Enhanced catalytic activities and selectivities in preferential oxidation of CO over ceria-promoted Au/Al_2O_3 catalysts

The preferential oxidation of CO （CO‐PROX） is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells （PEMFCs）. Au catalysts are highly active in CO oxidation. Howev‐er, their activities still need to be improved at the PEMFC operating temperatures of 80–120 ＆#176;C. In the present study, Au nanoparticles of average size 2.6 nm supported on ceria‐modified Al2O3 were synthesized and characterized using powder X‐ray diffraction, nitrogen physisorption, transmission electron and scanning transmission electron microscopies, temperature‐programmed hydrogen reduction （H2‐TPR）, Raman spectroscopy, and in situ diffuse‐reflectance infrared Fourier‐transform spectroscopy. Highly dispersed Au nanoparticles and strong structures formed by Au–support in‐teractions were the main active species on the ceria surface. The Raman and H2‐TPR results show that the improved catalytic performance of the Au catalysts can be attributed to enhanced strong metal–support interactions and the reducibility caused by ceria doping. The formation of oxygen vacancies on the catalysts increased their activities in CO‐PROX. The synthesized Au catalysts gave excellent catalytic performances with high CO conversions （＆gt;97%） and CO2 selectivities （＆gt;50%） in the temperature range 80–150 ＆#176;C.

Influence of preparation methods on CuO-CeO_2 catalysts in the preferential oxidation of CO in excess hydrogen

Influence of three different preparation methods, i.e. impregnation, coprecipitation, and inverse coprecipitation, on the preferential oxidation of CO in excess hydrogen （PROX） over CuO-CeO2 catalysts has been investigated and CuO-CeO2 catalysts are characterized using BET, XPS, XRD, UV Raman, and TPR techniques. The results show that the catalysts prepared by coprecipitation have smaller particle sizes, well-dispersed CuOx species, more oxygen vacancies, and are more active in the PROX than those prepared by the other methods. However. the inverse coprecipitation depresses the catalytic performance of CuO-CeO2 catalysts and causes the growth of CuO-CeO2 because of different pH value in the precipitation process.

Preferential oxidation of CO in excess H_2 over CeO_2/CuO catalyst:Effect of calcination temperature

Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selected to investigate the interaction between CeO2 and CuO support.It is found that as calcination temperature increased from 500 to 900 C,sintering of CeO2 particles on the support occurred together with the diffusion of a portion of Ce 4＋ ions into CuO crystals,forming solid solution.Formation of interface complex Ce-O-Cu was suggested by TPR measurements.The catalyst calcined at 700 C gives the highest activity for preferential oxidation of CO in excess H2 stream.

Influence of pH values in the preparation of CuO-CeO_2 on its catalytic performance for the preferential oxidation of CO in excess hydrogen

CuO-CeO2 catalyst prepared with co-precipitation showed high catalytic performance for the preferential oxidation of CO in excess hydrogen（PROX）.Influence of pH values in the preparation of CuO-CeO2 on its catalytic performance was investigated in this work.The CuO-CeO2 catalyst prepared at pH = 13.03 had the smallest particle size（5.4 nm）,the largest surface areas（138m 2/g） and the highest activity with CO conversion of 99.6% at 130 ℃.The CuO-CeO2 catalyst was characterized using BET,XRD and TPR techniques.The results showed that when the pH value of the mixed solution containing Cu and Ce species was properly adjusted,both the adsorption layers and diffusion layers of the formed colloidal particles in hydroxide precursor of CuO-CeO2 were modified,resulting in the better catalytic performance for PROX on the final CuO-CeO2 catalyst

Preferential Oxidation of CO in H_2 over CuO/CeO_2 Catalysts

A very active catalyst of CuO/CeO_2 was made by adsorption-impregnation method for preferential oxidation of CO in H_2. The CO conversion is close to 100% and selectivity to CO oxidation is 96% over this catalyst at a low reaction temperature of 95 ℃ and a space velocity of 40000 cm^3·g^(-1)·h^(-1) in the reaction mixture of 1%CO, 1%O_2, and 50%H_2 balanced with N_2. The effect of preparation conditions on catalytic performances was investigated. The catalytic performance of the CuO/CeO_2 catalysts was compared with that of other CO preferential oxidation catalysts reported in literature.

Preferential Oxidation of CO in Excess Hydrogen over CuO-CeO_2 Catalyst Prepared by Chelating Method

The CuO-CeO2 catalyst prepared by chelating method has a superior catalytic performance for the preferential oxidation of CO in rich hydrogen, compared with the CuO-CeO2 catalyst prepared by coprecipitation method. The CO conversions over these catalysts, at 120 ℃ and 120000 ml/（g-h） in the absence of CO2 and H2O, are 99.6% and 88.6%, respectively, and the selectivity of O2 over these catalysts is very close （i.e. 51.3% and 55.8%, respectively）. The influence of certain factors such as hydrogen concentration, carbon monoxide concentration, H2O, O2/CO ratios, and space velocity on the catalytic performance of CuO-CeO2 catalyst prepared by chelating method is also studied. The results show that the addition of hydrogen and H2O has a negative effect on the catalytic performance of CuO-CeO2 catalyst, however, the variation of space velocity and the O2/CO ratio causes a comparatively slight influence.

Recent advances on catalysts for preferential oxidation of CO

The trace amount of CO in H2-rich gas poisons Pt electrode when it is adopted as feedstock for proton-exchange-membrane fuel cells.Preferential oxidation of CO(PROX)is a promising approach to selectively oxidize the trace amount of CO while keeping H2 unoxidized.Catalyst plays important roles in PROX.To date,enormous catalysts have been developed for PROX.Summarizing the catalysts developed for PROX and unveiling the reaction mechanism could definitely advance this research field.Herein,in this review,according to the nature of the active sites on the catalysts,we classify the catalysts into group VIII metal-based catalyst,group IB metal-based catalysts,group VIII-group IB bimetallic catalysts,transitional metal oxide catalysts as well as others,describe the progress of the catalysts in PROX in the latest five years,and extract the underlying reaction mechanism,with the aim to provide guidance for the rational design of efficient catalysts in the future.

Preferential Oxidation of Carbon Monoxide in Excess Hydrogen over Au/Co_3O_4-CeO_2 Catalysts

Au/Co3O4-CeO2 mixed-oxide catalysts were shown tion of CO in hydrogen-rich mixture. Activity was markedly experimentally to be highly active and selective for the oxidainfluenced by the composition of the support, aging temperature and Au-loading temperature. It provided that single-step removal of CO from hydrogen-rich stream both in the absence and presence of CO2 and H2O to a PEMFC tolerant level. It was found that catalytic activity is greatly affected by adding CO2 in the mixture and increased by farther adding H2O. It recants H2O has the effect to rise catalytic activity. Moreover, it shows better stability with reaction time for the preferential CO oxidation.

Influence of reduction energy match among CuO species in CuO-CeO_2 catalysts on the catalytic performance for CO preferential oxidation in excess hydrogen

In the present study, we have investigated the reducibility of CuO species on CuO-CeO2 catalysts and the influence of CuO species on the catalytic performance for CO preferential oxidation （CO PROX） in excess hydrogen. It is revealed that the smaller the difference of reduction temperature （denoted as ？T） for two adjacent CuO species is, the higher the catalytic activity of CuO-CeO2 for the PROX in excess hydrogen may be obtained. It means that if the reduction energy of Cu0-Cu2＋ pairs matched better, the reduction-oxidation recycle of Cu0-Cu2＋ pairs would go on more easily, then the transferring energy of Cu0-Cu2＋ pairs would be lesser. Therefore, the CuO-CeO2 catalysts will be largely improved in their catalytic performance if the different CuO species on the catalysts have matched the reduction energy, which would allows them to cooperate effectively.

Promotion effect of adsorbed water/OH on the catalytic performance of Ag/activated carbon catalysts for CO preferential oxidation in excess H_2

Activated carbon （AC） supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation （PROX） in excess H2 was evaluated. Ag/AC catalysts, after reduction in H2 at low temperatures （≤200 ℃） following heat treatment in He at 200 ℃ （He200H200）, exhibited the best catalytic properties. Temperature-programmed desorption （TPD）, X-ray diffraction （XRD） and temperature-programmed reduction （TPR） results indicated that silver oxides were produced during heat treatment in He at 200 ℃ which were reduced to metal silver nanoparticles in H2 at low temperatures （≤200 ℃）, simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 ℃. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO2. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.

Influence of metal nuclearity and physicochemical properties of ceria on the oxidation of carbon monoxide

The redox properties of ceria make it suitable as a catalyst or support in oxidation reactions.Ceria-supported transition metal nanoparticles or isolated single atoms provide a metal-support interface that reduces the energy cost to remove interfacial oxygen atoms,providing active oxygen species that can participate in Mars van Krevelen oxidation processes.CO oxidation is a key probe reaction to test the reducibility of ceria-supported catalysts and is also practically important in the elimination of CO at relatively low temperatures in various applications.Preferential oxidation of CO(PROX)in excess H2 controls the CO concentration to ultra-low levels to prevent poisoning of hydrogen oxidation electrocatalysts.The reactivity of catalysts in CO oxidation and selectivity towards CO over H2 in PROX is dependent on the type and dispersion of metal species,the structural and chemical properties of Ce O2,and the synthetic preparation methods of the catalysts.In this review,we summarize recently published works on catalytic CO oxidation and PROX reactions on ceria-supported metal nanoparticles and single atoms.We summarize the reactivity on different supported metals,and on different Ce O2 surfaces with the same metal.We summarize the most likely reaction mechanisms as suggested by density functional theory calculations.The factors contributing to selectivity towards CO oxidation in PROX reactions on various supported metals are also discussed.

Valence State of Active Copper in CuO_x/CeO_2 Catalysts for CO Oxidation

CuOx/CeO2 catalysts were prepared by adsorption-impregnation method, CO conversion was tested over the catalysts pretreated under different conditions for preferential CO oxidation in H2, and the catalysts were characterized with X-ray photoelectron spectroscopy and temperature programmed reduction. Experimental results show that there are two kinds of copper, which are Cu^＋ and Cu^2＋ in calcined CuOx/CeO2, Among them, the Cu^＋ is the key active component for CO oxidation. The main reason is as follows： CO is activated by copper for CO oxidation over CuOx/CeO2, while CO can not be activated by Cu^2＋. Only when Cu^2＋ is reduced to Cu ^＋ or Cu^0, the copper may be active for CO oxidation, moreover, the experimental results show that the reduction of Cu^2＋ does not lead to an increase of catalytic activity. So the active species is Cu^＋ in CuOx/CeO2 catalysts.

Meso-macroporous Al_2O_3 supported Ru catalysts for CO preferential oxidation in hydrogen-rich gases

Series of meso-macroporous Al2O3 supported Ru catalysts with different loadings were prepared by incipient wetness method and applied to preferential oxidation of CO in hydrogen-rich gases. N2 adsorption-desorption, SEM, XRD, TEM, CO chemisorption and H2-TPR techniques were employed to characterize the catalysts. The results indicate that Ru/Al2O3 catalysts have meso-macroporous structure, high surface area and high metal dispersion. The characterization results of XRD and CO chemisorption indicate the entry of Ru ions into Al2O3 lattice. The results of catalytic performance tests indicate that the meso-macroporous Al2O3 supported Ru catalysts for CO preferential oxidation showed good activity under high space velocity. It is proposed that the macropores in the Ru/Al2O3 catalyst favor mass transfer and mesopores help to improve the dispersion of metal, resulting in the excellent catalytic performance.

Cu-Co Composite Oxides Supported on Multi-walled Carbon Nanotubes for Catalytic Removal of CO in a H2-rich Stream

Multi-walled carbon nanotubes （MWCNT） supported Cu-Co composite oxides catalysts were prepared by an ultrasonication treatment-aided impregnation method. The structure prop-erties of the catalysts were characterized by XRD, TEM, H2-TPR, XPS and Raman spectra, indicating the strong interactions between Cu and Co mixed oxides as well as between metal oxides and MWCNT support. The catalytic performance of CO removal in a H2-rich stream was examined. In contrast to the single Cu and Co catalyst, the unique performance was ob-served for Cu-Co composite catalysts, which features an unusual reaction pathway through the combination of CO preferential oxidation and CO methanation especially at high reac-tion temperature. The optimal catalyst with Cu/Co ratio of 1/8 can achieve the complete CO conversion in a wider temperature range of 150-250 ℃ under the space velocity as high as 120 L/（h·g）, which demonstrates a promising catalyst for the e ective CO removal in a H2-rich stream.

Oxidation induced ductility enhancement of Zr based metallic glass ribbons in vicinity of glass transition temperature

Zr-based metallic glasses(MGs)possess a wide supercooled liquid region,which gives a wide processing window for superplastic forming to make microdevices with demanding size accuracy and surface finishing.The existence of oxygen may have an influence on the thermoplastic deformation process.Therefore,the effect of oxidation on the mechanical behavior of the MGs in the vicinity of glass transition temperature is of great significance for practical forming of MG components.In the present study,the effect of oxidation on tensile properties of Zr50Cu40Al10 metallic glass was investigated.The tested samples were characterized by XRD and SEM analysis.For the samples tested in air,the strength decreases 187 MPa,61 MPa and 59 MPa and the ductility increases 0.31,0.36,and 0.77 at 420℃,430℃,and 440℃,respectively,compared with those tested in flowing argon.ZrO_(2) preferentially formed during the tensile testing at 420℃,and both ZrO_(2) and Al_(2)O_(3) oxides formed at 430℃.The dilution of Zr elements in the remaining amorphous matrix caused by preferential oxidation on the surface layer attributes to the decrease in strength and enhancement in ductility of the Zr_(50)Cu_(40)Al_(10) metallic glasses.

Elucidating the role of preferential oxidation during ablation:Insights on the design and optimization of multicomponent ultra-high temperature ceramics

Multicomponent ultra-high temperature ceramics(UHTCs)are promising candidates for thermal protection materials(TPMs)used in aerospace field.However,finding out desirable compositions from an enormous number of possible compositions remains challenging.Here,through elucidating the role of preferential oxidation in ablation behavior of multicomponent UHTCs via the thermodynamic analysis and experimental verification,the correlation between the composition and ablation performance of multicomponent UHTCs was revealed from the aspect of thermodynamics.We found that the metal components in UHTCs can be thermodynamically divided into preferentially oxidized component(denoted as MP),which builds up a skeleton in oxide layer,and laggingly oxidized component(denoted as ML),which fills the oxide skeleton.Meanwhile,a thermodynamically driven gradient in the concentration of MP and ML forms in the oxide layer.Based on these findings,a strategy for pre-evaluating the ablation performance of multicomponent UHTCs was developed,which provides a preliminary basis for the composition design of multicomponent UHTCs.

CuO-CeO_2/Al_2O_3/FeCrAl monolithic catalysts prepared by in situ combustion synthesis method for preferential oxidation of carbon monoxide

This work described in situ combustion synthesis method for depositing CuO-CeO2 on the FeCrAI honeycomb supports. The influence of the solution concentration and the role of the additive were studied and analyzed by scanning electron microscopy （SEM）, X-ray diffractometer （XRD）, and temperature programmed reduction （TPR） techniques. The results showed that 200 g/L of the active solution was the most appropriate concentration for preparing the monolithic catalysts, and the additives of praseodymium and lanthanum improved the adhesion stability of the monolithic catalysts. The addition of Pr did not greatly affect the catalytic performance, but CO could not be totally converted into CO2 after the addition of La into the CuO-CeO2/Al2O3/FeCrAl catalysts.

Gas-solid catalytic reactions over ruthenium-based catalysts

Ruthenium （Ru）‐based catalysts are widely employed in several types of gas‐solid reactions because of their high catalytic activities. This review provides theoretical research on Ru‐based catalysts and an analysis of their basic properties and oxidation behavior. There is particular emphasis on Ru‐catalyzed gas‐solid catalytic reactions, including the catalytic oxidation of VOCs, preferential oxidation of CO, synthesis of ammonia, oxidation of HCl and partial oxidation of CH4. Recent litera‐ture on catalysis is summarized and compared. Finally, we describe current challenges in the field and propose approaches for future development of Ru‐based catalysts.

Selective and stable Au-Cu bimetallic catalyst for CO-PROX

Gold-based catalysts are promising in CO preferential oxidation(CO-PROX)reaction in H_(2)-rich stream on account of their high intrinsic activity for CO elimination even at ambient temperature.However,the decrease of CO conversion at elevated temperature due to the competition of H_(2)oxidation,together with the low stability of gold nanoparticles,has posed a dear challenge.Herein,we report that Au-Cu bimetallic catalyst prepared by galvanic replacement method shows a wide temperature window for CO total conversion(30-100℃)and very good catalyst stability without deactivation in a 200-h test.Detailed characterizations combined with density functional theory(DFT)calculation reveal that the synergistic effect of Au-Cu,the electron transfer from Au to Cu,leads to not only strengthened chemisorption of CO but also weakened dissociation of H_(2),both of which are helpful in inhibiting the competition of H_(2)oxidation thus widening the temperature window for CO total conversion.