目的探讨不同前处理方法对使用电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry,ICP-MS)测定白酒中铅含量检测结果准确性的影响。方法采用直接酸化稀释法、蒸干乙醇酸化稀释法和微波消解法分别对3份白酒样品及质...目的探讨不同前处理方法对使用电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry,ICP-MS)测定白酒中铅含量检测结果准确性的影响。方法采用直接酸化稀释法、蒸干乙醇酸化稀释法和微波消解法分别对3份白酒样品及质控白酒样品进行前处理,使用10μg/L铋溶液作为在线内标,使用ICP-MS得到标准工作曲线后,测定白酒中的铅含量,并进行回收率实验。结果标准物质和加标回收率情况表明直接酸化稀释法处理的白酒样品铅平均含量偏低一些,但与其他2种方法相比差异不显著(P>0.05)。3种前处理方法对质控样品测定结果都在允许误差范围内。直接酸化稀释法存在一定的基体影响,蒸干乙醇酸化稀释法和微波消解法稳定性更好。结论蒸干乙醇酸化稀释法简化了白酒样品的前处理过程,减少了硝酸的用量,结果可靠,可在今后的检测工作中进行使用。展开更多
The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 （2006）and Angewa. Chem. In...The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 （2006）and Angewa. Chem. Int. Ed. 50, 1159 （2011）]. A kinetic model with formic acid adsorption （and probably the simultaneous C-H bond activation） as the rate determining step, which contributes to the majority of reaction current for formic acid oxi- dation, was proposed for the direct pathway. The model simulates well the IR spectroscopic results obtained under conditions where the poisoning effect of carbon monoxide （CO） is negligible and formic acid concentration is below 0.1 mol/L. The kinetic simulation predicts that in the direct pathway formic acid oxidation probably only needs one Pt atom as active site, formate is the site blocking species instead of being the active intermediate. We review in detail the conclusion that formate pathway （with either 1st or 2nd order reaction kinetics） is the direct pathway, possible origins for the discrepancies are pointed out.展开更多
Metal organic frameworks(MOFs)constructed from natural/biological units(amino acids)are prospective candidates as catalysts in CO2chemistry owing to their natural origin and high abundance of Lewis acid/base sites and...Metal organic frameworks(MOFs)constructed from natural/biological units(amino acids)are prospective candidates as catalysts in CO2chemistry owing to their natural origin and high abundance of Lewis acid/base sites and functional groups.Herein,we report the catalytic efficiency of an amino‐acid‐based Cu‐containing MOF,denoted as CuTrp(Trp=L‐tryptophan).The CuTrp catalyst was synthesized by direct mixing at room temperature using methanol as a solvent-a synthetic route with notable energy efficiency.The catalyst was characterized using various physicochemical techniques,including XRD,FT‐IR,TGA,XPS,ICP‐OES,FE‐SEM,and BET analysis.The catalytic activity of CuTrp was assessed in the synthesis of cyclic carbonates from epoxides and CO2.The CuTrp operated in synergy with the co‐catalyst tetrabutylammonium bromide under solvent‐free conditions.Several reaction parameters were studied to identify the optimal reaction conditions and a reaction mechanism was proposed based on experimental evidence and previous density functional theory studies.The CuTrp also exhibited satisfactory stability in water and could be reused more than three times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
The increasing demand for iron ore in the world causes the continuous exhaustion of magnetite resources.The utilization of high-phosphorus iron ore becomes the focus.With calcium carbonate(CaCO_(3)),calcium chloride(C...The increasing demand for iron ore in the world causes the continuous exhaustion of magnetite resources.The utilization of high-phosphorus iron ore becomes the focus.With calcium carbonate(CaCO_(3)),calcium chloride(CaCl_(2)),or calcium sulfate(CaSO_(4))as additive,the process of direct reduction and phosphorus removal of high-phosphorus iron ore(phosphorus mainly occurred in the form of Fe_(3)PO_(7) and apatite)was studied by using the technique of direct reductiongrinding-magnetic separation.The mechanism of calcium compounds to reduce phosphorus was investigated from thermodynamics,iron metallization degree,mineral composition and microstructure.Results showed that Fe_(3)PO_(7) was reduced to elemental phosphorus without calcium compounds.The iron-phosphorus alloy was generated by react of metallic iron and phosphorus,resulting in high phosphorus in reduced iron products.CaCO_(3) promoted the reduction of hematite and magnetite,and improved iron metallization degree,but inhibited the growth of metallic iron particles.CaCl_(2) strengthened the growth of iron particles.However,the recovery of iron was reduced due to the formation of volatile FeCl_(2).CaSO_(4) promoted the growth of iron particles,but the recovery of iron was drastically reduced due to the formation of non-magnetic FeS.CaCO_(3),CaCl_(2) or CaSO_(4) could react with Fe_(3)PO_(7) to form calcium phosphate(Ca_(3)(PO_(4))_(2)).With the addition of CaCO_(3),Ca_(3)(PO_(4))_(2) was closely combined with fine iron particles.It is difficult to separate iron and phosphorus by grinding and magnetic separation,resulting in the reduced iron product phosphorus content of 0.18%.In the presence of CaCl_(2) or CaSO_(4),the boundary between the generated Ca_(3)(PO_(4))_(2) and the metallic iron particles was obvious.Phosphorus was removed by grinding and magnetic separation,and the phosphorus content in the reduced iron product was less than 0.10%.展开更多
The two-stage and two-phase anaerobic process (TSTP) composed of hydrolytic acidification reactor,first-order and second-order external circulation anaerobic reactors (EC) was taken to treat methanol wastewater. Test ...The two-stage and two-phase anaerobic process (TSTP) composed of hydrolytic acidification reactor,first-order and second-order external circulation anaerobic reactors (EC) was taken to treat methanol wastewater. Test results show that TSTP process is quick start-up in 51 d, and the maximum VFA of hydrolytic acidification reactor effluent reaches 876 mg/L. Under the condition of volume loading of 6.56 kgCOD/m3·d, COD removal rate of the first-order EC reactor is about 85%, and under the condition of volume loading of 1.02 kgCOD/m3·d, COD removal rate of the second-order EC reactor is about 50%. When the inflow COD of TSTP process is between 7000-11000 mg/L, its effluent COD is lower than 600 mg/L. In the biological conversion process of methanol into methane,the production of acetic acids as an intermediate product can be ignored and the direct production of methane from methanol is predominant.展开更多
文摘目的探讨不同前处理方法对使用电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry,ICP-MS)测定白酒中铅含量检测结果准确性的影响。方法采用直接酸化稀释法、蒸干乙醇酸化稀释法和微波消解法分别对3份白酒样品及质控白酒样品进行前处理,使用10μg/L铋溶液作为在线内标,使用ICP-MS得到标准工作曲线后,测定白酒中的铅含量,并进行回收率实验。结果标准物质和加标回收率情况表明直接酸化稀释法处理的白酒样品铅平均含量偏低一些,但与其他2种方法相比差异不显著(P>0.05)。3种前处理方法对质控样品测定结果都在允许误差范围内。直接酸化稀释法存在一定的基体影响,蒸干乙醇酸化稀释法和微波消解法稳定性更好。结论蒸干乙醇酸化稀释法简化了白酒样品的前处理过程,减少了硝酸的用量,结果可靠,可在今后的检测工作中进行使用。
基金This work was supported by one hundred Tal- ents＇ Program of the Chinese Academy of Science, the National Natural Science Foundation of China （No.21273215）, 973 program from the Ministry of Sci- ence and Technology of China （No.2010CB923302）.
文摘The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 （2006）and Angewa. Chem. Int. Ed. 50, 1159 （2011）]. A kinetic model with formic acid adsorption （and probably the simultaneous C-H bond activation） as the rate determining step, which contributes to the majority of reaction current for formic acid oxi- dation, was proposed for the direct pathway. The model simulates well the IR spectroscopic results obtained under conditions where the poisoning effect of carbon monoxide （CO） is negligible and formic acid concentration is below 0.1 mol/L. The kinetic simulation predicts that in the direct pathway formic acid oxidation probably only needs one Pt atom as active site, formate is the site blocking species instead of being the active intermediate. We review in detail the conclusion that formate pathway （with either 1st or 2nd order reaction kinetics） is the direct pathway, possible origins for the discrepancies are pointed out.
文摘Metal organic frameworks(MOFs)constructed from natural/biological units(amino acids)are prospective candidates as catalysts in CO2chemistry owing to their natural origin and high abundance of Lewis acid/base sites and functional groups.Herein,we report the catalytic efficiency of an amino‐acid‐based Cu‐containing MOF,denoted as CuTrp(Trp=L‐tryptophan).The CuTrp catalyst was synthesized by direct mixing at room temperature using methanol as a solvent-a synthetic route with notable energy efficiency.The catalyst was characterized using various physicochemical techniques,including XRD,FT‐IR,TGA,XPS,ICP‐OES,FE‐SEM,and BET analysis.The catalytic activity of CuTrp was assessed in the synthesis of cyclic carbonates from epoxides and CO2.The CuTrp operated in synergy with the co‐catalyst tetrabutylammonium bromide under solvent‐free conditions.Several reaction parameters were studied to identify the optimal reaction conditions and a reaction mechanism was proposed based on experimental evidence and previous density functional theory studies.The CuTrp also exhibited satisfactory stability in water and could be reused more than three times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金Projects(51874017,52174236)supported by the National Natural Science Foundation of China。
文摘The increasing demand for iron ore in the world causes the continuous exhaustion of magnetite resources.The utilization of high-phosphorus iron ore becomes the focus.With calcium carbonate(CaCO_(3)),calcium chloride(CaCl_(2)),or calcium sulfate(CaSO_(4))as additive,the process of direct reduction and phosphorus removal of high-phosphorus iron ore(phosphorus mainly occurred in the form of Fe_(3)PO_(7) and apatite)was studied by using the technique of direct reductiongrinding-magnetic separation.The mechanism of calcium compounds to reduce phosphorus was investigated from thermodynamics,iron metallization degree,mineral composition and microstructure.Results showed that Fe_(3)PO_(7) was reduced to elemental phosphorus without calcium compounds.The iron-phosphorus alloy was generated by react of metallic iron and phosphorus,resulting in high phosphorus in reduced iron products.CaCO_(3) promoted the reduction of hematite and magnetite,and improved iron metallization degree,but inhibited the growth of metallic iron particles.CaCl_(2) strengthened the growth of iron particles.However,the recovery of iron was reduced due to the formation of volatile FeCl_(2).CaSO_(4) promoted the growth of iron particles,but the recovery of iron was drastically reduced due to the formation of non-magnetic FeS.CaCO_(3),CaCl_(2) or CaSO_(4) could react with Fe_(3)PO_(7) to form calcium phosphate(Ca_(3)(PO_(4))_(2)).With the addition of CaCO_(3),Ca_(3)(PO_(4))_(2) was closely combined with fine iron particles.It is difficult to separate iron and phosphorus by grinding and magnetic separation,resulting in the reduced iron product phosphorus content of 0.18%.In the presence of CaCl_(2) or CaSO_(4),the boundary between the generated Ca_(3)(PO_(4))_(2) and the metallic iron particles was obvious.Phosphorus was removed by grinding and magnetic separation,and the phosphorus content in the reduced iron product was less than 0.10%.
基金Sponsored by the National Hi-Tech Research and Development Program of China (Grant No.2003AA601090)Projects of Development Plan of the State Key Fundamental Research of China (Grant No.2004CB4185)
文摘The two-stage and two-phase anaerobic process (TSTP) composed of hydrolytic acidification reactor,first-order and second-order external circulation anaerobic reactors (EC) was taken to treat methanol wastewater. Test results show that TSTP process is quick start-up in 51 d, and the maximum VFA of hydrolytic acidification reactor effluent reaches 876 mg/L. Under the condition of volume loading of 6.56 kgCOD/m3·d, COD removal rate of the first-order EC reactor is about 85%, and under the condition of volume loading of 1.02 kgCOD/m3·d, COD removal rate of the second-order EC reactor is about 50%. When the inflow COD of TSTP process is between 7000-11000 mg/L, its effluent COD is lower than 600 mg/L. In the biological conversion process of methanol into methane,the production of acetic acids as an intermediate product can be ignored and the direct production of methane from methanol is predominant.
