Infrared(IR)absorption spectroscopy has been widely used for dynamic characterization of catalysts and mechanism of catalytic reactions.However,due to the strong infrared absorption of heterogeneous catalysts(mainly o...Infrared(IR)absorption spectroscopy has been widely used for dynamic characterization of catalysts and mechanism of catalytic reactions.However,due to the strong infrared absorption of heterogeneous catalysts(mainly oxides,or supported metal and metal oxides,etc.)below 1200 cm^(-1),and the intensity of regular infrared light source rapidly decays at low-wavenumber range,most in-situ infrared spectroscopy studies are limited to the detection of surface adsorbates in the range of 4000-900 cm^(-1).The change of catalytically active component itself(M-O,M-M bond,etc.,1200-50 cm^(-1))during the reaction is hard to be tracked under reaction conditions by in-situ IR.In this work,a home-made in-situ IR reactor was designed and a sample preparing method was developed.With such progresses,the changes of reactants,products,surface adsorbates,and catalysts themselves can be measured under the same reaction conditions with a spectral range of 4000-400 cm^(-1),providing a new opportunity for in-situ characterization of heterogeneous catalysis.CO oxidation on Pd/SiO_(2) and Cu/SiO_(2) catalysts were taken as examples,since both the two catalytic systems were extensively used commercially,and moreover reduction and oxidation of palladium and copper occur during the examined reaction conditions.The characteristic bands of Pd^(2+)-O(670,608 cm^(-1)),Cu^(+)-O(635 cm^(-1))and Cu^(2+)-O(595,535 cm^(-1))were observed by IR,and the changes during CO oxidation reaction were successfully monitored by IR.The oxidation/reduction of palladium and copper were also confirmed by ex-situ XPS.Moreover,Pd^(0) in Pd/SiO_(2) and Cu^(+)in Cu/SiO_(2) were found as the thermal dynamically stable phases under the examined conditions for CO oxidation.展开更多
An in-situ reflection ultramicroelectrode microscopic FTIR spectroelectrochemical cell was constructed and demonstrated by using hexacyanoferrate redox couple in aqueous sulphate solution.An excellent microscopic SNIF...An in-situ reflection ultramicroelectrode microscopic FTIR spectroelectrochemical cell was constructed and demonstrated by using hexacyanoferrate redox couple in aqueous sulphate solution.An excellent microscopic SNIFTIRS reflection spectra had been obtained with no difficulty of IR beam focusing.The cell is simple in construction and convenient for use,And it will have most of all advantages of micro-/ultramicroelectrode.展开更多
Mechanisms of electron transfer of carbazole （CZ） and 9-ethylcarbazole （ECZ） were studied by electrochemistry and in-situ spectroelectrochemistry. The result indicated that the electrochemical reaction mechanism o...Mechanisms of electron transfer of carbazole （CZ） and 9-ethylcarbazole （ECZ） were studied by electrochemistry and in-situ spectroelectrochemistry. The result indicated that the electrochemical reaction mechanism of ECZ was the same as that of CZ. Both of them undergo ECE process： the initial step is removal of one electron to generate very reactive cation radical, this species then proceeded by deprotonation-coupling reaction to form the corresponding dimer, which was oxidized continuously.展开更多
The multi-point simultaneous long-term measurement of CO_(2) concentration in seawater can provide more-valuable data for further understanding of the spatial and temporal distribution of CO_(2).Thus,the requirement f...The multi-point simultaneous long-term measurement of CO_(2) concentration in seawater can provide more-valuable data for further understanding of the spatial and temporal distribution of CO_(2).Thus,the requirement for a low-cost sensor with high precision,low power consumption,and a small size is becoming urgent.In this work,an in-situ sensor for CO_(2) detection in seawater,based on a permeable membrane and non-dispersive infrared(NDIR)technology,is developed.The sensor has a small size(Ф66 mm×124 mm),light weight(0.7 kg in air),low power consumption(<0.9 W),low cost(<US$1000),and high-pressure tolerance(<200 m).After laboratory performance tests,the sensor was found to have a measurement range of(0–2000)×10^(-6),and the gas linear correlation R^(2) is 0.99,with a precision of about 0.98%at a sampling rate of 1 s.A comparison measurement was carried out with a commercial sensor in a pool for 7 days,and the results showed a consistent trend.Further,the newly developed sensor was deployed in Qingdao nearshore water for 35 days.The results proved that the sensor could measure the dynamic changes of CO_(2) concentration in seawater continuously,and had the potential to carry out long-term observations on an oceanic platform.It is hoped that the sensor could be applied to field ocean observations in near future.展开更多
Redox mechanism of ferrocene, acetylferrocene, ferrocenyl cinnamenyl ketone at a platinum electrode was studied with cyclic voltammetry (CV) and in-situ Fourier transform infrared (FTIR) spectroelectrochemistry. The ...Redox mechanism of ferrocene, acetylferrocene, ferrocenyl cinnamenyl ketone at a platinum electrode was studied with cyclic voltammetry (CV) and in-situ Fourier transform infrared (FTIR) spectroelectrochemistry. The IR bands in the range of 2000-1000 cm-1 attributed to the stretching and ring vibrations of these materials show the main spectral changes in the processes.展开更多
A comprehensive understanding of the microscopic reaction mechanisms at the gas-solid-liquid electrochemical interfaces is urgently required for the development of advanced electrocatalysts applied in burgeoning susta...A comprehensive understanding of the microscopic reaction mechanisms at the gas-solid-liquid electrochemical interfaces is urgently required for the development of advanced electrocatalysts applied in burgeoning sustainable energy conversion systems. In-situ synchrotron radiation Fourier transform infrared(SR-FTIR) spectroscopy is one of the most powerful techniques for investigating the evolving dynamics of reactive intermediates during electrocatalytic reactions. In this review, we methodically summarize the recent progress in the research of dynamic mechanisms for valuable electrocatalytic reactions based on in-situ SR-FTIR methodology. Moreover, the merits and drawbacks of SRFTIR spectroscopy, the design principles of infrared beam setups and in-situ cells, as well as the in-situ measurement criteria are also discussed in detail. Lastly, the potential challenges and opportunities in this field are prudently stated. This review is expected to stimulate a broad interest in the material science and electrochemistry communities for exploring the dynamic mechanisms of prominent catalysis at the atomic/molecular level by using SR-based spectroscopy.展开更多
文摘Infrared(IR)absorption spectroscopy has been widely used for dynamic characterization of catalysts and mechanism of catalytic reactions.However,due to the strong infrared absorption of heterogeneous catalysts(mainly oxides,or supported metal and metal oxides,etc.)below 1200 cm^(-1),and the intensity of regular infrared light source rapidly decays at low-wavenumber range,most in-situ infrared spectroscopy studies are limited to the detection of surface adsorbates in the range of 4000-900 cm^(-1).The change of catalytically active component itself(M-O,M-M bond,etc.,1200-50 cm^(-1))during the reaction is hard to be tracked under reaction conditions by in-situ IR.In this work,a home-made in-situ IR reactor was designed and a sample preparing method was developed.With such progresses,the changes of reactants,products,surface adsorbates,and catalysts themselves can be measured under the same reaction conditions with a spectral range of 4000-400 cm^(-1),providing a new opportunity for in-situ characterization of heterogeneous catalysis.CO oxidation on Pd/SiO_(2) and Cu/SiO_(2) catalysts were taken as examples,since both the two catalytic systems were extensively used commercially,and moreover reduction and oxidation of palladium and copper occur during the examined reaction conditions.The characteristic bands of Pd^(2+)-O(670,608 cm^(-1)),Cu^(+)-O(635 cm^(-1))and Cu^(2+)-O(595,535 cm^(-1))were observed by IR,and the changes during CO oxidation reaction were successfully monitored by IR.The oxidation/reduction of palladium and copper were also confirmed by ex-situ XPS.Moreover,Pd^(0) in Pd/SiO_(2) and Cu^(+)in Cu/SiO_(2) were found as the thermal dynamically stable phases under the examined conditions for CO oxidation.
文摘An in-situ reflection ultramicroelectrode microscopic FTIR spectroelectrochemical cell was constructed and demonstrated by using hexacyanoferrate redox couple in aqueous sulphate solution.An excellent microscopic SNIFTIRS reflection spectra had been obtained with no difficulty of IR beam focusing.The cell is simple in construction and convenient for use,And it will have most of all advantages of micro-/ultramicroelectrode.
基金the National Natural Science Foundation of China(No.20475001)for the financial support.
文摘Mechanisms of electron transfer of carbazole （CZ） and 9-ethylcarbazole （ECZ） were studied by electrochemistry and in-situ spectroelectrochemistry. The result indicated that the electrochemical reaction mechanism of ECZ was the same as that of CZ. Both of them undergo ECE process： the initial step is removal of one electron to generate very reactive cation radical, this species then proceeded by deprotonation-coupling reaction to form the corresponding dimer, which was oxidized continuously.
基金Supported by the National Nature Science Foundation of China(No.41527901)the Provincial Key Research and Development Program of Shandong,China(No.2019JZZY010417)the Special Program of Shandong Province for Qingdao Pilot National Laboratory of Marine Science and Technology(No.2021QNLM020002).
文摘The multi-point simultaneous long-term measurement of CO_(2) concentration in seawater can provide more-valuable data for further understanding of the spatial and temporal distribution of CO_(2).Thus,the requirement for a low-cost sensor with high precision,low power consumption,and a small size is becoming urgent.In this work,an in-situ sensor for CO_(2) detection in seawater,based on a permeable membrane and non-dispersive infrared(NDIR)technology,is developed.The sensor has a small size(Ф66 mm×124 mm),light weight(0.7 kg in air),low power consumption(<0.9 W),low cost(<US$1000),and high-pressure tolerance(<200 m).After laboratory performance tests,the sensor was found to have a measurement range of(0–2000)×10^(-6),and the gas linear correlation R^(2) is 0.99,with a precision of about 0.98%at a sampling rate of 1 s.A comparison measurement was carried out with a commercial sensor in a pool for 7 days,and the results showed a consistent trend.Further,the newly developed sensor was deployed in Qingdao nearshore water for 35 days.The results proved that the sensor could measure the dynamic changes of CO_(2) concentration in seawater continuously,and had the potential to carry out long-term observations on an oceanic platform.It is hoped that the sensor could be applied to field ocean observations in near future.
文摘Redox mechanism of ferrocene, acetylferrocene, ferrocenyl cinnamenyl ketone at a platinum electrode was studied with cyclic voltammetry (CV) and in-situ Fourier transform infrared (FTIR) spectroelectrochemistry. The IR bands in the range of 2000-1000 cm-1 attributed to the stretching and ring vibrations of these materials show the main spectral changes in the processes.
基金supported by the National Natural Science Foundation of China (Nos. 1932212, U1932109, 11875257)。
文摘A comprehensive understanding of the microscopic reaction mechanisms at the gas-solid-liquid electrochemical interfaces is urgently required for the development of advanced electrocatalysts applied in burgeoning sustainable energy conversion systems. In-situ synchrotron radiation Fourier transform infrared(SR-FTIR) spectroscopy is one of the most powerful techniques for investigating the evolving dynamics of reactive intermediates during electrocatalytic reactions. In this review, we methodically summarize the recent progress in the research of dynamic mechanisms for valuable electrocatalytic reactions based on in-situ SR-FTIR methodology. Moreover, the merits and drawbacks of SRFTIR spectroscopy, the design principles of infrared beam setups and in-situ cells, as well as the in-situ measurement criteria are also discussed in detail. Lastly, the potential challenges and opportunities in this field are prudently stated. This review is expected to stimulate a broad interest in the material science and electrochemistry communities for exploring the dynamic mechanisms of prominent catalysis at the atomic/molecular level by using SR-based spectroscopy.
