Temperature programmed reduction wr the tpr equipment has been described in detail elsewhere 26. Temperature progr arnme d reduction of platinum group metals. Tds reduction reaction tds tds new sample reduction tds. An important aspect of tpr analyses is that the sample need not have any special characteristics other than containing reducible metals. Characterization by temperature programmed techniques of. The application of this technique in the frame of the eurocat oxide1 project has been reported previously. A temperature programmed reduction study of pt on al2o3 and tio2.
Aalto temperatureprogrammed dd methods for probing. From the fact that the colour of the catalyst changes during this stage we conclude that at least 408 11 temperature programmed reduction and sulphiding 400 4 600 800 10 00 1200 temperature k fig. Temperature profiles of hydrogen consumption for calcined samples from a stream of 10% h2 in n2 were monitored by a thermal conductivity detector. Temperatureprogrammed desorption reduction oxidation. The reducibility of magnesiasupported nickel catalysts and niomgo physical mixture has been studied by the temperature programmed reduction tpr technique in the temperature range 3731273 k. Reduction kinetic models reported in the literature were evaluated by model estimation techniques. Temperatureprogrammed desorption reduction oxidation tpdtprtpo and pulsesorption chemisorption instrument. The process must be reversible or at least temperature insensitive to the ramp employed for observation never fully correct but sometimes a valid approximation. Temperature progr arnme d reduction of platinum group metals catalysts recent trends in characterisation techniques by s. Temperature programmed desorption, reduction, oxidation. When the technique is applied to a system in which the adsorption process is, at least in part, irreversible and t programming leads to surface reactions, then this technique is often known as. The main objective of this work is to use information from temperature programmed reduction tpr that is both quantitative and qualitative, based on the existing literature, experimental data, and the researchers. Temperatureprogrammed reduction tpr has been widely used to characterize supported metal catalysts.
A temperature programmed reduction study of pt on a1203 and tio2 t. Pdf characterization by temperature programmed reduction. May 15, 2018 temperature programmed reduction tpr is an analytical technique that examines the surface chemistry of metal oxides under varying thermal conditions, an important factor in catalysis studies. Of these, the most useful for single crystal studies is. It describes the recent trends, instrumentation needed, as well as the application of tpr in heterogeneous catalysis, materials science, and analytical chemistry. Theoretical aspects, instrumentation and applications m. Tprenabled mass spectrometry equipment can acquire quantitative and qualitative data relating to the reduction of gas mixtures that are made to flow. Tpr stands for temperatureprogrammed reduction also temperature, pulse, respiration and 310 more what is the abbreviation for temperatureprogrammed reduction. Technique temperatureprogrammed oxidation tpo temperatureprogrammed oxidation tpo examines the extent to which a catalyst can be oxidized or the extent to which it was previously reduced. Temperatureprogrammed methods 19 19 gaps temperatureprogrammed methods are a prototype area for the existence of gaps between surface science and catalysis characterisation. Temperature programmed reduction tpr is a technique for the characterization of solid materials and is often used in the field of heterogeneous catalysis to find the most efficient reduction conditions, an oxidized catalyst precursor is submitted to a programmed temperature rise while a reducing gas mixture is flowed over it. Koninklijkeshell laboratorium, badhuisweg 3, amsterdam. Temperature programmed reduction and xray diffraction. Temperature programmed reduction tpr with hydrogen is a widely used technique for the characterization of reducible solids and catalysts.
Effects of calcination treatment on samples of monometallic pd and pd77ag23 alloy with primary particles around 8 nm were studied with the temperature programmed reduction technique. Ustav anorganicke technologie uvodni stranka vscht. Combined temperatureprogrammed reduction tpr temperature. Temperatureprogrammed reduction of al2o3, sio2, and.
Then the reactant gas, typically 25% oxygen in helium, is applied to the sample in pulses or, alternatively, as a steady stream. Fresh and used eurocat oxide2 catalyst made up of v 2 o 5, wo 3 and tio 2 with sio 2, al 2 o 3 and cao as main additives have been studied by means of temperature programmed reduction tpr. A thermal conductivity detector tcd or mass spectrometer records the effluent concentration. Kinetics of temperature programmed reduction tpr of nio.
Temperature progr arnme d reduction of platinum group. Temperature programmed desorption tpd is the method of observing desorbed molecules from a surface when the surface temperature is increased. When changing a temperature program, confirmation of peak identities in the new chromatogram is essential. Subramanian chemical engineering department, ford motor company, dearborn, michigan the characterisation of platinum group metals catalysts is commonly carried out by temperature programmed reduction, the spectrum of which has been used as a tfinger. In some cases this mixture was saturated with h20 at room tempera ture, resulting in 2. Technique temperature programmed reduction tpr temperatureprogrammed reduction tpr determines the number of reducible species present on the catalyst surface and reveals the temperature at which the reduction of each species occurs. Temperature programmed reduction for solid materials. The furnace heats the sample tube and sample according to the userselected temperature program. Technique temperature programmed reduction tpr temperature programmed reduction tpr determines the number of reducible species present on the catalyst surface and reveals the temperature at which the reduction of each species occurs. Recent literature suggests that the utility of temperature programmed reduction can be further enhanced by combining it with other techniques, such as temperature programmed. Technique temperatureprogrammed oxidation tpo temperature programmed oxidation tpo examines the extent to which a catalyst can be oxidized or the extent to which it was previously reduced. Temperature programmed reduction for solid materials characterization chemical industries series, volume 24. Temperature programmed oxidation tpo is a material characterization process that heats a sample of an element or compound, then, in the thermal excitation that takes place it can establish the oxidation.
An assignment of tpr signals to the different bulk phases was attempted. Jones, alan, 1941 temperatureprogrammed reduction for solid materials characterization. Aalto temperatureprogrammed dd methods for probing surface. Pdf a temperature programmed reduction study of pt on al2o3. Programmed reduction and oxidation a list of symbols used in the text is provided at the end of the chapter. Temperatureprogrammed reduction of nickel steam reforming. Temperatureprogrammed reduction of metalcontaminated. Tpr reveals information about the temperature range where reduction occurs, oxidation state of the metals. During temperature programmed reduction the composition of the gas flowing over the catalytic precursor is monitored during a welldefined temperature change, which is usually linear in time. May 15, 2018 temperature programmed oxidation tpo is a material characterization process that heats a sample of an element or compound, then, in the thermal excitation that takes place it can establish the oxidation.
Temperature programmed reduction tpr characterizes the oxido. This guide discusses the principles and theory of temperature programmed reduction tpr used for sold materials characterization. Kinetic analysis of temperatureprogrammed reduction. Peak retention orders can shift upon a change in the temperature program called peak inversions.
Temperatureprogrammed reduction and dispersive xray. Al2o3 composite oxides article pdf available in journal of the chemical society faraday transactions 8912 june 1993. During temperature programmed reduction the composition of the gas flowing over the catalytic precursor is monitored during a well defined temperature change, which is usually linear in time. A highpurity mix ture of 67% hxar flow rate 12 pmoys. Temperatureprogrammed reduction study on calcination of nano. The influences of carbon monoxide concentration on the reducibility of iron oxides have been investigated. There are various models for solid state kinetics and a few are listed in table 1. A temperature programmed reduction study of pt on al2o3. In tpr, a reducible catalyst or catalyst precursor is exposed to a flow of a reducing gas mixture typically a few vol. In tpr, a reducible catalyst or catalyst precursor is exposed to a flow of a reducing gas mixture. T 2 max20181614 wet h 2 172 kjmol dry h 2 111 kjmol.
This study deals with the comparison in the reduction of fe2o3 between 5% to 20% of co concentration in the temperature. Temperature programmed reduction 500 550 600 650 700 750 fe 2o3 wet h 2 dry h 2 temperature k t 1. Reduction of fe2o3 by carbon monoxide co have been studied by temperature programmed reduction tpr and xray diffraction spectroscopy xrd. Temperature programmed reduction tpr has been employed to study nimo mixed oxides which were previously used as model hydrodesulphurization hds catalysts, using compositions ranging from pure moo3 to pure nio. It was developed by john ward jenkins whilst developing. Al2o3 catalyst prepared by atomic layer deposition ald was used as the test reaction. Temperature programmed reduction tpr belongs to a class of chemical techniques to evaluate how readily hydrogen or co reduces the oxidation state of solids and in particular catalysts. The characterisation of platinum group metals catalysts is commonly carried out by temperature programmed reduction, the spectrum of which has been used as a fingerprint of the reducibility of the catalyst.
Temperature programmed reduction and oxidation tprh 2 and tpoo 2 shed light of a possible reduction of the active phase and. Characterization by temperature programmed reduction. The success or otherwise of catalyst preparation or modification depends on the availability of suitable characterization techniques to determine the condition of the. Temperature programmed reduction of platinum group metals. Temperatureprogrammed reduction of nimo oxides springerlink.
Twiggb a energy research institute, school ofchemical and process engineering, the university leeds, ls2 9jt, uk b twigg scienti. Pdf a temperature programmed reduction study of pt on. The applicability of tps is highlighted by an example in this chapter. Good agreement between tpr spectra and structural data obtained previously from xray. In this paper, the term catalytic precursor is used to refer to the entity before reduction. Temperature programmed desorption, reduction, oxidation and. Temperature programmed reduction behaviour tpr the typical first temperature programmed reduction cycle tpr of substituted samples and unsubstituted sample, are shown in fig. Temperatureprogrammed reduction of nickel steam reforming catalyst with glucose feng chenga.
Unlimited viewing of the articlechapter pdf and any associated supplements and figures. The kinetic modeling of hydrogen reduction was studied with the use of experimental data obtained by temperature programmed method. As in the eurocat oxide1 project v 2 o 5 tio 2 catalysts for similar conditions similar profiles were obtained in the different laboratories. Lucarellib astate university of milan, chemical physical department, via golgi 19, 203 milan, italy. Temperature programmed reduction and dispersive xray absorption spectroscopy studies of ceo 2based nanopowders for intermediate temperature solidoxide fuel cell anodes. Temperatureprogrammed reduction tpr is a technique for the characterization of solid materials and is often used in the field of heterogeneous catalysis to find the most efficient reduction conditions, an oxidized catalyst precursor is submitted to a programmed temperature rise while a reducing gas mixture is flowed over it. Successive temperature programmed desorption tpd after temperature programmed reduction tpr combined tprtpd was performed in order to characterize supported platinum catalysts ptsio 2, ptal 2 o 3, ptzro 2 and pttio 2 as well as to judge the validity of the apparent tpr profiles. Tpdro 1100 by thermo scientific measurement principle this technique offers the ability to investigate the temperature dependence of specific ad or. Pdf temperatureprogrammed reduction and oxidation of. The temperature programmed reduction tpr technique allows determining the reduction temperature of metallic oxides of a catalyst, and the amount of hydrogen consumed, revealing its reducibility. Reduction of moo 3 to moo 2 by co was suggested to follow two reduction stages which are shown as equation 1 and equation 2. Temperature programmed reducti on tpr is a technique for the characterization of solid materials and is often used in the field of heterogeneous catalysis to find the most effi cient reduct ion conditions, an oxidized catalyst precursor is submitt ed to a programmed tempe rature rise wh ile a reduci ng gas mixture is flowed over it. Temperature programmed reduction tpr is an analytical technique that examines the surface chemistry of metal oxides under varying thermal conditions, an important factor in catalysis studies. Good agreement between tpr spectra and structural data obtained previously from xray and electron.
When experiments are performed using welldefined surfaces of singlecrystalline samples in a continuously pumped ultrahigh vacuum uhv chamber, then this experimental technique is often also referred to as thermal desorption spectroscopy or thermal. Temperatureprogrammed reduction study on calcination of. Chapter 11 temperature programmed reduction and sulphiding. Temperature programmed reduction tpr determines the number of reducible species present on the catalyst surface and reveals the temperature at which the reduction of each species occurs. Temperatureprogrammed reduction of al2o3, sio2, and carbon. Temperature programmed reduction tpr has been widely used to characterize supported metal catalysts. Temperatureprogrammed techniques chemistry libretexts.
Temperature programmed reduction thermodynamic data for reduction 400c metal ti v cr mn fe co ni cu mo ru rh pd ag ir p h2o p h2eq 4 1016 2 109 6 104 2 1011 3 109 10 2 1010 0. Usually the sample is pretreated to reduce the metal oxides present to the base metals. The influences of calcination temperature 6731273 k, treatment. Key wordscalcination, nickel particle size, takovite, temperature programmed reduction. Temperature programmed reductionoxidation tprtpo methods. Temperatureprogrammed reduction wr the tpr equipment has been described in detail elsewhere 26. Temperature programmed desorption, reduction, oxidation and flow chemisorption for the characterisation of heterogeneous catalysts. Aug 24, 2001 effects of calcination treatment on samples of monometallic pd and pd77ag23 alloy with primary particles around 8 nm were studied with the temperature programmed reduction technique. Tpdro 1100 by thermo scientific measurement principle this technique offers the ability to investigate the temperaturedependence of specific ad or. Kinetics of temperature programmed reduction tpr of n io.
Standard free energy, ago, as a function of temperature for the process. Temperatureprogrammed reduction for solid materials. The goal of this work is to characterize commercial samples of fresh v 2 o 5f and spent v 2 o 5s vanadium catalysts by temperature programmed techniques. Prinsb laboratory for inorganic chemistry and catalysis, eindhoven university of technol ogy, p. Temperatureprogrammed reduction and oxidation of nickel supported on wo3.
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