Environ. Sci. Technol. 2010, 44, 1875–1880
Bio-Electro-Fenton Process Driven by Microbial Fuel Cell for Wastewater Treatment C H U N - H U A F E N G , † F A N G - B A I L I , * ,‡ HONG-JIAN MAI,† AND XIANG-ZHONG LI§ The Key Lab of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, PR China, Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650, PR China, and Department of Civil and Structural Engineering, The Hong Kong Polytechnic University, Hong Kong, PR China
Received October 31, 2009. Revised manuscript received January 10, 2010. Accepted January 14, 2010.
In this study, we proposed a new concept of utilizing the biological electrons produced from a microbial fuel cell (MFC) to power an E-Fenton process to treat wastewater at neutral pH as a bioelectro-Fenton (Bio-E-Fenton) process. This process can be achieved in a dual-chamber MFC from which electrons were generated via the catalyzation of Shewanella decolorationis S12 in its anaerobic anode chamber and transferred to its aerated cathode chamber equipped with a carbon nanotube (CNT)/γ-FeOOH composite cathode. In the cathode chamber, the Fenton’s reagents including hydrogen peroxide (H2O2) and ferrous irons (Fe2+) were in situ generated. This Bio-EFenton process led to the complete decolorization and mineralization of Orange II at pH 7.0 with the apparent firstorder rate constants, kapp ) 0.212 h-1 and kTOC ) 0.0827 h-1, respectively, and simultaneously produced a maximum power output of 230 mW m-2 (normalized to the cathode surface area). The apparent mineralization current efficiency was calculated to be as high as 89%. The cathode composition was an important factor in governing system performance. When the ratio of CNT to γ-FeOOH in the composite cathode was 1:1, the system demonstrated the fastest rate of Orange II degradation, corresponding to the highest amount of H2O2 formed.
Introduction The electro-Fenton (E-Fenton) process has been widely studied for the destruction of organic and biorefractory pollutants contained in wastewaters by highly oxidative hydroxyl radicals formed from the reaction of electrogenerated H2O2 with Fe2+ (1-11). It offers more advantages than the chemical Fenton process owing to the high efficiency of Fenton’s reagents (e.g., H2O2) utilization and saving costs induced by the chemical storage and transportation. The * Corresponding author phone: 86-20-87024721; fax: 86-2087024123; e-mail:
[email protected]. † South China University of Technology. ‡ Guangdong Institute of Eco-Environmental and Soil Sciences. § The Hong Kong Polytechnic University. 10.1021/es9032925
2010 American Chemical Society
Published on Web 01/28/2010
power consumption in the E-Fenton process will mainly contribute to its operating costs. It should be very attractive and also challenging to develop an energy-saving E-Fenton system. Many reports (12-15) studied the microbial fuel cell (MFC) and showed that electrons can be continuously supplied from the organics existed in wastewaters. The bioelectro-Fenton (Bio-E-Fenton) concept is thus possible by using these bioelectrons produced from the microbial metabolism to drive an E-Fenton process. This can be achieved by properly configuring a MFC (16) reactor which consists of two chambers separated by a cation-exchange membrane: an anaerobic anode chamber filled with biodegradable organic substrates and an aerated cathode chamber with biorefractory pollutants. The electrons are released from the bioreactions at the anode and transported to the cathode through an external load circuit. The twoelectron reduction of oxygen at the cathode results in H2O2 formation (17), which then reacts with a Fe2+ source (e.g., FeSO4 (16)) to produce hydroxyl radicals for pollutant oxidative degradation. With respect to the E-Fenton reaction, it has been found that acidic pH between 2 and 4 is important in facilitating oxidative degradation of pollutants (1-9). This, however, requires an initial pH adjustment with acids and final neutralization of the treated water before it is released into the environment; thus results in an increase in the treatment cost and also sludge production. Recently, it has been shown that using these low soluble iron oxides as iron sources in the electro-Fenton process has the advantages of the ability to self-regulate the supply of a constant amount of iron ions all along the reaction time and also the easy recycling of the iron catalyst after treatment (10, 11, 18, 19). Moreover, it can allow the E-Fenton reaction to proceed under a neutral condition (10, 11). Taking advantages of both the neutral E-Fenton reaction and utilization of bioelectrons as a power supply, in this study we proposed a MFC-driven E-Fenton process as a Bio-E-Fenton reaction system for wastewater treatment at neutral pH. To attain high degradation efficiency at neutral pH, we fabricated a carbon nanotube (CNT)/γ-FeOOH composite cathode for the Bio-E-Fenton system. CNTs were used as the cathode materials for the in situ generation of H2O2 owing to their advantages of large surface area, good conductivity and superior electrochemical activity over other carbon materials toward the two-electron oxygen reduction (11, 20). The lepidocrocite (γ-FeOOH), an iron oxide with higher solubility in water than goethite and hematite, functioned mainly as the Fe2+ source of the E-Fenton reactions. Fe2+ was in situ produced at neutral pH by direct electroreduction of γ-FeOOH to adsorbed ferrous ion, Feads2+, followed by its desorption to aqueous solution as Fe2+ (21). The aim of this study was at demonstrating the feasibility of using such a Bio-E-Fenton system to degrade Orange II, a model azo dye (1-3) that is widely used in a variety of industries such as textile, food, and cosmetics and abundant in their wastewaters, in aqueous solution at neutral pH.
Experimental Section Configuration and Operation of the Bio-E-Fenton Process. A MFC configuration is shown in Figure 1. It consists of two equal rectangular chambers (anode chamber and cathode chamber), which were separated by a cation exchange membrane (Zhejiang Qianqiu Group Co., Ltd. China). Each chamber has an effective volume of 75.6 mL (6.0 × 6.0 × 2.1 cm). The anode is a piece of carbon felt (4.4 × 4.4 × 0.5 cm) which was washed in a hot H2O2 (10%, 90 °C) solution for VOL. 44, NO. 5, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 1. Schematic diagram of the Bio-E-Fenton system having an MFC configuration. 3 h to develop local quinone sites on the carbon surface for improving the anode biocompatibility (22). The cathode is a composite electrode of cabon nanotube (CNT) and γ-FeOOH which was prepared by (1) mixing CNTs (10-15 nm wide and 3-5 µm long, Shenzhen NanoHarbo Co., China) and γ-FeOOH (homemade according to the procedures described elsewhere (23)) with polytetrafluoroethylene (PTFE) solution (Dupont) and ethanol in an ultrasonic bath to form a dough-like paste; (2) assembling the paste between two pieces of Ti mesh (0.1 mm thickness) at a pressure of 10 MPa and 60 °C. The PTFE functions as a promoter (11) for oxygen diffusion in the cathode. Four types of cathodes with different CNT/γ-FeOOH ratios of 1:0, 1:0.5, 1:1, and 1:2 were fabricated with the same amounts of CNT (5 g) and PTFE (0.5 g), but different γ-FeOOH contents. A Ti wire (0.5 mm in diameter) was used to connect the anode and cathode by passing through an external load. Unless otherwise stated, the cathode used was composed of CNT and γ-FeOOH with a ratio of 1:1. The inoculation and operation of the MFC with a pure culture of Shewanella decolorationis S12 (24) were described in the Section S1 of the Supporting Information (SI). Four MFC units including one experimental sample (MFC-A) and three control samples (MFC-B, MFC-C, and MFC-D) were used to account for the decolorization and mineralization of Orange II. Same anode was used in four MFC units, but experiments were conducted under different cathode conditions as summarized in SI Table S1. Each MFC was initiated with an Orange II-free cathode solution (100 mM phosphate buffer solution, PBS) purged with air. When the cell voltage remained unchanged for over one day, the cathode solution was replaced with the fresh solution containing 0.1 mM Orange II dye and 100 mM PBS. The decolorization and mineralization of Orange II occurred in MFC-A once air was continuously purged to its cathode chamber. The MFC-B and MFC-C experiments were designed in the absence of H2O2 and Fe2+, respectively. MFC-B consisted of a N2-purged cathode solution in which Orange II is the sole electron acceptor (25) susceptible for reduction and no H2O2 was generated due to the lack of the dissolved O2. MFC-C used a CNT only electrode without γ-FeOOH as the cathode and no Fe2+ was produced in the absence of an iron source. MFC-D with the same configuration of MFC-A was conducted under an open-circuit condition to avoid any electrochemical reactions and study the effects of adsorption on Orange II removal. Analytical Methods. The concentration of Orange II was determined by a UV-vis spectrophotometry (TU1800-PC, 1876
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Beijing China) at 484 nm. The concentration of H2O2 was determined spectrophotometrically using the iodide method at 351 nm (26). The concentration of Fe2+ was measured based on the light absorption of its complex after reaction with 1, 10-phenantroline at 508 nm. It should be noted that H2O2 and Fe2+ concentrations were detected when Orange II was absent in the cathode chamber. Total organic carbon (TOC) analysis was carried out with a Shimadzu TOC-VSCN analyzer. X-ray power diffraction (XRD) measurements were performed on a Bruker D8 Advance X-ray diffractometer with Cu Ka radiation (1.54178 Å). To evaluate the power performance of the system, the cell polarization curves as well as the anode and cathode polarization curves were measured by varying an external resistor in the range of 10-6000 Ω. The anode and cathode potentials were measured by placing a saturated calomel electrode (SCE, +0.242 V vs SHE) in the anode and cathode chambers for reference. Current density (I) and power density (P) were calculated as follows: U RA
(1)
P ) UI
(2)
I)
where U is the cell voltage measured; R is the electrical resistance; I is the current normalized to the cathode surface area; A is the cathode surface area, and P is the power density. To evaluate the catalytic activity of the cathode toward oxygen reduction, linear sweep voltammetry (LSV) measurements were performed in 100 mM PBS at pH 7.0 using an Autolab potentiostat (PGSTAT30, Eco Chemie). The CNT/ γ-FeOOH composite electrode was used as the working electrode, while a Pt mesh (2 × 2 cm) and a SCE were used as the counter and reference electrodes, respectively. Before the measurements, the solution was saturated with oxygen. A scan rate was set at 50 mV s-1 and temperature was 30 °C.
Results and Discussion Degradation of Orange II. Figure 2 shows the decolorization and mineralization of Orange II in the cathode chamber at pH 7.0 against time. In Figure 2A, a gradual decolorization of the solution in MFC-A was observed with eye as time proceeded. Approximately 100% of the initial Orange II was degraded by the Bio-E-Fenton process within 14 h. However, the Orange II degradations in MFC-B and MFC-C were only achieved by 10 and 8%, respectively, after 14 h. These results
kinetics (eq 4) with an apparent mineralization constant (kTOC) value of 0.0827 h-1. ln
TOCt ) - kTOCt TOC0
(4)
where TOCt and TOC0 are the concentrations of TOC at time t and time 0, respectively, and t is the reaction time. The much lower value of kTOC than that of kapp indicates that the Orange II dye was first oxidized to colorless intermediates and then further oxidized to a final product of CO2 (2, 3). Taking into account the results shown in Figure 2, it can be seen that this Bio-E-Fenton system enables the complete mineralization of Orange II dye at neutral pH and does not need any power input for in situ generation of Fenton’s reagents. The process efficiency was further evaluated in terms of the apparent mineralization current efficiency (MCE) (4, 5, 27, 28) as defined by eq 5. MCE )
∆(TOC)exp × 100 ∆(TOC)theor
(5)
where ∆(TOC)exp is the experimental TOC removal at a given time and ∆(TOC)theor is the theoretical TOC removal calculated according to the reaction indicated by eq 6, if the electrons reaching the cathode are fully utilized for the mineralization of Orange II. In the light of eq 6, the destruction of each molecule of Orange II consumed 84 electrons. C16H11N2NaO4S + 38 H2O f 16CO2 + Na+ + SO4 + + 2 NO(6) 3 + 87 H + 84 e
Accordingly, ∆(TOC)theor can be calculated based on eq 7.
FIGURE 2. Decolorization (A) and mineralization (B) kinetics of Orange II in four MFC units. The inset shows the color change over time in MFC-A. The data point shown represents the average on triplicate measurements obtained from three independent experiments ( standards deviations. demonstrated much less degradation of Orange II in the absence of the Fenton’s regents due to the lack of the dissolved O2 in MFC-B to produce H2O2 and the lack of Fe2+ in MFC-C. In addition, the concentration of Orange II in MFC-D decreased only by 3%, showing that its adsorption on the electrode material under the open circuit condition was insignificant. Figure 2B indicated that the complete mineralization of Orange II within 43 h in MFC-A. As anticipated, there was no TOC reduction for the three control samples. In contrast, a slight TOC increase was observed in MFC-B, MFC-C, and MFC-D possibly due to the release of organic matters from the CNT surfaces and transport of organic species from the anode to the cathode through membrane. In agreement with previous studies (2, 3) concerning Orange II degradation in traditional E-Fenton systems, the exponential decrease of its concentration was observed in the Bio-E-Fenton process at neutral pH. The experimental data in Figure 2A were fitted by the apparent first-order logarithmic decay model (eq 3) and an apparent rate constant (kapp) value of 0.212 h-1 was determined. ln
Ct ) - kappt C0
(3)
where Ct and C0 are the concentrations of Orange II at time t and time zero, respectively, and t is the reaction time. It was found that TOC removal also followed the pseudo first-order
∆(TOC)theor )
∫ It 84FV
×M
(7)
where I is the current generated in the MFC, t is the reaction time, F is the Faraday constant, V is the effective volume of the cathode chamber, and M is the total molecule weight of carbon. The value of MCE in this system was determined to be 89%, much higher than the reported values in other studies ¨ zcan et al. (27) reported a (4, 5, 27, 28). For example, O maximum MCE value of 35% when concerning the mineralization of basic blue 3 dye via the traditional E-Fenton process. The higher MCE value obtained in this study is likely due to the fact that the electrical energy from the MFC can be better utilized for in situ generation of Fenton’s reagents than that from an external energy source, and that the parasite reactions of hydroxyl radicals with H2O2 and Fe2+ (27, 28) are suppressed owing to low amounts of H2O2 and Fe2+ (Table 1) available in this system. To investigate the performance stability of the Bio-EFenton system, the degradation experiments were repeatedly conducted for up to 10 runs. The rate constants of kapp and kTOC were determined as shown in Figure 3. It can be noted that both the values decreased slightly during the first four runs and then dropped dramatically in the fifth run. This phenomenon is the consequence of the gradual decline in anode performance along with the increased number of runs. As shown in SI Figure S2, the curves of anode polarization moved toward less negative potential values with increased slopes when more experiments were run. The curves of cathode polarization, however, showed little variation. The decrease of pH in the anolyte due to accumulation of protons and the depletion of fuel (particularly in the fifth run) should be responsible for the loss of anode activity. More detailed explanations can be found in SI Section S2. After replenishment with the fresh substrate in the anode chamber, the VOL. 44, NO. 5, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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TABLE 1. Dependence of Fe2+ and H2O2 Concentrations, Kinetic Parameters (kapp and kTOC) of Orange II Degradation, And Mineralization Current Efficiency (MCE) on the Cathode Compositiona MFC no.
CNT:γ-FeOOH weight ratio
concentration of Fe2+ (mg L-1)b
concentration of H2O2 (mg L-1)b
kapp (h-1)
kTOC (h-1)
MCE (%)
1 2 3
1:0.5 1:1 1:2
1.52 ( 0.21 1.62 ( 0.18 1.71 ( 0.12
1.61 ( 0.15 3.24 ( 0.08 2.68 ( 0.10
0.119 ( 0.009 0.212 ( 0.011 0.161 ( 0.015
0.0360 ( 0.0011 0.0827 ( 0.0015 0.0504 ( 0.0020
99 ( 1 89 ( 1 62 ( 2
a The data point shown represents the average on triplicate measurements obtained from three independent experiments ( standards deviations. b Concentrations of Fe2+ and H2O2 were determined after a 50 h reaction.
FIGURE 3. Variations in kapp and kTOC values as a function of numbers of experiments. During the first five tests, the anode solution remained unchanged and the repeatable experiments were conducted by changing the cathode solution. The anode solution was replenished with the fresh substrate (20 mM lactate) since the sixth test and remained unchanged in the following tests. The data point shown represents the average on triplicate measurements obtained from three independent experiments ( standards deviations. values of kapp and kTOC were well maintained from the sixth run. Further replacements of the cathode solution only resulted in slight decrease in both values, and the tenth test gave substantially decreased values also due to the consumption of anode substrate and the decrease of pH in anolyte solution. These results showed the durability of the Bio-E-Fenton system operated at neutral pH over 20 d. The XRD analysis (SI Section S3 and Figure S3) on the treated CNT/γ-FeOOH (1:1, 20 day reaction) and the freshly prepared electrodes demonstrated a negligible difference in their patterns and indicated that the composite cathode can be reused. Effect of Cathode Composition on the Process Performance. In the composite cathode, the CNTs can generate H2O2 through a two-electron reduction of oxygen, whereas the γ-FeOOH can release free Fe2+ for the Fenton reactions and also catalyzed oxygen reduction. The ratio of CNT to γ-FeOOH by weight was an important factor to affect performance of the Bio-E-Fenton process. Table 1 shows the effects of the cathode composition on the kinetics of Orange II decolorization and mineralization. By comparing both values of kapp and kTOC among three samples, it can be seen that the rate of Organge II degradation with respect to different cathode compositions increased in an order of 1:0.5 CNT/γ-FeOOH < 1:2 CNT/γ-FeOOH < 1:1 CNT/γ-FeOOH. To understand the differences, the accumulated concentrations of H2O2 and Fe2+ in the three reactors as a function of the reaction time were monitored and the results are presented in Figure 4. The generation of H2O2 on three cathodes showed similar behaviors characterized by three periods: a static stage when there is weakly detectable H2O2 because of the start-up of the MFC; a fast-grown stage when H2O2 is progressively produced; and an equilibrium stage when H2O2 generation rate and its decomposition rate 1878
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FIGURE 4. Concentrations of in situ generated H2O2 (A) and Fe2+ (B) in the cathode chamber with different cathode compositions as a function of time. The data point shown represents the average on triplicate measurements obtained from three independent experiments ( standard deviations. becomes equal. It can be seen that the H2O2 concentrations at the steady-state stage were determined to be 1.61, 3.24, and 2.68 mg L-1 for the composite cathode with the weight ratio (CNT/γ-FeOOH) of 1:0.5, 1:1 and 1:2, respectively. The Fe2+ concentration, however, presented very similar values for all three cases. These observations suggest that H2O2 formation is more sensible to the cathode composition than Fe2+. The observed orders of kapp and kTOC values (Table 1) were consistent with the order of the H2O2 concentration rather than that of the Fe2+concentration. When the ratio of CNT to γ-FeOOH was 1:1, the highest amount of H2O2 was obtained and the fastest rate of Orange II degradation was achieved. These results indicate that the H2O2 concentration plays a more important role in the generation of hydroxyl radicals than Fe2+ for Orange II degradation under the current experimental conditions. Furthermore, the effect of the cathode composition on the power output in MFCs was investigated. Figure 5A shows the power density curves of four MFCs operated with different cathode compositions. A comparison on the maximum power
FIGURE 5. Effects of cathode composition on (A) the power density curves and (B) the anode and cathode polarization curves of different MFCs. The data point shown represents the average on triplicate measurements obtained from three independent experiments ( standard deviations. density of each MFC reactor indicated that more γ-FeOOH was beneficial to the power generation in MFCs and that the CNT/γ-FeOOH (1:2) cathode performed the best among four MFCs. A maximum power density of 312 mW m-2 was obtained at a current density of 0.90 mA m-2. Evidence from the cathode and anode polarization curves (Figure 5B) showed that the different cathode potentials were responsible for the differences in the overall power output. Increasing the content of γ-FeOOH increased the cathode performance in terms of the enhanced cathode open circuit potential (OCP) and working potentials. The comparison between both the data of Orange II degradation kinetics and MFC power densities indicates that
they do not follow the same trend as a function of the cathode composition. To further understand such results, some additional electrochemical experiments in the cathode chamber were performed using the composite cathode as the working electrode. SI Figure S4 shows the linear sweep voltammograms of oxygen reduction on four cathodes in 100 mM PBS at pH 7.0. Note that each voltammetric curve exhibits two reduction peaks. The first reduction peak appears at less negative potential owing to the two-electron reduction from oxygen to H2O2, and the second reduction peak appears at more negative potential owing to further two-electron reduction from H2O2 to water. Increasing the content of γ-FeOOH in the cathode resulted in a positive shift of these two reduction peaks and an increase in the peak currents, showing that the reduction of oxygen can be catalyzed by the iron oxide. The catalytic effect of γ-FeOOH in the cathode thus leads to the enhancement in power output of MFCs. However, owing to the facts that not only γ-FeOOH catalyzed the reduction of oxygen to H2O2, but also accelerated the decomposition of H2O2 to water, a further increase in the content of γ-FeOOH could cause a loss of H2O2 which leads to the decline in kapp and kTOC. This effect was also reflected by the change in MCE as a function of the cathode composition (Table 1). The value of MCE decreased with the increase in γ-FeOOH content because more electrons were decomposed to water and not used for the production of hydroxyl radicals contributing to pollutant degradation. Electron-Transfer Mechanism. Based on the above data, the mechanism of electron transfer in the Bio-E-Fenton process is proposed, as shown in Figure 6. There are three types of reactions available in the process for electron production, transfer and consumption, as bioelectrochemical reactions, electrochemical reactions and chemical reactions. For the bioelectrochemical reactions occurring in the anode chamber, electrons are produced during microbial metabolism. Specifically, upon the biocatalyzation of the S12 strain, lactate is oxidized to produce electrons and protons. Because no artificial mediators were added to the anode chamber, a direct electron-transfer pathway was suggested for the electrons transport from the cell to the anode (29). Subsequently, the electrons collected in the anode pass through an external load and arrive at the cathode chamber where the electrochemical reactions happen. These reactions include the electrochemical reduction of dissolved oxygen to H2O2; electrochemical reduction of γ-FeOOH to Feads2+, followed by its desorption to aqueous Fe2+; and electrochemical reduction of Orange II azo dye. The first two kinds of cathodic reactions were evidenced from the detectable amounts of H2O2 and Fe2+ present in the cathode (Figure 4). The last one was evidenced from the direct utilization of Orange II as the cathode solution in a MFC, as illustrated in our previous report (25). The chemical reactions in the
FIGURE 6. Electron-transfer mechanism in the Bio-E-Fenton system. VOL. 44, NO. 5, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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cathode are associated with Fenton reactions from which the hydroxyl radicals are produced. The radicals with highly oxidative capability then reacted with the organic pollutants, resulting in their mineralization. Some hydroxyl radicals may also react with the H2O2 and Fe2+ available in the cathode solution, known as the parasitic reactions causing a reduction in MCE (27). In addition to the homogeneous reactions, the mineral surface-catalyzed heterogeneous reactions (30) may coexist in such a system. However, it has been reported that the heterogeneous reactions are less significant and play a negligible role in pollutant mineralization as compared to the homogeneous reactions (19). Environmental Perspectives. The Bio-E-Fenton process developed in this study has demonstrated the capability to completely degrade and also mineralize Orange II in aqueous solution at neutral pH. This process by combining two techniques of MFC for bioelectron generation and E-Fenton reaction for pollutant degradation has several advantages of (1) no requirement of an external power supply for the in situ generation of Fenton’s reagents as the E-Fenton reaction is driven by MFC; (2) treating wastewater at neutral pH using a CNT/γ-FeOOH composite cathode as a solid Fe2+ source to avoid any excessive use of acids to adjust pH and to accelerate the cycling rate of Fe3+ reduced to Fe2+ (18, 19); (3) better utilization of H2O2 and Fe2+ than any dosing methods because both the Fenton reagents can be in situ generated and rapidly used for producing hydroxyl radicals. However, it should be noted that there are still several steps before its practical application in wastewater treatment. One concern with this system relates to the improvement of H2O2 production that may be achieved by imposing a small potential to the cathode to facilitate H2O2 production, as suggested by Rozendal et al (17). Furthermore, from an engineering point of view, continuous feeding of the anode and cathode solutions is important; thus another step is to verify this concept with a continuous flow mode and optimize its operational parameters such as retention time, removal efficiency, and work loading in the system.
Acknowledgments The work was financially supported by the National Natural Science Foundation of P. R. China (No. 40771105, 20577007 and 20803025) and the Natural Science Foundation of Guangdong Province, China (No. 8451064101000891).
Supporting Information Available Sections S1-S3, Table S1. and Figures S1-S4. This material is available free of charge via the Internet at http:// pubs.acs.org.
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