Zeolite Surface Research Articles

Theoretical insight into the polymerization of ethylene on the surface of 3A zeolite: A DFT + kMC study

Separation is the core process of ethylene production, in which the reaction gas is usually dried using 3A zeolite. In this work, ethylene polymerization on the surface of 3A zeolite were investigated by the combination of Density Functional Theory (DFT) and kinetic Monte Carlo (kMC). DFT calculations showed that stepwise mechanism is the dominant path of ethylene dimerization on the surface of 3A zeolite. Then the effect of temperature on the polymerization of ethylene was studied by kMC simulation. When the temperature is higher than 473 K, ethylene begins to polymerize to form corresponding species, which cover the surface and reduce the dehydration performance of 3A zeolite. Based on these, the desorption process with low temperature using pure ethylene as desorption gas for 3A zeolite regeneration is proposed, which can avoid the use of N2, and reduce the equipment investment and energy consumption.

An investigation on the effect of cross-linking state of silicon species on the distribution of framework Al atoms in ZSM-5 zeolite and its catalytic performance for MTO reaction

Controllable regulation of Al atoms distribution in ZSM-5 zeolite framework can effectively modulate product selectivity for MTO reaction. Here, the Al atoms distribution of ZSM-5 zeolite can be adjusted by controlling the cross-linking state of silicon species. Detailed explorations show that, the surface of ZSM-5 zeolite is rich in silicon when low cross-linking state silicon species is silicon source, while the surface of ZSM-5 zeolite is rich in aluminum when high cross-linking state silicon species is silicon source. When the cross-linking state of silicon species presents a “gripper-like” states, Al atoms of ZSM-5 zeolites are homogeneously distributed, and thus, Al atoms tends to be distributed in straight or sinusoidal channels, resulting in high olefin selectivity and low double cycle index in the catalytic MTO reaction process. This work would be beneficial to the design of ZSM-5 zeolite catalyst with desirable acid site distribution for specific reactions.

Catalytic pyrolysis of cellulose and hemicellulose: Investigation on furans selectivity with different zeolite structures at microporous scale

Furans, as high-value chemicals, are very important target products for catalytic pyrolysis of biomass. In this work, the comparative performance of several different zeolites (SAPO18, SAPO11, SAPO34, and SSZ13 with different Si/Al ratios) for catalytic pyrolysis of cellulose and hemicellulose to generate furan compounds was investigated. SSZ13 was firstly found to improve the selectivity of the catalytic conversion of cellulose and hemicellulose to furans with up to 51.83% and 70.03%, respectively. The high selectivity of SSZ-13 was attributed to its smaller crystal size and higher total acid. SAPO11 was found for the first time to have a positive effect on the conversion of 5-HMF to 5-MFF. Correlation analysis suggested that isomerization was the limiting step in converting the cellulose to furans, while dehydration may be the determining step for hemicellulose. GC-MS results indicated the compound in the inner surface after pyrolysis was dominated by polycyclic aromatics and no furans were detected, supporting the hypothesis that the furans were formed on the external surface of zeolite. The difference in mass transfer rates formed on the inner and outer surfaces of the microporous zeolites contributed to the generation and transfer of furans. Compared to complex multifunctional catalysts, simple zeolite structures may have more application potential.

Fly Ash-Based Na-X Zeolite Application in Separation Process of Bovine Serum Albumin from Aqueous Solution in the Presence of Organic Substances with Anionic Character.

The main purpose of the investigations was to explore the protein adsorption on porous materials, as well as to identify the mechanisms of protein attachment without and with other common environmental contaminants, such as drugs, polymers or surfactants. This study applied the Na-X zeolite for the adsorption of bovine serum albumin (BSA) from solutions with various pH values. Electrophoretic mobility measurements and potentiometric titrations were conducted in systems containing both protein and/or PAA (poly(acrylic acid) polymer/DCF (diclofenac) drug/SDS (sodium dodecyl sulfate) surfactant to investigate the protein binding mechanisms in the complex adsorbate systems. In addition, aggregate size and stability measurements were performed in the investigated systems. Based on the research results, it was possible to conclude that the protein adsorbed most preferably on the zeolite surface at a pH value close to its isoelectric point (pI) (102.15 mg/g), and protein adsorption was the lowest in the solutions with strongly alkaline (29.61 mg/g) or acidic (77.45 mg/g) pH values. Thus, the examined zeolitic material can be considered an effective adsorbent for protein removal from an aqueous solution.

Ni − Promoted Cu/ZSM-5 for selective hydrodeoxygenation of furfural to produce 2 − Methylfuran

Catalytic hydrodeoxygenation (HDO) of furfural (FUR) to produce 2 − methylfuran (2 − MeF) is a green way to produce hydrocarbons with fuel − like properties. In this work, bimetallic Ni − Cu alloys supported on ZSM − 5 zeolite catalysts were prepared by wetness impregnation and used for HDO of FUR to produce 2 − MeF. Cu/ZSM − 5 catalyst favoured the adsorption of CO bonding in FUR through a tilted adsorption orientation, avoiding the saturation of furan ring. Moderate addition of Ni in Cu/ZSM-5 accelerated the conversion rate with enhanced adsorption of the FUR and H2, leading to high selectivity of 2 − MeF in the product through sequenced hydrogenation and deoxygenation procedures. Moreover, zeolite surface acid benefited the scission of CO bonding in the intermediate furfuryl alcohol (FOL), further promoting the yield of 2 − MeF. The optimized 2Ni − 6Cu/CZ catalyst (with 2 wt% Ni and 6 wt% Cu on ZSM − 5) gave 2 − MeF yield of 78.8 wt% at 220 °C after 30 min reaction. With further increased Ni concentrations, the hydrogenation of furan ring was accelerated with tetrahydrofurfuryl alcohol (THFOL) as the main product.

Confined Ru Sites in a 13X Zeolite for Ultrahigh H2 Production from NH3 Decomposition.

Catalytic NH3 synthesis and decomposition offer a new promising way to store and transport renewable energy in the form of NH3 from remote or offshore sites to industrial plants. To use NH3 as a hydrogen carrier, it is important to understand the catalytic functionality of NH3 decomposition reactions at an atomic level. Here, we report for the first time that Ru species confined in a 13X zeolite cavity display the highest specific catalytic activity of over 4000 h-1 for the NH3 decomposition with a lower activation barrier, compared to most reported catalytic materials in the literature. Mechanistic and modeling studies clearly indicate that the N-H bond of NH3 is ruptured heterolytically by the frustrated Lewis pair of Ruδ+-Oδ- in the zeolite identified by synchrotron X-rays and neutron powder diffraction with Rietveld refinement as well as other characterization techniques including solid-state nuclear magnetic resonance spectroscopy, in situ diffuse reflectance infrared transform spectroscopy, and temperature-programmed analysis. This contrasts with the homolytic cleavage of N-H displayed by metal nanoparticles. Our work reveals the unprecedented unique behavior of cooperative frustrated Lewis pairs created by the metal species on the internal zeolite surface, resulting in a dynamic hydrogen shuttling from NH3 to regenerate framework Brønsted acid sites that eventually are converted to molecular hydrogen.

Features of the deactivation of Mg/HZSM-5 catalysts for the synthesis of lower olefins from dimethyl ether in a slurry reactor

In a slurry reactor, the formation of compaction products on Mg/HZSM-5 catalysts, irrespective of the SiO2 /Al2O3 molar ratio in the zeolite, proceeds predominantly on strong acidic sites. The composition of compaction products (mostly trimethyl- and tetramethylbenzenes) virtually does not change with a growth of the molar ratio; however, their amount decreases, which is related to a growth of the mesopore volume with an increase in the SiO2 /Al2O3 ratio. This leads to a decrease in diffusion limitations and contribution of secondary reactions and enhances the removal of coke precursors from the zeolite surface, thus promoting the catalyst activity (the conversion of DME increases twofold). The composition of reaction products changes only slightly with a growth of the SiO2 /Al2O3 molar ratio, the total selectivity to lower olefins is ca. 70 wt.%. A rapid loss of the Mg/HZSM-5 activity with extending the operation time in a slurry reactor is caused not by coking, but rather by «clogging» of the catalyst with decomposition products of the dispersion medium (polydimethylsiloxane).

High-Temperature Behavior of Laser Electrodispersion-Prepared Pd/ZSM-5 Hydrocarbon Traps under CO Oxidation Conditions.

Zeolites and metal-doped zeolites are now widely considered as low-temperature hydrocarbon traps to be a part of emission control systems in automobiles. However, due to the high temperature of exhaust gases, the thermal stability of such sorbent materials is of great concern. To avoid the thermal instability problem, in the present work, laser electrodispersion was used to deposit Pd particles on the surface of ZSM-5 zeolite grains (SiO2/Al2O3 = 55 and SiO2/Al2O3 = 30) to obtain Pd/ZSM-5 materials with a Pd loading as low as 0.03 wt.%. The thermal stability was evaluated in a prompt thermal aging regime involving thermal treatment at temperatures up to 1000 °C in a real reaction mixture (CO, hydrocarbons, NO, an excess of O2, and balance N2) and a model mixture of the same composition with the exception of hydrocarbons. Low-temperature nitrogen adsorption and X-ray diffraction analysis were used to examine the stability of the zeolite framework. Special attention was paid to the state of Pd after thermal aging at varied temperatures. By means of transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance UV-Vis spectroscopy, it was shown that palladium, having been initially located on the surface of zeolite, undergoes oxidation and migrates into the zeolite's channels. This enhances the trapping of hydrocarbons and their subsequent oxidation at lower temperatures.

Zeolite performance in removal of multicomponent heavy metal contamination from wastewater

Efficient removal of heavy metal pollutants from wastewater by ion-exchange sorbents requires knowledge and understanding of the interplay between the adsorption patterns of the different components. The present study elucidates the simultaneous adsorption characteristics of six toxic heavy metal cations (Cd2+, Cr3+, Cu2+, Ni2+, Pb2+, and Zn2+) by two synthetic (13X and 4 A) and one natural (clinoptilolite) zeolite from solutions containing equimolar mixtures of the six metals. Equilibrium adsorption isotherms and equilibration dynamics were obtained by ICP-OES and complemented by EDXRF. An order of magnitude lower adsorption efficiency was exhibited by clinoptilolite (maximum of 0.12 mmol ions/g zeolite), relative to that obtained by the synthetic zeolites 13X and 4 A (a maximum of 2.9 and 1.65 mmol ions/g zeolite respectively). The strongest affinities to both zeolites were demonstrated by Pb2+ and Cr3+ (1.5 and 0.85 mmol/g zeolite respectively for 13X, and 0.8 and 0.4 mmol/g zeolite respectively for 4 A adsorbed from the highest solution concentration). The weakest affinities were observed by Cd2+ (0.1 mmol/g for both zeolites), Ni2+ (0.2 and 0.1 mmol/g for 13X and 4 A respectively), and Zn2+ (0.1 mmol/g for both zeolites). Large differences were observed between the two synthetic zeolites in terms of their equilibration dynamics and adsorption isotherms. Pronounced maxima were displayed in the adsorption isotherms for zeolites 13X and 4 A. The decline in adsorption of the weaker adsorbing ions with the increase in total solution concentration was attributed to the thermodynamic equilibrium between the ions adsorbed on the zeolite surface and those in the solution. Regeneration by 3 M KCL eluting solution resulted in considerable reduction in adsorption capacities following each desorption cycle.

Regulate the mesopores and acidic structure of Pt/USY zeolite catalyst for improved performance in the hydroisomerization of phenanthrene to alkyl-adamantane

Adamantane-based high energy density fuels (HEDFs) play a key role in military and aerospace applications due to their high volumetric calorific value and high density. In the preparation of adamantane-based HEDFs by hydroisomerization of polycyclic aromatic hydrocarbons (PAHs) in coal tar, there is competition between cracking and ring-opening reactions. Therefore, USY zeolites were etched with NaOH solution to expand the mesoporous and regulate the acidity, inhibit the cracking reaction, and promote the ring-shift isomerization of perhydrophenanthrene (PHP) to alkyl-adamantane (AlA), increasing the yield of AlA from 19% to 32%. There are two processes in the conversion of PAHs to AlA, hydrogenation and ring-shift isomerization. Phenanthrene was first hydrogenated to PHP, then isomerized to alkyl-adamantane, the product distribution of alkyl-adamantanes with different side chains was discovered, part of the C14 alkyl-adamantanes cracked, and the hydroisomerization reaction of PHP occurred only on the outer surface or pore mouth of USY zeolite. It provides a new perspective for the hydroconversion of PAHs to HEDFs.

Protein-assisted synthesis of zeolite-supported pseudo-single-atom cobalt catalyst for nitrobenzene hydrogenation

A novel pseudo-single-atom cobalt catalyst based on a hollow zeolite microsphere (HZM) constructed by MWW nanosheets was prepared with the aid of bovine serum albumin (BSA). BSA was adsorbed on the external surface of nanosheets, forming a protein coating which prevented cobalt ions getting into micropores of HZM and at the same time induced their implantation on the outer surface through specific ion-protein interaction. The cobalt ions on BSA layer were highly dispersive in that one BSA tended to bind no more than one cobalt ion in a specific region, which constituted the basis of single-atom. Cobalt ions were reduced and trapped in the N-doped carbon layer derived from BSA coating during pyrolysis, obtaining the pseudo-single-atom cobalt catalyst (Co@CN@HZM). Co@CN@HZM exhibited high catalytic efficiency and favorable cycle stability in the reaction from nitrobenzene to aniline. The excellent performance of the catalyst mainly benefited from the highly exposed active sites on the outer surface, the hierarchical porous structure facilitating diffusion, and the oscillating effect of substrate in the cavity of microsphere. This work proposed a facile strategy for preparing single-atom or pseudo-single-atom materials with metal atom uniformly dispersed on the outer surface of zeolites or other similar supports.

Unveiling the elusive roles of Cu species in determining the hydrocarbon trap performance during cold start in Cu-impregnated MFI type zeolites

High-performance zeolite-based hydrocarbon (HC) traps were developed by impregnating MFI zeolites with Cu species. The corresponding cold-start test (CST) results revealed that the optimal Cu loading (ca. 5–7 wt%) led to high CST performance. To the best of our knowledge, our unprecedented complementary investigation based on both experimental and theoretical approaches revealed that Cu+ ions rather than Cu2+ ions were key for securing high HC adsorption (especially propene) in the presence of copious amounts of water vapor. Moreover, tiny CuO nanoparticles (≤ 4 nm) on the exterior zeolite surface resulted in effective HC oxidation. This preferential HC adsorption and oxidation synergistically contributed to effective hydrocarbon trapping, making the Cu-impregnated MFI zeolites active HC traps. However, after hydrothermal treatment, a lower Cu content (3 wt% instead of 5–7 wt%) was rather desirable for preserving the marked CST performance, indicating that the original physicochemical properties were more damaged at higher Cu content.

Machine learning-aided modeling of the hydrogen storage in zeolite-based porous media

Zeolites are among the most popular porous solids for hydrogen storage. Hydrogen attaches to the surface and microporous structure of zeolites. The literature mainly inspected the hydrogen adsorption capacity of zeolites (HACZ) experimentally and paid little attention to its modeling. Furthermore, there is no tool to compare/reveal the role of surface and pore characteristics of zeolites in hydrogen storage. This work applies several well-established artificial intelligence techniques to correlate the HACZ to surface and pore characteristics of zeolites, pressure, and temperature. The topology-tuned multi-layer perceptron neural network is the best model to simulate the hydrogen storage of fourteen systems (NH4Y, X, and ZSM-5). This model predicts the HACZ of a vast experimental databank with a regression coefficient of 0.99875 and an absolute average relative deviation of 6.43%. Results approve that the role of the BET surface area of zeolites on the HACZ is more vital than the pore volume.

Magnetic Adsorbent Based on Faujasite Zeolite Decorated with Magnesium Ferrite Nanoparticles for Metal Ion Removal

Magnetic nanoparticles are a promising alternative as a support in adsorption processes, aiming at the easy recovery of the aqueous medium. A faujasite zeolite (FAU) surface was decorated with magnesium ferrite (MgFe2O4) nanoparticles. FAU is a porous adsorbent with high specific surface area (SSA) and chemical stability. The FAU:MgFe2O4 nanocomposite 3:1 ratio (w w−1) promotes the combination of the surface and magnetic properties. The results showed the effectiveness of the MgFe2O4 immobilization on the FAU surface, exhibiting a high SSA of 400 m2 g−1. The saturation magnetization (Ms) was verified as 5.9 emu g−1 for MgFe2O4 and 0.47 emu g−1 for FAU:MgFe2O4, an environmentally friendly system with soft magnetic characteristics. The magnetic nanocomposite achieved high adsorption values of around 94% removal for Co2+ and Mn2+ ions. Regarding its reuse, the nanocomposite preserved adsorption activity of above 65% until the third cycle. Thus, the FAU:MgFe2O4 nanocomposite presented favorable adsorptive, magnetic, and recovery properties for reuse cycles in polluted water.

Carbon Nanotubes Deposited on Mordenite Zeolite/NiAl-Layered Double Hydroxide Composites as Electrocatalysts for 2,5-Furandicarboxylic Acid Production from 5-Hydroxymethylfurfural

The nanostructured free-standing NiAl-MOR-CNTs electrocatalysts containing carbon nanotubes (CNTs) deposited on mordenite (MOR) zeolite/NiAl-layered double hydroxide (NiAl-LDH) have been successfully fabricated. Initially, the core-shell NiAl-LDH-MOR with hierarchical structures was observed via an aqueous miscible organic solvent treatment process to deposit nanosized NiAl-LDH homogeneously on a zeolite surface. The synthesized NiAl-LDH-MOR composites were calcined to produce highly dispersed metal oxides catalyzing the CNTs formation via chemical vapor deposition using bioethanol as a feedstock, eventually producing the NiAl-MOR-CNTs composites. To illustrate the beneficial aspect of the prepared composite, they were mixed with Nafion as a binder and pressed into circular pellets used as free-standing electrodes for electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), an important renewable monomer of bioplastic. The prepared free-standing electrodes exhibited an excellent catalytic performance of 100% conversion of HMF with a high selectivity of FDCA up to 92% under ambient conditions. Moreover, the synthesized electrocatalysts can be recycled even after several consecutive cycles without any loss of catalytic activity, confirming a high stability of the synthesized electrodes. This work illustrates the design of electrocatalysts by using conductive CNTs grown on highly dispersed metal active sites on zeolite/LDH composites without using commercial conductive supports such as nickel foam or carbon fiber paper.

Strengthening spillover hydrogenation of quinoline compounds over platinum-encapsulated amorphized HA zeolite catalyst

Hydrogen spillover has been widely used in heterogeneous catalysis, yet how to explore the potential of catalyst support to further promote catalytic function of hydrogen spillover has rarely been investigated. Herein, platinum encapsulated into amorphized HA zeolite (denoted as Pt@HA) with generated hydroxyl groups was used as model catalyst to study the role of HA zeolite support on the promotion of catalytic performance in hydrogenation of quinolines to tetrahydroquinolines. Benefiting from small pore size of amorphized HA zeolite to prevent direct interaction of quinoline with encapsulated platinum, Pt@HA showed good catalytic selectivity in this transformation through hydrogen spillover. This remarkable catalytic selectivity was resulted from the interaction of hydroxyl groups at surface of HA zeolite with pyridine moiety through the formation NH bond to facilitate adsorption to make much lower apparent activation energy of Pt@HA for hydrogenation of pyridine moiety than that of benzene moiety, thus exhibiting enhanced catalytic selectivity.

Direct hydrogenation of CO2 into valuable aromatics over K/Fe-Cu-Al @HZSM-5 tandem catalysts: Effects of zeolite surface acidity on aromatics formation

Direct hydrogenation of carbon dioxide (CO2) to value-added aromatics can not only provide a sustainable aromatics synthesis route but also realize CO2 mitigation. However, it remains a great challenge to identify the optimal surface acidity and regulate the selective formation of aromatics during CO2 hydrogenation. Herein, we designed and prepared a series of K/Fe-Cu-Al@HZSM-5 tandem catalysts, and deeply investigated the effects of zeolite surface acidity on the catalytic performance, by changing the SiO2/Al2O3 ratios of HZSM-5 from 25 to 400. It was found that the surface acidity, especially for the Brønsted acidity, plays a crucial role in the aromatics formation. With an increasing Brønsted acidity from 0 to 290 μmol/g, the CO2 conversion keeps relatively stable (around 44%), however, the aromatics yield monotonously increases from 0.9 to 12.8%, indicating a distinct correlation with the Brønsted acidity. Among the obtained aromatics, the majority ones are C6–8 light aromatics, accounting for c.a. 30–60% within time on stream (TOS) of 24 h, but their proportion tends to gradually decrease with TOS, probably due to the catalyst deactivation by coking. Moreover, the possible reaction pathways for aromatics formation over the prepared K/Fe-Cu-Al@HZSM-5 tandem catalysts were also proposed.

Ugi‐modified nano NaY zeolite for the synthesis of new 1,5‐dihydro‐2H‐pyrrol‐2‐ones under mild conditions

In this study, it was aimed to modify the nano zeolite surface via a multi‐component reaction to obtain high functionality in one pot process. For this purpose, the Ugi‐reaction was applied for the first time to develop a novel hydrogen‐bonding nanocatalyst. The nano NaY zeolite was post‐modified using 3‐aminopropyltriethoxysilane (APTES), followed by the Ugi reaction with salicylaldehyde, tert‐butyl isocyanide, and acetic acid to create carboxamide‐functionalized nano NaY. The presence of hydroxyl groups, pores, and carboxamide moieties on the surface of nano zeolite could improve the reactivity, dispersibility, and hydrogen bonding formation capability of the nano zeolite. The formation of the nanocatalyst was investigated by Dynamic Light Scattering (DLS), X‐Ray Diffraction (XRD), Differential Thermal Analysis (DTA), Fourier Transform Infrared spectroscopy (FT‐IR), Thermogravimetric Analysis (TGA), Transmission Electron Microscopy (TEM), Brunauer–Emmett–Teller (BET), Scanning Electron Micrograph (SEM), Elemental analyses, and Energy Dispersive Spectroscopy (EDS). The catalytic activity of the synthesized modified nano zeolite was examined in the three component‐reaction of aldehydes, amines, and ethyl pyruvate to obtain new pyrrol derivatives in high yields under mild conditions. After separation by filtration, the catalyst can be recycled for up to seven subsequent runs without any appreciable activity loss. Thus, the titled heterocycles can be prepared in an eco‐friendly manner since the catalyst is easily recovered and reused, and the procedure is simple to perform. The results indicated that the catalytic system developed in this study may be useful for the preparation of other beneficial heterocyclic compounds under environmentally benign conditions.

Activation of silver nanoparticles by hydrophilic encapsulation for antimicrobial powder coated surfaces

Silver nanoparticles (AgNP) are known as an antimicrobial agent, but they cannot be efficiently converted to active silver ions due to the lack of hydrophilic reaction environment when incorporated into a dry powder coating film. To make these agents effective in the powder coated surface, a novel encapsulation approach was proposed. Silver nanoparticles were first synthesized on the surface of synthetic zeolite A by in-situ chemical reduction method, which was followed by the addition of copper ions through ion exchange. The functionalized zeolite was then encapsulated with different water-soluble hydrophilic polymers to facilitate the generation of silver ions from nanoparticles. The encapsulated additives were incorporated into the resin system for making the antimicrobial powder coating film. The properties of the additives and films were carefully analyzed, and results show that appropriate loading of silver guarantees a high concentration and uniform distribution of silver nanoparticles on the zeolite surface. The strength of the encapsulation with the additive is found to depend on the cations present in the additives. Anionic polymer encapsulation is the most effective solution for releasing silver ions from antimicrobial coated surface. Excessive hydrophilicity is not beneficial to antimicrobial ability and brings cracks on the surface. Additives with non-polymeric hydrophilic encapsulation made from the precipitation of calcium nitrate and sodium phosphate also shows acceptable antimicrobial efficiency. The proposed hydrophilic encapsulation method can well facilitate the activation of silver nanoparticles and ensure an effective antimicrobial property of the powder coating film.

MnFe2O4/zeolite composite catalyst for activating peroxymonosulfate to efficiently degrade antibiotic

To design a catalyst with high catalytic activity and reusability for activating peroxymonosulfate (PMS) to degrade antibiotic, magnetic MnFe2O4/zeolite (MFZ) catalyst was prepared by one-pot co-precipitation hydrothermal method. Comprehensive characterizations indicate MnFe2O4 nanoparticles were supported on the surface of Na-A zeolite. The saturation magnetization of MFZ is 12.85 emu/g, which is sufficient for magnetic solid–liquid separation. The removal of tetracycline in MFZ/PMS oxidation system could reach 96.4%, which was more than 2.7 times of that using PMS alone. And after 5 cycles, the degradation could still reach 80.4%. Mechanism analysis suggests that 1O2 and O2•- played predominant roles in the advanced oxidation process.