogenation of 4-nitrophenol and degradation of azo dye [J].Microporous and Mesoporous Materials, 2023,354:112547.
[5]
Soltani M, Zabihi M.Hydrogen generation by catalytic hydrolysis of sodium borohydride using the nano-bimetallic catalysts supported on the core-shell magnetic nanocomposite of activated carbon [J].International Journal of Hydrogen Energy, 2020,45(22):12331-12346.
[6]
Karimi S, Gholinejad M, Khezri R, et al.Gold and palladium supported on an ionic liquid modified Fe-based metal-organic framework (MOF) as highly efficient catalysts for the reduction of nitrophenols, dyes and Sonogashira-Hagihara reactions [J].RSC Advances, 2023,13(12):8101-8113.
[7]
Zhu Q, Zhang W, Cai J, et al.Morphology-controlled synthesis of gold nanoparticles with chitosan for catalytic reduction of nitrophenol [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2022,640:128471.
[8]
Hu C, Yang C, Wang X, et al.Rapid and facile synthesis of Au nanoparticle-decorated porous MOFs for the efficient reduction of 4‑nitrophenol [J].Separation and Purification Technology, 2022,300:121801.
[9]
Liu Y, Dong H, Huang H, et al.Electron-deficient Au nanoparticles confined in organic molecular cages for catalytic reduction of 4-nitrophenol [J].ACS Applied Nano Materials, 2022,5(1):1276-1283.
[10]
Devi A P, Padhi D K, Mishra P M, et al.Bio-surfactant mediated synthesis of Au/g-C3N4 plasmonic hybrid nanocomposite for enhanced photocatalytic reduction of mono-nitrophenols [J].Journal of Industrial and Engineering Chemistry, 2022,108:118-129.
[11]
Wu K, Wang X Y, Guo L L, et al.Facile synthesis of Au embedded CuOx-CeO2 core/shell nanospheres as highly reactive and sinter-resistant catalysts for catalytic hydrogenation of p-nitrophenol [J].Nano Research, 2020,13:2044-2055.
[12]
Ge T, Guo H, Zuo C, et al.Synthesis, characterization, catalytic performance of magnetically recoverable nano-Au/MCeOx (M:Fe, Co and Ni) in direct oxidative esterification of methacrolein and methanol [J].Separation and Purification Technology, 2022,300:121815.
[13]
Yang X, Wei G, Wu P, et al.Novel halloysite nanotube-based ultrafine CoMn2O4 catalyst for efficient degradation of pharmaceuticals through peroxymonosulfate activation [J].Applied Surface Science, 2022,588:152899.
[14]
Wu H, Jian W, Zhang L, et al.Boosting carrier separation in Ag/AgBr/halloysite-nanotubes composites for enhanced photocatalytic performance [J].Materials Science in Semiconductor Processing, 2021,121:105373.
[15]
Deb A K, Biswas B, Goswami N, et al.Synthesis of environmentally benign ultra-small copper nanoclusters-halloysite composites and their catalytic performance on contrasting azo dyes [J].Applied Surface Science, 2021,546:149122.
[16]
Zhang M, Wang L, Yan H, et al.Palladium-halloysite nanocomposites as an efficient heterogeneous catalyst for acetylene hydrochlorination [J].Journal of Materials Research and Technology, 2021,13:2055-2065.
[17]
Yu J, Niedenthal W, Smarsly B M, et al.Au nanoparticles supported on piranha etched halloysite nanotubes for highly efficient heterogeneous catalysis [J].Applied Surface Science, 2021,546:149100.
[18]
Yuan S, Lv X, Zhang Y, et al.Fabrication of mesoporous SiO2/Au/Co3O4 hollow spheres catalysts with core-shell structure for liquid phase oxidation of benzyl alcohol to benzaldehyde [J].Journal of the Taiwan Institute of Chemical Engineers, 2019,103:138-148.
[19]
Fontánez K, García D, Ortiz D, et al.Biomimetic catalysts based on Au@TiO2-MoS2-CeO2 composites for the production of hydrogen by water splitting [J].International Journal of Molecular Sciences, 2023,24(1):363.
[20]
Wei X, Barkaoui S, Chen J, et al.Investigation of Au/Co3O4 nanocomposites in glycol oxidation by tailoring Co3O4 morphology [J].Nanoscale Advances, 2021,3(6):1741-1746.
[21]
Bakhsh E M, Ismail M, Sharafat U, et al.Highly efficient and recoverable Ag-Cu bimetallic catalyst supported on taro-rhizome powder applied for nitroarenes and dyes reduction [J].journal of materials research and technology, 2022,18:769-787.
[22]
Huang J, Tan X, Li C, et al.Green synthesis of Au-NPs on g-C3N4 hybrid nanomaterials based on supramolecular pillar
[6]
arene and its applications for catalysis [J].ACS omega, 2022,7(21):18085-18093.
[23]
Qin L, Huang D, Xu P, et al.In-situ deposition of gold nanoparticles onto polydopamine-decorated g-C3N4 for highly efficient reduction of nitroaromatics in environmental water purification [J].Journal of colloid and interface science, 2019,534:357-369.
[24]
Zeng T, Niu H, Ma Y, et al.In situ growth of gold nanoparticles onto polydopamine-encapsulated magnetic microspheres for catalytic reduction of nitrobenzene [J].Applied Catalysis B:Environmental, 2013,134:26-33.
[25]
Zhang H, Zhang Y, Zhou Y, et al.Synthesis and characterization of a multifunctional nanocatalyst based on a novel type of binary-metal-oxide-coated Fe3O4-Au nanoparticle [J].RSC advances, 2016,6(22):18685-18694.
[26]
Liu B, Yu S, Wang Q, et al.Hollow mesoporous ceria nanoreactors with enhanced activity and stability for catalytic application [J].Chemical communications, 2013,49(36):3757-3759.
[27]
Chang Y C, Chen D H.Catalytic reduction of 4-nitrophenol by magnetically recoverable Au nanocatalyst [J].Journal of hazardous materials, 2009,165(1-3):664-669.
[28]
Li Y, Lu H, Wang Y, et al.Deposition of Au nanoparticles on PDA-functionalized PVA beads as a recyclable catalyst for degradation of organic pollutants with NaBH4in aqueous solution [J].Journal of Alloys and Compounds, 2019,793:115-126.
[29]
Luo J, Zhang N, Lai J, et al.Tannic acid functionalized graphene hydrogel for entrapping gold nanoparticles with high catalytic performance toward dye reduction [J].Journal of hazardous materials, 2015,300:615-623.
[30]
Iqbal K, Iqbal A, Kirillov A M, et al.A new Ce-doped MgAl-LDH@Au nanocatalyst for highly efficient reductive degradation of organic contaminants [J].Journal of Materials Chemistry A, 2017,5(14):6716-6724.
[31]
Malik A, Nath M.Ultrafast catalytic reduction of toxic nitroaromatics and organic colouring dyes by using Au/ZIF-11:Efficient wastewater treatment [J].Journal of Water Process Engineering, 2021,44:102362.
[32]
Esmaeili N, Mohammadi P, Abbaszadeh M, et al.Au nanoparticles decorated on magnetic nanocomposite (GO-Fe3O4/Dop/Au) as a recoverable catalyst for degradation of methylene blue and methyl orange in water [J].International Journal of Hydrogen Energy, 2019, 44(41):23002-23009.
[33]
Fu Y, Qin L, Huang D, et al.Chitosan functionalized activated coke for Au nanoparticles anchoring:Green synthesis and catalytic activities in hydrogenation of nitrophenols and azo dyes [J].Applied Catalysis B:Environmental, 2019,255:117740.
[34]
Yang Z, Liu X, Xia S, et al.Au/Boron organic frameworks for efficient removal and degradation of azo dye pollutants [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2022,646:128884.
[35]
Fang J, Zhang Y, Zhou Y, et al.Synthesis of novel ultrasmall Au-loaded magnetic SiO2/carbon yolk-shell ellipsoids as highly reactive and recoverable nanocatalysts [J].Carbon, 2017,121:602-611.
[36]
Cai L, Zhang L, Xu X.One-step synthesis of ultra-small silver nanoparticles-loaded triple-helix β-glucan nanocomposite for highly catalytic hydrogenation of 4-nitrophenol and dyes [J].Chemical Engineering Journal, 2022,442:136114.
