An energy-effective polyaniline coated graphite felt (PANI@GF) composite cathode for the elec- tro-Fenton (E-Fenton) process was synthesized through an electro-polymerization method. The electrocatalytic activity ...An energy-effective polyaniline coated graphite felt (PANI@GF) composite cathode for the elec- tro-Fenton (E-Fenton) process was synthesized through an electro-polymerization method. The electrocatalytic activity of the cathode for the 2e- ORR process was investigated and dimethyl phthalate (DMP) was used as a model substrate to evaluate its performance in the E-Fenton process. The as-prepared PANI@GF composite possessed a three-dimensional porous structure, which is favorable for 02 diffusion, while the large amount of N atoms in the conductive polyaniline (PANI) enhanced 2e- ORR reactivity. The DMP degradation of the E-Fenton system using PANI@GF was significantly enhanced owing to the improvement in ORR performance. The apparent kinetic con- stant for DMP degradation was 0.0753 min-1, five times larger than that of GF. The optimal carboni- zation temperature and polymerization time for the preparation of the PANI@GF composite cath- ode was found to be 900 ℃ and 1 h, respectively. Measurement conditions are a crucial factor for proper evaluation of cathode electrocatalytic performance. Accordingly, the 02 flow rate, Fe^2+ con- centration, and pH for DMP degradation were optimized at 0.4 L/min, 1.0 mmol/L, and 3.0, respec- tively. These results indicate that the present PANI@GF composite cathode is energy-effective and promising for potential use as an E-Fenton system cathode for the removal of organic pollutants in wastewater.展开更多
The structures of 26 different congeners of polychlorinated biphenyls(PCBs, including monothrough deca-chlorinated) were optimized using density functional theory(DFT) calculations with the 6-31+G(d,p) basis se...The structures of 26 different congeners of polychlorinated biphenyls(PCBs, including monothrough deca-chlorinated) were optimized using density functional theory(DFT) calculations with the 6-31+G(d,p) basis set. The activation energies for the dechlorination of these systems were calculated for direct photodegradation and photosensitized degradation reaction pathways in the presence of natural organic matter(NOM). The dechlorination mechanism of these PCBs and the ring-opening reaction mechanisms(using QST3 method) of the photosensitive degradation products were analyzed. The results showed that(i) the activation energy for the photosensitized degradation of PCBs was much lower than that of direct photodegradation;(ii) the degradation activities(i.e., C–Cl bond cleavage energies) were the same for both degradation pathways and followed the order ortho 〉 meta 〉 para;(iii) the degradation activities of asymmetric PCBs were higher than those of the corresponding symmetrical PCBs for the direct photodegradation and it was completely opposite in the photosensitive degradation;(iv) there was no correlation between the dissociation energy and the number of C–Cl bonds for the direct photodegradation and dechlorination products were all biphenyl;(v) the degradation activity of PCBs decreased as the number of C–Cl bonds increased in the presence of NOM; and(vi) even when the dechlorination reaction was incomplete, it produced chlorophenol. Furthermore, the free radicals of NOM led to the ring-opening reactions of PCBs via an initial addition step. The main site of these ring-opening reactions was the ortho position. Notably, the likelihood of ring-opening reactions occurring involving the degradation products increased as the degradation degree of PCBs increased.展开更多
The geopolymer synthesized by alkali-activated fly ash was firstly used as a novel photocatalyst for degradation of methylene blue (MB) dye from wastewater. The geopolymer is composed of nanoparticulates with an ave...The geopolymer synthesized by alkali-activated fly ash was firstly used as a novel photocatalyst for degradation of methylene blue (MB) dye from wastewater. The geopolymer is composed of nanoparticulates with an average particle size of about 50 nm, More than 90% of pore volume in the fly ash-based geopolymet predominately centralized on the pore size in the range of 17-700 nm. The degradation efficiency of MB dye by fly ash-based geopolymer catalyst was up to 92.79% under UV irradiation due to the synergistic effect of adsorption and semiconductor photocatalysis. The pseudo-first-order and pseudo-second-order rate equations as well as intra-particle diffusion rate equation were employed to correlate analysis for the adsorption kinetics of MB dye, The experimental data agreed well with pseudo-second-order rate equation in both cases of with UV and without UV irradiations. The intra-particle diffusion process is not the rate determining step. The photocatalytic degradation of MB dye in solution obeys third-order reaction kinetics.展开更多
How to directionally design the hollow zeolite via a green route is of great significance. Here, we successfully synthesized the hollow Fe-silicate-1 encapsulated ultra-small Fe_(2)O_(3) nanoparticles (2.5 nm) with hi...How to directionally design the hollow zeolite via a green route is of great significance. Here, we successfully synthesized the hollow Fe-silicate-1 encapsulated ultra-small Fe_(2)O_(3) nanoparticles (2.5 nm) with higher yield (85.2%) by mother liquid than traditional dissolution-recrystallization for the first time, which was achieved by precisely regulating the number and distribution of defects in zeolite and cleverly utilizing the TPAOH and nuclei in mother liquor. The effects of synthetic temperature, synthetic period and addition amount of parent zeolite on the formation of hollow zeolite have been investigated and the effect of synthetic conditions on the defects in parent zeolite has been also firstly quantified. The corresponding formation mechanism has been proposed. The abundant inner defects provided by the zeolite synthesized at 130 °C for 1 day and large amount of TPAOH remaining in mother liquid are conducive to the formation of hollow zeolite. Meanwhile, both parent zeolite and nuclei (4-, 5-member rings and structure units) in mother liquid obtained at 130 °C play the crucial roles in enhancing the zeolite yield. Notably, Fe_(2)O_(3) nanoparticles could decompose into small fragments by the interaction with nuclei in mother liquid. Partial ultra-small Fe_(2)O_(3) nanoparticles would be encapsulated in cavity and the rest could be inserted in the zeolite framework, which is significantly different from the conventional dissolution-recrystallization mechanism. The obtained encapsulated catalyst shows the superior catalytic performance and stability in phenol and tetracycline degradation reactions.展开更多
In this study, the effect of heat treatment on the room temperature strength of W-core Si C fiber produced by chemical vapor deposition(CVD) was investigated. Thermal exposure in the temperature range of 900–1000?...In this study, the effect of heat treatment on the room temperature strength of W-core Si C fiber produced by chemical vapor deposition(CVD) was investigated. Thermal exposure in the temperature range of 900–1000?C decreases the strength of the Si C fiber. Fracture morphology analysis indicates that failure initiations predominantly take place at the W-core/Si C interface. A reaction layer that formed at the W-core/Si C interface during thermal exposure degraded the fiber strength and an empirical linear relationship of strength vs thickness of the reaction layer can be obtained. The kinetics of the growth of the W-core/Si C reaction layer were determined.展开更多
基金supported by the Sino-Greek Science and Technology Cooperation Project (2013DFG62590)the National Natural Science Foundation of China (21575299, 21576300, 21276290)+1 种基金Guangdong Province Nature Science Foundation (2014A030313150)Guangzhou Science and Technology Plan Project (201607010104)~~
文摘An energy-effective polyaniline coated graphite felt (PANI@GF) composite cathode for the elec- tro-Fenton (E-Fenton) process was synthesized through an electro-polymerization method. The electrocatalytic activity of the cathode for the 2e- ORR process was investigated and dimethyl phthalate (DMP) was used as a model substrate to evaluate its performance in the E-Fenton process. The as-prepared PANI@GF composite possessed a three-dimensional porous structure, which is favorable for 02 diffusion, while the large amount of N atoms in the conductive polyaniline (PANI) enhanced 2e- ORR reactivity. The DMP degradation of the E-Fenton system using PANI@GF was significantly enhanced owing to the improvement in ORR performance. The apparent kinetic con- stant for DMP degradation was 0.0753 min-1, five times larger than that of GF. The optimal carboni- zation temperature and polymerization time for the preparation of the PANI@GF composite cath- ode was found to be 900 ℃ and 1 h, respectively. Measurement conditions are a crucial factor for proper evaluation of cathode electrocatalytic performance. Accordingly, the 02 flow rate, Fe^2+ con- centration, and pH for DMP degradation were optimized at 0.4 L/min, 1.0 mmol/L, and 3.0, respec- tively. These results indicate that the present PANI@GF composite cathode is energy-effective and promising for potential use as an E-Fenton system cathode for the removal of organic pollutants in wastewater.
基金supported by the Fundamental Research Funds for the Central Universities in 2013(JB2013146)the Key Projects in the National Science&Technology Pillar Program in the Eleventh Five-Year Plan Period(2008BAC43B01)
文摘The structures of 26 different congeners of polychlorinated biphenyls(PCBs, including monothrough deca-chlorinated) were optimized using density functional theory(DFT) calculations with the 6-31+G(d,p) basis set. The activation energies for the dechlorination of these systems were calculated for direct photodegradation and photosensitized degradation reaction pathways in the presence of natural organic matter(NOM). The dechlorination mechanism of these PCBs and the ring-opening reaction mechanisms(using QST3 method) of the photosensitive degradation products were analyzed. The results showed that(i) the activation energy for the photosensitized degradation of PCBs was much lower than that of direct photodegradation;(ii) the degradation activities(i.e., C–Cl bond cleavage energies) were the same for both degradation pathways and followed the order ortho 〉 meta 〉 para;(iii) the degradation activities of asymmetric PCBs were higher than those of the corresponding symmetrical PCBs for the direct photodegradation and it was completely opposite in the photosensitive degradation;(iv) there was no correlation between the dissociation energy and the number of C–Cl bonds for the direct photodegradation and dechlorination products were all biphenyl;(v) the degradation activity of PCBs decreased as the number of C–Cl bonds increased in the presence of NOM; and(vi) even when the dechlorination reaction was incomplete, it produced chlorophenol. Furthermore, the free radicals of NOM led to the ring-opening reactions of PCBs via an initial addition step. The main site of these ring-opening reactions was the ortho position. Notably, the likelihood of ring-opening reactions occurring involving the degradation products increased as the degradation degree of PCBs increased.
基金financially supported by Industrial Key Project of Shaanxi Province(No.2010K01-080)Open Fund of State Key Laboratory of Architecture Science and Technology in West China(XAUAT)+1 种基金Xi'an University of Architecture and Technology(No.10KF05)Scientific Research Program Funded by Shaanxi Provincial Education Department(No.12JK0579)
文摘The geopolymer synthesized by alkali-activated fly ash was firstly used as a novel photocatalyst for degradation of methylene blue (MB) dye from wastewater. The geopolymer is composed of nanoparticulates with an average particle size of about 50 nm, More than 90% of pore volume in the fly ash-based geopolymet predominately centralized on the pore size in the range of 17-700 nm. The degradation efficiency of MB dye by fly ash-based geopolymer catalyst was up to 92.79% under UV irradiation due to the synergistic effect of adsorption and semiconductor photocatalysis. The pseudo-first-order and pseudo-second-order rate equations as well as intra-particle diffusion rate equation were employed to correlate analysis for the adsorption kinetics of MB dye, The experimental data agreed well with pseudo-second-order rate equation in both cases of with UV and without UV irradiations. The intra-particle diffusion process is not the rate determining step. The photocatalytic degradation of MB dye in solution obeys third-order reaction kinetics.
基金This work was supported by the National Natural Science Foundation of China(Nos.21978198 and 22002052).
文摘How to directionally design the hollow zeolite via a green route is of great significance. Here, we successfully synthesized the hollow Fe-silicate-1 encapsulated ultra-small Fe_(2)O_(3) nanoparticles (2.5 nm) with higher yield (85.2%) by mother liquid than traditional dissolution-recrystallization for the first time, which was achieved by precisely regulating the number and distribution of defects in zeolite and cleverly utilizing the TPAOH and nuclei in mother liquor. The effects of synthetic temperature, synthetic period and addition amount of parent zeolite on the formation of hollow zeolite have been investigated and the effect of synthetic conditions on the defects in parent zeolite has been also firstly quantified. The corresponding formation mechanism has been proposed. The abundant inner defects provided by the zeolite synthesized at 130 °C for 1 day and large amount of TPAOH remaining in mother liquid are conducive to the formation of hollow zeolite. Meanwhile, both parent zeolite and nuclei (4-, 5-member rings and structure units) in mother liquid obtained at 130 °C play the crucial roles in enhancing the zeolite yield. Notably, Fe_(2)O_(3) nanoparticles could decompose into small fragments by the interaction with nuclei in mother liquid. Partial ultra-small Fe_(2)O_(3) nanoparticles would be encapsulated in cavity and the rest could be inserted in the zeolite framework, which is significantly different from the conventional dissolution-recrystallization mechanism. The obtained encapsulated catalyst shows the superior catalytic performance and stability in phenol and tetracycline degradation reactions.
基金the Raman Spectroscopy Laboratory of Institute of Metal Research, Chinese Academy of Sciences for the support in the accomplishment of this paper
文摘In this study, the effect of heat treatment on the room temperature strength of W-core Si C fiber produced by chemical vapor deposition(CVD) was investigated. Thermal exposure in the temperature range of 900–1000?C decreases the strength of the Si C fiber. Fracture morphology analysis indicates that failure initiations predominantly take place at the W-core/Si C interface. A reaction layer that formed at the W-core/Si C interface during thermal exposure degraded the fiber strength and an empirical linear relationship of strength vs thickness of the reaction layer can be obtained. The kinetics of the growth of the W-core/Si C reaction layer were determined.