Fe-containing Metal-organic Frameworks Research Articles

MIL-101(Fe)/BiOBr S-scheme photocatalyst for promoting photocatalytic abatement of Cr(VI) and enrofloxacin antibiotic: Performance and mechanism

The development of highly active, economical, and robust bifunctional photocatalysts is a priority for sustainable photocatalytic water remediation. Inadequately available reactive sites and sluggish interface photocarrier transfer and separation remain significant challenges in the photoreaction progress. In this study, the Fe-containing metal-organic framework (MOF) MIL-101(Fe) was integrated with BiOBr microspheres to form a competent S-scheme heterostructure for the photocatalytic mitigation of Cr(VI) and enrofloxacin (ENR) antibiotics. The optimal MIL-101(Fe)/BiOBr exhibited the highest photoactivity, with 99.4% of Cr(VI) and 84.4% of ENR eliminated upon visible-light illumination in a single-pollutant system. The photoactivity of MIL-101(Fe)/BiOBr in the decontamination of the Cr(VI)-ENR co-existence system exhibited a substantial enhancement when compared to that in a single system, owing to the improved utilization of electrons and holes resulting from the synergism between Cr(VI), ENR, and the photocatalyst. The enhanced photoactivity is attributed to two aspects: (1) the incorporation of MIL-101(Fe) results in an increased number of available reactive sites and improved solar harvesting properties; and (2) the S-scheme mechanism enables the effective spatial disassociation of photoexcited carriers and optimization of the photo-redox capability of the system. Through scavenging experiments, electron spin resonance characterization, liquid chromatography-tandem mass spectrometry analysis, and T.E.S.T. theoretical estimation, the catalytic mechanism, antibiotic degradation process, and biotoxicities of the degraded products were analyzed and confirmed. This study provides a viable strategy for building competent MOF-inorganic semiconductor S-scheme photocatalysts with superior photocatalytic decontamination performance.

Fe-containing metal-organic framework with D-penicillamine for cancer-specific hydrogen peroxide generation and enhanced chemodynamic therapy.

Chemodynamic therapy (CDT) is based on the production of cytotoxic reactive oxygen species, such as hydroxyl radicals (•OH). Thus, CDT can be advantageous when it is cancer-specific, in terms of efficacy and safety. Therefore, we propose NH2-MIL-101(Fe), a Fe-containing metal-organic framework (MOF), as a carrier of Cu (copper)-chelating agent, d-penicillamine (d-pen; i.e., the NH2-MIL-101(Fe)/d-pen), as well as a catalyst with Fe-metal clusters for Fenton reaction. NH2-MIL-101(Fe)/d-pen in the form of nanoparticles was efficiently taken into cancer cells and released d-pen in a sustained manner. The released d-pen chelated Cu that is highly expressed in cancer environments and this produces extra H2O2, which is then decomposed by Fe in NH2-MIL-101(Fe) to generate •OH. Therefore, the cytotoxicity of NH2-MIL-101(Fe)/d-pen was observed in cancer cells, not in normal cells. We also suggest a formulation of NH2-MIL-101(Fe)/d-pen combined with NH2-MIL-101(Fe) loaded with the chemotherapeutic drug, irinotecan (CPT-11; NH2-MIL-101(Fe)/CPT-11). When intratumorally injected into tumor-bearing mice in vivo, this combined formulation exhibited the most prominent anticancer effects among all tested formulations, owing to the synergistic effect of CDT and chemotherapy.

Hydroxylation of Phenol Catalyzed by Iron Metal-Organic Framework (Fe-BTC) with Hydrogen Peroxide

Liquid phase catalytic hydroxylation of phenol by Fe-containing metal-organic framework, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate) using 30% H2O2 as an oxidant and H2O as solvent showed good activity and stability under mild reaction conditions. Phenol reacts with hydrogen peroxide over Fe-BTC to produce two main products, viz., catechol and hydroquinone. The effect of temperature, time, substrate/hydrogen peroxide mole ratio and amount of catalyst on catalytic performance were studied. The catalyst could be reused four times without losing significant loss of catalytic performance. The crystallinity and structure of catalyst were unchanged during the catalysis reaction, as confirmed by comparison of XRD and SEM of the fresh and reused catalyst. A reaction mechanism is proposed based on the experimental results.

Enhanced catalytic performance of nitrogen-doped carbon supported FeOx-based catalyst derived from electrospun nanofiber crosslinked N, Fe-containing MOFs for efficient hydrogenation of nitroarenes

Rational design and development of stable nitrogen-doped carbon supported non-noble metal based nanocatalysts with unique natures of active species and support for highly chemoselective hydrogenation of nitroarenes to arylamines remains a grand challenge. Here, firstly, an N, Fe-containing metal-organic frameworks (MOFs) has been designed and synthesized. Furthermore, an efficient N-doped carbon fiber supported FeOx-based nanocatalyst (FeOx@CN-hpes) was prepared via pyrolysis of MOF@polymer composite towards electrospun nanofiber crosslinked N, Fe-containing MOFs. Remarkably, the developed FeOx@CN-hpes enables the hydrogenation of nitrobenzene to aniline with unprecedented performance (215.8 h−1) compared to those of FeOx@CN-hp (176.2 h−1) and FeOx@CN-pes (45.2 h−1) catalysts prepared by conventional approaches. The comparative characterizations have revealed that the high dispersion of FeOx species, enhanced basicity, and more structural defects and Fe-Nx species towards FeOx@CN-hpes are responsible for the high performance. Moreover, the effect of the pyrolysis temperature towards FeOx@CN-hpes on the performance of hydrogenation reaction was also systematically investigated. The results indicated that the FeOx@CN-hpes-400 catalyst prepared at 400 °C was identified as the best hydrogenation catalyst. More importantly, the FeOx@CN-hpes-400 catalyst exhibited excellent activity and exclusive selectivity for the hydrogenation of functionalized nitroarenes to corresponding arylamines, as well as successive recyclability without any loss in both activity and selectivity. Therefore, this work provides a feasible strategy for the synthesis of other heterogeneous MOFs-based derived catalysts with superior catalytic performance for diverse industrial processes.

FeOF nanoparticles wrapped by graphitic carbon layers prepared from Fe-MIL-88B as a cathode material for sodium-ion batteries

Sodium-ion batteries (SIBs) are considered a promising alternative for lithium-ion batteries because of the abundance and economic benefits of sodium. Iron oxyfluoride (FeOF) is attractive as a cathode material for SIBs because of its high theoretical capacity (∼855 mA h g−1), low cost, and environmental friendliness. However, FeOF often suffers from poor rate capability and cycling stability because of its low electronic conductivity and ion diffusion coefficient. In this work, we synthesize FeOF nanoparticles wrapped in graphitic carbon layers in situ prepared from an Fe-containing metal organic framework, Fe-MIL-88B. The FeOF electrode exhibits excellent cycling performance with reversible capacities above 338 mA h g−1 at the 100th cycle and a current density of 100 mA g−1. In addition, the rate capability is significantly improved in comparison with that of FeOF alone.

Reduction of Interferences Using Fe-Containing Metal-Organic Frameworks for Matrix Separation and Enhanced Photochemical Vapor Generation of Trace Bismuth.

Photochemical vapor generation (PVG) has emerged as a promising sample introduction method for atomic spectrometry in recent years. Despite its great success, a major impediment for the wide application of PVG is the interferences from the coexisting ions, especially transition-metal ions. In this work, iron and 1,3,5-benzenetricarboxylic (Fe-BTC), a Fe-containing metal-organic framework (MOF) material, was synthesized and first used as a platform integrating the sample matrix separation, preconcentration, and photocatalysis for the highly selective determination of elements by PVG. Bismuth was selected as a model analyte. Fe-BTC served not only as the photocatalyst for the PVG of Bi3+ but also as an efficient absorbent for the separation of analytes from the sample matrix. Compared with the previous PVG system, the performance of tolerating interferences toward coexisting ions of the proposed method has been greatly improved after using Fe-BTC-based matrix separation. Thus the excess of 10 mg L-1 of Co2+ and 100 mg L-1 of Cu2+, Ni2+, and Fe3+ caused no obvious interferences for 1 μg L-1 of Bi determination. Under the optimal conditions, the limit of detection (LOD, 3σ) of the developed method was 0.3 ng L-1 with the inductively coupled plasma-mass spectrometry (ICPMS) measurement, which could be lowered down to 0.04 ng L-1 after ten times of preconcentration with Fe-BTC prior to analysis. This method was successfully applied for the analysis of Bi in complicated sample matrices of soil (GBW07401), sediment (GBW07310), nickel-iron alloy (GBW01622), and nickel alloys (GBW01641) by the external calibration method.

Olefin Epoxidation over Metal-Organic Frameworks Modified with Transition Metals

Mixed aluminum-containing metal-organic frameworks (MOF) modified with Fe, V, and Ti are synthesized in two steps. At the first step, the amorphous precursors of metal-organic frameworks containing various amounts of transition metals are obtained by the electrochemical method. At the second step, the precursors are crystallized under solvothermal conditions. Study of the effect of synthesis conditions shows that Fe-containing metal-organic frameworks crystallize in the presence of dimethylformamide; V- and Ti-containing counterparts crystallize in the presence of water. The time and temperature of crystallization are varied in the range from 150 to 200°С and 24 to 72 h depending on the concentration of the transition metals. The resulting samples are investigated by low-temperature nitrogen adsorption, scanning electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and thermogravimetric and differential thermal analysis (TGA-DTA). Research into the influence of catalyst composition on its activity in 1-octene epoxidation by tert-butyl hydroperoxide suggests that that the titanium-containing samples are catalytically inactive, while the vanadium-containing samples are more active than the iron-containing ones. Testing of the vanadium-containing samples in propylene epoxidation demonstrates that their activity is comparable with the activity of a commercial titanium silicate catalyst.

Ferrocene-modified iron-based metal-organic frameworks as an enhanced catalyst for activating oxone to degrade pollutants in water

Ferrocene (Fc) has been regarded as a useful catalyst for activating Oxone to generate sulfate radicals (SR) in degradation of organic pollutants. Nevertheless, direct usage of Fc molecules in aqueous solutions may lead to difficult recovery and aggregation. While a few attempts have immobilized Fc on several substrates, these substrates exhibit very low surface areas/porosities and, especially, do not offer significantly additional contributions to catalytic activities. In this study, a Fe-containing metal organic frameworks (MOFs), MIL-101, is particularly selected for the first time as a support to immobilize Fc chemically. Through the Schiff base reaction, ferrocenecarboxaldehyde can react with amine-functionalized MIL-101 (namely, MIL-101-NH2) to form Fc-modified MIL-101 (Fc-MIL). As Fc-MIL consists of both Fe from MIL-101 and Fc and also exhibits high surface areas, it appears as a promising catalyst for activating Oxone. Catalytic activities for Oxone activation by Fc-MIL are studied using batch-type experiments of amaranth dye degradation. Fc-MIL shows higher catalytic activities than its precursor MIL-101-NH2 owing to the modification of Fc, which equips with MIL-101 with more catalytic sites for activating Oxone. Besides, Fc-MIL also outperforms the benchmark catalyst of Oxone activation, Co3O4, to degrade amaranth. In comparison to the other reported catalysts, Fc-MIL shows the much smaller activation energy for amaranth degradation, proving its advantage over other catalysts. The synthesis technique proposed here can be also employed to develop other Fc-modified MOFs for other environmental catalysis applications.

Size-Tunable Atomic Iron Catalysts Derived from Metal-Organic Framework for Oxygen Reduction in Acid Media

The high cost platinum (Pt) catalyst used for the electrocatalysis of oxygen reduction reaction (ORR) is one of the bottlenecks for the widespread deployment of polymer membrane electrolyte fuel cells (PEMFCs). Fe-N-C catalysts, produced by the pyrolysis of iron, nitrogen and carbon precursors together, have been found as one of the promising alternatives to replace Pt with abundant elements and low cost.1-3 The Fe-N coordination structure bonded with carbon, generated during high-temperature pyrolysis, has been identified as the active site for the high ORR activity of Fe-N-C catalysts. However, it remains a grand challenge to prepare Fe-N-C catalysts with abundant Fe-N active sites to achieve high ORR activity, since undesired inactive species (e.g., Fe/Fe3C) are easily obtained during high-temperature pyrolysis due to the improper design and the poor chemistry control in the integration of all precursors, lowering the active sites density of catalysts. We have developed an approach to synthesize Fe-N-C catalysts with exclusively atomic Fe-N active sites instead of inactive Fe agglomeration by using well-defined Fe-containing metal-organic frameworks (MOFs) precursors.4 The morphology of MOF precursors can be directly transferred to Fe-N-C catalysts with the retained and homogenous morphology after pyrolysis. Such well-defined precursors and resulting homogenous catalysts allow us to precisely control and tune the composition and morphology of final Fe-N-C catalysts to understand how the property change of catalysts impact their ORR activity of catalysts. In this presentation, we will discuss the effect of particle size of catalysts on their ORR activity and the critical role of pyrolysis temperature on the formation of Fe-N active sites. The Fe-N-C catalysts with size from 20 nm to 1000 nm are prepared by adjusting the size of MOF crystals in the precursor synthesis. Similar to Pt nanoparticles, the unique size control of the Fe-N-C catalysts enables us to increase the accessible number of Fe-N active sites for ORR. The 50 nm catalyst shows the best ORR activity with a half-wave potential of 0.85 V vs. RHE, only leaving 30 mV gap with Pt/C (60 µgPt/cm2) in 0.5 M H2SO4 along with the excellent stability. When the particle size of catalyst is reduced to 20 nm, significant agglomeration of particles are found in the catalyst, resulting in ORR activity decrease of the catalyst. Using our homogenous model catalysts, the formation of active sites during pyrolysis is investigated by correlated the measured-ORR activity with the bonds change of precursors at various pyrolysis temperature. 800 oC is found to be the critical temperature to form the Fe-N active sites with notable ORR activity, which is related to the generation of new Fe species likely bonded with pyridinic N in the carbon structure. These high performance Fe-N-C catalysts exhibit a promising potential to replace Pt for ORR in future PEMFCs. (1) Wu, G.; More, K. L.; Johnston, C. M.; Zelenay, P. Science 2011, 332, 443. (2) Zhang, H.; Osgood, H.; Xie, X.; Shao, Y.; Wu, G., Nano Energy, 2017, 31, 331-350. (3) Wu, G.; Santandreu, A.; Kellogg, W.; Gupta, S.; Ogoke, O.; Zhang, H.; Wang, H.-L.; Dai, L., Nano Energy, 2016, 29, 83–110. (4) Zhang, H.; Hwang, S.; Wang, M.; Feng, Z.; Karakalos, S.; Luo, L.; Qiao, Z.; Xie, X.; Wang, C.; Su, D.; Shao, Y.; Wu, G. Journal of the American Chemical Society, 2017, 139, 14143–14149.

Atomically Dispersed (AD)Fe-N-C Oxygen Reduction Catalysts for Polymer Electrolyte Membrane Fuel Cells

Atomically dispersed (AD)Fe-N-C catalysts are the ultimate goal towards achieving Fe catalyst size reduction. Such catalysts are expected to have unique properties that can be exploited for the purpose of developing highly active and durable oxygen reduction reaction (ORR) catalysts. The biggest challenge during the fabrication of atomically dispersed catalysts is to prevent clustering of atoms on the support during synthesis. In this work we address this challenge by employing metal organic frameworks (MOFs) as the structural precursor for (AD)Fe-N-C catalysts. Specifically, we (i) synthesize Fe-containing MOFs (Fe-MOFs) followed by (ii) heat treatment of the Fe-MOFs to produce (AD)Fe-N-C catalysts. The heat treatment converts Fe-MOFs to N-doped carbons, with the Fe atoms contained in the MOF being uniformly distributed on the N-doped carbons without observable agglomeration. In the approach used, maintaining the initial morphology of MOFs after the heat treatment step is key to taking advantage of the MOF structural features. In a preliminary experiment, we synthesized an Fe-containing nano platelet-shaped MOF support and heat-treated it at 1000 °C in an oxygen-free atmosphere to obtain atomically dispersed Fe atoms anchored on N-doped carbon nano-plates, (AD)Fe-N-Cnano-plates. Figure 1a (high angle annular dark field scanning transmission electron microscopy (STEM) images)demonstrates that the initial plate-like shape of the MOF, which is typically 30-50 nm wide and up to hundreds of nm long, is successfully maintained during the heat treatment at 1000 °C. Microporosity within the nano-plates is generated during the heat treatment, assuring high accessibility to the Fe atoms within the catalyst. The nitrogen content in the nano-plates measured by X-ray photoelectron spectroscopy is ca. 5 at.%. X-ray diffraction (XRD) confirms the absence of crystalline particles in (AD)Fe-N-Cnano-plates,, e.g., Fe-rich particles in particular. As shown in Figure 1b, aberration-corrected (AC)-STEM clearly indicates that all of the Fe is atomically dispersed over the N-doped carbon nano-plates (individual white dots in the image). No Fe-rich clusters or particles are observed, corroborating successful synthesis of atomically dispersed Fe-N-Cnano-plates catalysts. Electrochemical and fuel cell performance data will be presented attesting to high ORR activity of the (AD)Fe-N-Cnano-plates catalysts. Figure 1

Iron-based metal–organic frameworks (MOFs) for visible-light-induced photocatalysis

Photocatalysis is one of the best solutions to solve the problems of global energy shortage and environmental deterioration since it can utilize the abundant and ubiquitous solar light for chemical transformations. In addition to traditional semiconductor-based photocatalysts, metal–organic frameworks (MOFs), a class of micro–mesoporous hybrid materials, are recently emerging as a new type of photocatalytic materials due to their unique structural characteristics. Among all the MOFs, Fe-containing MOFs are extremely appealing in photocatalysis since most of the Fe-based MOFs are visible light responsive due to the existence of extensive iron–oxo (Fe–O) clusters. In addition, Fe is an earth-abundant metal and Fe-containing complexes are commonly used in catalysis and photocatalysis. In this short review, we summarized the recent progress in using Fe-based MOFs for several photocatalytic applications, including pollutants degradation, water oxidation/reduction, CO2 reduction and organic transformations, with a focus on their different light-harvesting properties as compared with that of Ti- and Zr-containing MOFs as well as the structural influence on photocatalysis due to the existence of the diversified Fe-based MOFs. We hope that such a review can stimulate intensive research for rational design of Fe-based MOFs, one of the most promising MOF-based systems, for photocatalysis.

Facile visual colorimetric sensor based on iron carbide nanoparticles encapsulated in porous nitrogen-rich graphene

Herein, via one-step pyrolysis of glucose, dicyandiamide (DCDA) and Fe containing metal–organic framework (Fe-MOF), small Fe3C nanoparticles were in-situ decorated in 3D porous network of N-rich graphene (NGr). The Fe-MOF served as size regulating precursor, layered g-C3N4 (derived from pyrolysis of DCDA) acted as not only a template to guide the growth of small Fe3C nanoparticles, but also the carbon source for 3D porous NGr network. The intrinsic peroxidase-like catalytic activity of Fe3C/NGr was unpredictably discovered, by taking the oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) with H2O2 as a protocol. Fast and distinguished color change, improved stability in exposure to extreme H2O2 concentration and high temperature were obtained. The Michaelis–Menten kinetics was investigated. The detection of glucose was accomplished over a wide concentration range of 2.0~500.0μM with a detection limit lower than most of other similar systems. The reliability of the present sensor was further evaluated by practical monitoring glucose in diluted serum samples. Low cost and simple preparation, fast and distinguished color change, high tolerance to extreme H2O2 concentration and high temperature, endow Fe3C/NGr as one of the promising materials for fast visual colorimetry.

Controlled synthesis of mixed-valent Fe-containing metal organic frameworks for the degradation of phenol under mild conditions.

A series of MIL-53(Fe)-type materials, Fe(BDC)(DMF,F), were prepared by using different ratios of n(FeCl3)/n(FeCl2), which have varied amounts of Fe(2+) in their frameworks. From FeCl3 to FeCl2, the structures of the synthesized samples transform from MIL-53(Fe) to Fe(BDC)(DMF,F). Along with this structure transformation, the crystal morphology goes through a striking change from a small irregular shape to a big triangular prism. This phenomenon indicates that the addition of FeCl2 is beneficial for the formation of a Fe(BDC)(DMF,F) structure. The catalytic activity of these iron-containing MOFs was tested in phenol degradation with hydrogen peroxide as an oxidant at near neutral pH and 35 °C. The degradation efficiency of these samples increases gradually from MIL-53(Fe) to Fe(BDC)(DMF,F). (57)Fe Mössbauer spectra reveal that Fe(2+) and Fe(3+) coexist in the Fe(BDC)(DMF,F) framework, and the highest amount of Fe(2+) in the sample prepared with mixed FeCl3 and FeCl2 is 26.0%. The result illustrates that the amount of Fe(2+) in the samples can be controlled using varied n(FeCl3)/n(FeCl2) in the feed. The diverse amount of Fe(2+) in this series of FeMOF materials exactly explains the distinction of reaction efficiency. The iron leaching tests, structures of the fresh and used catalysts, and the data of the recycling runs show that the Fe-containing MOFs are stable in this liquid-phase reaction.

Facile synthesis of Fe-containing metal–organic frameworks as highly efficient catalysts for degradation of phenol at neutral pH and ambient temperature

In this work, MIL-53(Fe) was synthesized using a solvothermal method under static conditions. However, it was interesting to find that another MIL-53 type material, Fe(BDC)(DMF,F), was obtained when stirring conditions were used while keeping the other conditions fixed. The Fe-containing metal–organic frameworks (MOFs) were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), 57Fe Mossbauer spectrometry and thermogravimetric analysis (TGA). By simply increasing the crystallization time under agitation, the morphology of the Fe(BDC)(DMF,F) crystals went through a striking transition from a bulky irregular shape to a rod-like morphology. The catalytic performance of the Fe-MOFs was evaluated in the degradation of phenol solution at near neutral pH at 35 °C. A significantly better catalytic activity was achieved for Fe(BDC)(DMF,F) than for MIL-53(Fe) and NH2-MIL-53(Fe) due to the existence of Fe(II) in its framework. Phenol was almost completely decomposed in 3 hours, and the conversions of hydrogen peroxide and chemical oxygen demand (COD) were 74.1% and 78.7%, respectively.

Non-precious electrocatalysts synthesized from metal–organic frameworks

Proton exchange membrane fuel cells (PEMFCs) are considered as clean and efficient energy conversion devices with great potential to replace currently used internal combustion engines (ICEs) in the near future. Developing high-performance and less expensive non-precious metal electrocatalysts for oxygen reduction reaction (ORR) at the cathode side is crucial for widespread application of PEMFCs. Herein an Fe-containing metal–organic framework (MOF) was employed as the sole precursor for preparing a cathode electrocatalyst. The Fe-MOF was synthesized and subsequently subjected to thermolysis under a non-reactive gas atmosphere followed by acid leaching and heat treatment under NH3 at different temperatures between 700 and 1000 °C. Upon pyrolysis, iron–nitrogen containing carbon active sites (Fe/N/C) were formed in parallel with development of an electronically conductive carbon medium produced through pyrolytic carbonization of the organic component of the MOF material. The prepared electrocatalysts were characterized by XRD, N2 physisorption, TEM and XPS. In a H2SO4 (pH = 1) electrolyte, the ORR onset potential of 0.915 V, and the half-wave potential of 0.811 V are achieved using the most promising electrocatalyst (C700/950). The membrane electrode assemblies (MEAs) made of these electrocatalysts were also tested as a cathode in a H2/air single fuel cell. The most promising electrocatalyst (C700/950) demonstrated an open circuit voltage of 0.945 V and a maximum power density of 0.302 W cm−2 reached at 0.391 V.

Solvothermal Synthesis of Fe-MOF-74 and Its Catalytic Properties in Phenol Hydroxylation

A Fe-containing metal-organic framework, Fe-MOF-74, was solvothermally synthesized using FeCl2.4H2O and 2,5-di-hydroxy-1,4-benzenedicarboxylic acid. Characterization was conducted by XRD, BET surface area measurement, FT-IR spectroscopy, TGA, and elemental analysis, which confirmed successful preparation of Fe-MOF-74 having an identical framework structure to that reported for MOF-74. Fe-MOF-74 was found to be an effective heterogeneous catalyst for the hydroxylation of phenol using H2O2 as an oxidant; 60% phenol conversion was achieved at 20 degrees C in water with 68 and 32% selectivity to catechol and hydroquinone, respectively. The effect of temperature, phenol/H2O2 mole ratio, catalyst quantity, and solvent on catalytic performance was discussed, and a reaction mechanism is proposed based upon the experimental results.