By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was as...By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was assumed that the epoxidation reaction would take place between ethylene and the un-dissociated adsorbed oxygen O2 a on the solo active sites, while the deep oxidation would occur between ethylene and the dissociated adsorbed oxygen Oa on the adjacent multi-active sites. In order to describe the effect of 1,2-C2H4Cl2(EDC) inhibitor on the ethylene epoxidation process, the reversible reactions between EDC and vinyl chloride(VC) on the active sites of silver catalyst was introduced. According to the assumed mechanism, the hyperbolic macro-kinetic model of ethylene epoxidation over the A-type silver catalyst was established, and the macrokinetic experiments were carried out in an internal-recycle gradientless reactor operating at a pressure of 2.1 MPa and a temperature in the range of 217.8—249.0 ℃, with the gas composition(molar fraction) consisting of 15.82%—34.65% C2H4, 2.55%—7.80% O2, 0.88%—6.15% CO2, 0.15—2.61 μmol/mol of 1,2-C2H4Cl2 and 0.14—1.28 μmol/mol of C2H3 Cl. By means of the Simplex Optimal Method, the parameters of the macrokinetic models were estimated. Statistical test showed that the macrokinetic models developed for the A-type silver catalyst agree well with the experimental results.展开更多
Thermal treatment either in the presence of oxygen (calcination) or of a reducing agent (reduction) result is all the time a key issue within the preparation of a catalyst. In this work, a microwave plasma treatment w...Thermal treatment either in the presence of oxygen (calcination) or of a reducing agent (reduction) result is all the time a key issue within the preparation of a catalyst. In this work, a microwave plasma treatment was chosen as an alternative to typical calcinations, because it is a more energy efficient process. Thus, a Microwave Fluidized Bed Plasma reactor (MFBP) was employed in catalyst synthesis process under different gas compositions, such as argon and argon/oxygen mixtures over g-alumina supported silver catalysts, which are generally used for selective reduction of NOx by ethanol. After the first catalytic tests performed in the presence of plasma treated catalyst, it can be concluded that plasma treatment process represents an interesting alternative to conventional calcination during catalyst synthesis, resulting in a more sustainable process, moreover in view of its industrial application. In order to understand the particular effect of plasma treatment, the catalysts submitted to this treatment were carefully characterized by means of thermo gravimetric analysis (TGA), differential thermal analysis (DTA) and UV-VIS-NIR.展开更多
The interactions of oxygen with pre-reduced silver catalysts as well as theircatalytic properties for CO selective oxidation in H_2 after oxygen pre-treatment are studied inthis paper. It is found that the pretreatmen...The interactions of oxygen with pre-reduced silver catalysts as well as theircatalytic properties for CO selective oxidation in H_2 after oxygen pre-treatment are studied inthis paper. It is found that the pretreatment exerts a strong influence on the activity andselectivity of the silver catalyst. A drop in activity and selectivity is observed after treating apre-reduced catalyst with oxygen at low temperatures, whereas a converse result is obtained after anoxidizing treatment at high temperatures (T ≥ 350℃). O_2-TPD results show that surface oxygenspecies adsorbs on silver surface after the oxygen treatment at low temperatures. However,penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile thesurface oxygen species disappear. No other silver species except metallic silver are observed on allthe catalysts by XRD, and the size of silver particle is not changed after the treatment withoxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also beremoved by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorptionand diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing thedecrease in CO oxidation activity, in other words, it is important to obtain a clean silver surfacefor increasing the catalyst activity in CO removal from H_2-rich feed gas. The differences inactivity and selectivity due to the oxygen pretreatment at different temperatures are discussed interms of the changes in the surface/subsurface oxygen species of the silver particles.展开更多
以AgNO_(3)和Na_(2)CO_(3)为原料,聚乙二醇为辅助剂,采用水热法合成Ag_(2)CO_(3)光催化剂,再以Ag_(2)CO_(3)、AgNO_(3)与卤化钠为反应物,采用原位沉淀法制得卤化银/碳酸银复合光催化剂。分别用X射线衍射仪、扫描电镜、紫外-可见光谱仪...以AgNO_(3)和Na_(2)CO_(3)为原料,聚乙二醇为辅助剂,采用水热法合成Ag_(2)CO_(3)光催化剂,再以Ag_(2)CO_(3)、AgNO_(3)与卤化钠为反应物,采用原位沉淀法制得卤化银/碳酸银复合光催化剂。分别用X射线衍射仪、扫描电镜、紫外-可见光谱仪及荧光光谱仪等分析产物的结构、形貌和性能,并以甲基橙(MO)溶液为模拟染料溶液,对卤化银/碳酸银复合光催化剂的光催化活性和循环使用稳定性进行评价。结果表明:AgBr/Ag_(2)CO_(3)复合光催化剂(其中AgBr质量分数为90%)的光催化活性最佳;可见光光照5 min后,0.1 g AgBr/Ag_(2)CO_(3)复合光催化剂对MO的光催化降解率为96.6%,分别是单相AgBr、Ag_(2)CO_(3)、TiO2降解率的1.2倍、4.7倍和5.3倍;复合催化剂循环使用3次后对MO降解率达92.7%。卤化银/碳酸银复合光催化剂对甲基橙溶液的降解过程符合准一级动力学模型。展开更多
Traditionally,Ag-containing solid wastes are leached by nitric acid in order to recycle the noble metal.However,the huge amounts of emission of toxic nitrogen oxides demand the development of a new method for silver r...Traditionally,Ag-containing solid wastes are leached by nitric acid in order to recycle the noble metal.However,the huge amounts of emission of toxic nitrogen oxides demand the development of a new method for silver recycling.Recently,considering the Ce(Ⅳ)solution could be regenerated with electrolyzation method,our group invented a novel environmentally friendly process by using Ce(Ⅳ)as the oxidant to dissolve silver from the spent Ag/ɑ-Al_2O_3 catalysts without NO_x emission.To find out the optimal parameters,in this work,the leaching reaction was thoroughly investigated with respect to the temperature,oxidant and HNO_3 concentrations,stirring speed,and time.The optimized leaching reaction gave the leaching silver rate 99.8% in 1 h.The kinetic plots suggested a shrinking core model with the internal diffusion-controlled process and the activation energy of 38.83 k J·mol^(-1).The order in which the experimental conditions influence the reaction was determined through orthogonal analysis:temperature N oxidant concentration N HNO_3 concentration N stirring speed.展开更多
The use of silver metal for hydrodeoxygenation(HDO) applications is scarce and different studies have indicated of its varying HDO activity. Several computational studies have reported of silver having almost zero tur...The use of silver metal for hydrodeoxygenation(HDO) applications is scarce and different studies have indicated of its varying HDO activity. Several computational studies have reported of silver having almost zero turnover frequency for HDO owing to its high C\\O bond breaking energy barrier and low carbon and oxygen binding energies.Herein this work, titania supported silver catalysts were synthesized and firstly used to examine its phenol HDO activity via experimental reaction runs. BET, XRD, FESEM, TEM, EDX, ICP–OES, Pyridine-FTIR, NH_3-TPD and H_2-TPD analyses were done to investigate its physicochemical properties. Phenomena of hydrogen spillover and metal–acid site synergy were examined in this study. With the aid of TiO_2 reducible support, hydrogen spillover and metal–acid site interactions were observed to a certain extent but were not as superior as other Pt, Pd, Ni-based catalysts used in other HDO studies. The experimental findings showed that Ag/TiO_2 catalyst has mediocre phenol conversion but high benzene selectivity which confirms the explanation from other computational studies.展开更多
A new highly efficient, visible light active, silver vanadate/polymeric carbonitride “core/shell” photocatalyst was prepared mechano-chemically prepared by grinding mixtures of <i><span><span style=&q...A new highly efficient, visible light active, silver vanadate/polymeric carbonitride “core/shell” photocatalyst was prepared mechano-chemically prepared by grinding mixtures of <i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate and mesoporous graphitic carbonitride. Besides the core/shell photocatalyst, </span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate/mesoporous polymeric carbonitride composites and supported mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span><span style="white-space:nowrap;">@</span></span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadates were prepared. The materials were characterized by transmission elec</span><span>tron microscopy (TEM), X-ray diffraction (XRD), nitrogen ad- and</span><span> de-sorption, diffuse reflectance UV-Vis measurement (DRS), infrared spectroscopy, Raman microscopy, and time-resolved photoluminescence spectroscopy. The photocatalytic performance of the materials was investigated in the degradation of organics using pharmaceutical ibuprofen and 4-(isobutyl phenyl) propionic acid sodium salt as model compounds under batch conditions. Reaction intermediates were studied by electrospray ionization and time-of-flight mass spectrometry (ESI-TOF-MS). Additionally, the degree of mineralization was determined by total organic carbon TOC measurements. The core/shell photocatalyst has shown superior photocatalytic activity compared to the other prepared composites or supported photocatalysts as well as the single mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span>. Scavenger experiments showed that valence band holes and anio</span><span>nic superoxide radicals are the main active species in the photocatalytic</span><span> process. TOC measurement confirmed the mineralization of the organic compound, which was in line with ESI-TOF-MS experiments. Time-resolved photoluminescence measurements indicated that charges generated in carbonitride migrate via diffusive hopping and exhibit increased mobility in the case of the silver vanadate/polymeric carbonitride composite.</span>展开更多
文摘By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was assumed that the epoxidation reaction would take place between ethylene and the un-dissociated adsorbed oxygen O2 a on the solo active sites, while the deep oxidation would occur between ethylene and the dissociated adsorbed oxygen Oa on the adjacent multi-active sites. In order to describe the effect of 1,2-C2H4Cl2(EDC) inhibitor on the ethylene epoxidation process, the reversible reactions between EDC and vinyl chloride(VC) on the active sites of silver catalyst was introduced. According to the assumed mechanism, the hyperbolic macro-kinetic model of ethylene epoxidation over the A-type silver catalyst was established, and the macrokinetic experiments were carried out in an internal-recycle gradientless reactor operating at a pressure of 2.1 MPa and a temperature in the range of 217.8—249.0 ℃, with the gas composition(molar fraction) consisting of 15.82%—34.65% C2H4, 2.55%—7.80% O2, 0.88%—6.15% CO2, 0.15—2.61 μmol/mol of 1,2-C2H4Cl2 and 0.14—1.28 μmol/mol of C2H3 Cl. By means of the Simplex Optimal Method, the parameters of the macrokinetic models were estimated. Statistical test showed that the macrokinetic models developed for the A-type silver catalyst agree well with the experimental results.
文摘Thermal treatment either in the presence of oxygen (calcination) or of a reducing agent (reduction) result is all the time a key issue within the preparation of a catalyst. In this work, a microwave plasma treatment was chosen as an alternative to typical calcinations, because it is a more energy efficient process. Thus, a Microwave Fluidized Bed Plasma reactor (MFBP) was employed in catalyst synthesis process under different gas compositions, such as argon and argon/oxygen mixtures over g-alumina supported silver catalysts, which are generally used for selective reduction of NOx by ethanol. After the first catalytic tests performed in the presence of plasma treated catalyst, it can be concluded that plasma treatment process represents an interesting alternative to conventional calcination during catalyst synthesis, resulting in a more sustainable process, moreover in view of its industrial application. In order to understand the particular effect of plasma treatment, the catalysts submitted to this treatment were carefully characterized by means of thermo gravimetric analysis (TGA), differential thermal analysis (DTA) and UV-VIS-NIR.
文摘The interactions of oxygen with pre-reduced silver catalysts as well as theircatalytic properties for CO selective oxidation in H_2 after oxygen pre-treatment are studied inthis paper. It is found that the pretreatment exerts a strong influence on the activity andselectivity of the silver catalyst. A drop in activity and selectivity is observed after treating apre-reduced catalyst with oxygen at low temperatures, whereas a converse result is obtained after anoxidizing treatment at high temperatures (T ≥ 350℃). O_2-TPD results show that surface oxygenspecies adsorbs on silver surface after the oxygen treatment at low temperatures. However,penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile thesurface oxygen species disappear. No other silver species except metallic silver are observed on allthe catalysts by XRD, and the size of silver particle is not changed after the treatment withoxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also beremoved by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorptionand diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing thedecrease in CO oxidation activity, in other words, it is important to obtain a clean silver surfacefor increasing the catalyst activity in CO removal from H_2-rich feed gas. The differences inactivity and selectivity due to the oxygen pretreatment at different temperatures are discussed interms of the changes in the surface/subsurface oxygen species of the silver particles.
文摘以AgNO_(3)和Na_(2)CO_(3)为原料,聚乙二醇为辅助剂,采用水热法合成Ag_(2)CO_(3)光催化剂,再以Ag_(2)CO_(3)、AgNO_(3)与卤化钠为反应物,采用原位沉淀法制得卤化银/碳酸银复合光催化剂。分别用X射线衍射仪、扫描电镜、紫外-可见光谱仪及荧光光谱仪等分析产物的结构、形貌和性能,并以甲基橙(MO)溶液为模拟染料溶液,对卤化银/碳酸银复合光催化剂的光催化活性和循环使用稳定性进行评价。结果表明:AgBr/Ag_(2)CO_(3)复合光催化剂(其中AgBr质量分数为90%)的光催化活性最佳;可见光光照5 min后,0.1 g AgBr/Ag_(2)CO_(3)复合光催化剂对MO的光催化降解率为96.6%,分别是单相AgBr、Ag_(2)CO_(3)、TiO2降解率的1.2倍、4.7倍和5.3倍;复合催化剂循环使用3次后对MO降解率达92.7%。卤化银/碳酸银复合光催化剂对甲基橙溶液的降解过程符合准一级动力学模型。
基金Supported by the Key Research Program of Frontier Sciences of CAS(QYZDJ-SSWJSC021)the Science and Technology Cooperation for Yunnan Provinces and CAS(2016IB002)+1 种基金Science and Technology Service Network Initiative of CAS(KFJ-SW-STS-148)National Natural Science Foundation of China(21506233,51402303,21606241,51374191)
文摘Traditionally,Ag-containing solid wastes are leached by nitric acid in order to recycle the noble metal.However,the huge amounts of emission of toxic nitrogen oxides demand the development of a new method for silver recycling.Recently,considering the Ce(Ⅳ)solution could be regenerated with electrolyzation method,our group invented a novel environmentally friendly process by using Ce(Ⅳ)as the oxidant to dissolve silver from the spent Ag/ɑ-Al_2O_3 catalysts without NO_x emission.To find out the optimal parameters,in this work,the leaching reaction was thoroughly investigated with respect to the temperature,oxidant and HNO_3 concentrations,stirring speed,and time.The optimized leaching reaction gave the leaching silver rate 99.8% in 1 h.The kinetic plots suggested a shrinking core model with the internal diffusion-controlled process and the activation energy of 38.83 k J·mol^(-1).The order in which the experimental conditions influence the reaction was determined through orthogonal analysis:temperature N oxidant concentration N HNO_3 concentration N stirring speed.
基金GSP-MOHE,University of Malaya for fully funding this study through the project number "MO008-2015"Ministry of Higher Education of Malaysia (MOHE) for MyBrain15 (MyPhD) programIPPP for project "PG081-2016A"
文摘The use of silver metal for hydrodeoxygenation(HDO) applications is scarce and different studies have indicated of its varying HDO activity. Several computational studies have reported of silver having almost zero turnover frequency for HDO owing to its high C\\O bond breaking energy barrier and low carbon and oxygen binding energies.Herein this work, titania supported silver catalysts were synthesized and firstly used to examine its phenol HDO activity via experimental reaction runs. BET, XRD, FESEM, TEM, EDX, ICP–OES, Pyridine-FTIR, NH_3-TPD and H_2-TPD analyses were done to investigate its physicochemical properties. Phenomena of hydrogen spillover and metal–acid site synergy were examined in this study. With the aid of TiO_2 reducible support, hydrogen spillover and metal–acid site interactions were observed to a certain extent but were not as superior as other Pt, Pd, Ni-based catalysts used in other HDO studies. The experimental findings showed that Ag/TiO_2 catalyst has mediocre phenol conversion but high benzene selectivity which confirms the explanation from other computational studies.
文摘A new highly efficient, visible light active, silver vanadate/polymeric carbonitride “core/shell” photocatalyst was prepared mechano-chemically prepared by grinding mixtures of <i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate and mesoporous graphitic carbonitride. Besides the core/shell photocatalyst, </span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate/mesoporous polymeric carbonitride composites and supported mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span><span style="white-space:nowrap;">@</span></span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadates were prepared. The materials were characterized by transmission elec</span><span>tron microscopy (TEM), X-ray diffraction (XRD), nitrogen ad- and</span><span> de-sorption, diffuse reflectance UV-Vis measurement (DRS), infrared spectroscopy, Raman microscopy, and time-resolved photoluminescence spectroscopy. The photocatalytic performance of the materials was investigated in the degradation of organics using pharmaceutical ibuprofen and 4-(isobutyl phenyl) propionic acid sodium salt as model compounds under batch conditions. Reaction intermediates were studied by electrospray ionization and time-of-flight mass spectrometry (ESI-TOF-MS). Additionally, the degree of mineralization was determined by total organic carbon TOC measurements. The core/shell photocatalyst has shown superior photocatalytic activity compared to the other prepared composites or supported photocatalysts as well as the single mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span>. Scavenger experiments showed that valence band holes and anio</span><span>nic superoxide radicals are the main active species in the photocatalytic</span><span> process. TOC measurement confirmed the mineralization of the organic compound, which was in line with ESI-TOF-MS experiments. Time-resolved photoluminescence measurements indicated that charges generated in carbonitride migrate via diffusive hopping and exhibit increased mobility in the case of the silver vanadate/polymeric carbonitride composite.</span>
