Investigating the impact of dynamic structural changes of Au/rutile catalysts on the catalytic activity of CO oxidation

The surface properties of oxidic supports and their interaction with the supported metals play critical roles in governing the catalytic activities of oxide‐supported metal catalysts.When metals are supported on reducible oxides,dynamic surface reconstruction phenomena,including strong metal–support interaction(SMSI)and oxygen vacancy formation,complicate the determination of the structural–functional relationship at the active sites.Here,we performed a systematic investigation of the dynamic behavior of Au nanocatalysts supported on flame‐synthesized TiO_(2),which takes predominantly a rutile phase,using CO oxidation above room temperature as a probe reaction.Our analysis conclusively elucidated a negative correlation between the catalytic activity of Au/TiO_(2) and the oxygen vacancy at the Au/TiO_(2) interface.Although the reversible formation and retracting of SMSI overlayers have been ubiquitously observed on Au/TiO_(2) samples,the catalytic consequence of SMSI remains inconclusive.Density functional theory suggests that the electron transfer from TiO_(2) to Au is correlated to the presence of the interfacial oxygen vacancies,retarding the catalytic activation of CO oxidation.

Tandem catalysis for enhanced CO oxidation over the Bi-Au-SiO_(2)interface

Bimetallic catalysts typically exploit unique synergetic effects between two metal species to achieve their catalytic effect.Understanding the mechanism of CO oxidation using hybrid heterogeneous catalysts is important for effective catalyst design and environmental protection.Herein,we report a Bi-Au/SiO_(2)tandem bimetallic catalyst for the oxidation of CO over the Au/SiO_(2)surface,which was monitored using near-ambient-pressure X-ray photoelectron spectroscopy.The Au-decorated SiO_(2)catalyst exhibited scarce activity in the CO oxidation reaction;however,the introduction of Bi to the Au/SiO_(2)system promoted the catalytic activity.The mechanism is thought to involve the dissociation O_(2)molecules in the presence of Bi,which results in spillover of the O species to adjacent Au atoms,thereby forming Au^(δ+).Further CO adsorption,followed by thermal treatment,facilitated the oxidation of CO at the Au-Bi interface,resulting in a reversible reversion to the neutral Au valence state.Our work provides insight into the mechanism of CO oxidation on tandem surfaces and will facilitate the rational design of other Au-based catalysts.

High catalytic performance of CuCe/Ti for CO oxidation and the role of TiO_(2)

CuCe/Ti-A and CuCe/Ti-R catalysts were prepared using anatase TiO_(2)(TiO_(2)-A)and rutile TiO_(2)(TiO_(2)-R)as supports using the incipient wetness impregnation method for the carbon monoxide(CO)oxidation reaction and were compared with a CuCe-C catalyst prepared using the co-precipitation method.The CuCe/Ti-A catalyst exhibited the highest activity,with complete CO conversion at 90℃,when the gas hourly space velocity was 24000 ml.g^(-1).h^(-1) and the CO concentration was approximately 1%(vol).A series of characterizations of the catalysts revealed that the CuCe/Ti-A catalyst has a larger specific surface area,more Cu+species and oxygen vacancies,and the Cu species of CuCe/Ti-A catalyst is more readily reduced.In situ FT-IR results indicate that the bicarbonate species generated on the CuCe/Ti-A catalyst have lower thermal stability than the carbonate species on CuCe/Ti-R,and will decompose more readily to form CO_(2).Therefore,CuCe/Ti-A has excellent catalytic activity for CO oxidation.

A comparative study of CuO/TiO_2-SnO_2,CuO/TiO_2 and CuO/SnO_2 catalysts for low-temperature CO oxidation

Nanometer SnO2 particles were synthesized by sol-gel dialytic processes and used as a support to prepare CuO supported catalysts via a deposition-precipitation method. The samples were characterized by means of TG-DTA, XRD, H2-TPR and XPS. The catalytic activity of the CuO/TiO2-SnO2 catalysts was markedly depended on the loading of CuO, and the optimum CuO loading was 8 wt.% （Tloo = 80 ℃）. The CuO/TiO2-SnO2 catalysts exhibited much higher catalytic activity than the CuO/TiO2 and CuO/SnO2 catalysts. H2-TPR result indicated that a large amount of CuO formed the active site for CO oxidation in 8 wt.% CuO/TiO2-SnO2 catalyst.

Insights into support effects on Ce-Zr-O mixed oxide-supported gold catalysts in CO oxidation

Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.

Optimization of preparation conditions of Fe-Co nanoparticles in low-temperature CO oxidation reaction by taguchi design method

Mixed iron-cobalt oxide （Co/Fe molar ratio = 1/5） are prepared using a simple co-precipitation procedure and studied for the catalytic oxidation of carbon monoxide. In particular, the effects of a range of preparation variables such as pH value when precipitation, aging temperature, precipitation agent type and aging time are investigated on the catalytic performance of synthesized Fe-Co oxides in CO oxidation reaction. In addition, the preparation factors were optimized by Taguchi design method. The optimized sample was characterized by XRD, N2 adsortion/desorption, TEM and TGA/DTA techniques. The results reveal that the optimized sample shows a mesoporous structure with a narrow pore size distribution centered in the range of 2-7 nm. The sample prepared under optimized conditions has high activity and stability toward removal of carbon monoxide at lower temperatures. It is shown that different preparation variables influence the catalytic performance of Fe-Co oxide in CO oxidation reaction.

CeO_2-Co_3O_4 Catalysts for CO Oxidation

CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method. In combination with the characterization methods of N2 adsorption/desorption, XRD, temperature-programmed reduction （TPR）, and FT-IR, the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated. The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4. The catalyst with the Ce/Co atomic ratio 1 ： 16 exhibits the best activity, which converts 77% of CO at room temperature and completely oxidizes CO at 45 ℃.

Single-atom catalysts for CO oxidation,CO_(2) reduction,and O_(2) electrochemistry

CO_(x)(x=1,2)and O_(2) chemistry play key roles in tackling global severe environmental challenges and energy issues.To date,the efficient selective electrocatalytic transformations of COx-carbon chemicals,and O_(2)-hydrogenated products are still huge challenges.Single-atom catalysts(SACs)as atomic-scale novel catalysts in which only isolated metal atoms are dispersed on supports shed new insights in overcome these obstacles in CO_(x) and O_(2) chemistry,including CO oxidation,CO_(2) reduction reaction(CO_(2)RR),oxygen reduction reaction(ORR),and oxygen evolution reaction(OER).In this review,the unique features and advanced synthesis strategies of SACs from a viewpoint of fundamental synthesis design are first highlighted to guide future strategy design for controllable SAC synthesis.Then,the to-date reported CO_(2)RR,CO oxidation,OER,and ORR mechanism are included and summarized.More importantly,the design principles and design strategies of improving the intrinsic activity,selectivity,and stability are extensively discussed and the engineering strategy is classified as neighbor coordination engineering,metal-atom engineering,and substrate engineering.Via the comprehensive review and summary of state-of-the-art SACs,the synthesis–structure–property–mechanism–design principle relation can be revealed to shed lights into the structural construction of SACs.Finally,we present an outlook on current challenges and future directions for SACs in CO_(x) and O_(2) chemistry.

Highly active and sintering-resistant heteroepitaxy of Au nanoparticles on ZnO nanowires for CO oxidation

Gold was supported on commercial ZnO powders(P) and homemade ZnO nanowires(NWs) by a modified deposition–precipitation method. X-ray diffraction and transmission electron microscopy investigation indicated that the size of the Au nanoparticles(NPs) depended strongly on the calcination temperature.The Au NPs were highly dispersed(< 5 nm) on both supports with calcination temperatures < 400 °C.However, after calcination at 600 °C the Au NPs aggregated much more severely on ZnO P than on ZnO NWs. Gold NPs epitaxially grew into the {10–10} facets of the ZnO NWs after calcination at temperatures > 400 °C. Such unique anchoring mechanism accounts for the much better experimentally observed sintering resistance. X-ray photoelectron spectra showed that Au existed as both metallic Au0 and Auδ+species in all the synthesized catalysts with or without calcination treatment; the ratios of Auδ+/Au0,however, varied, depending on the treatment conditions. Catalytic tests showed that the activity for CO oxidation strongly depended on the size of the Au NPs. After calcination at 600 °C, the specific rate for CO oxidation at room temperature decreased about 30 times on Au/ZnO P but only about 4 times on Au/ZnO NW. Stability tests demonstrated that the Au/ZnO NW catalysts had better stability for CO oxidation.

Evolution of Gold Species in an Au/CeO_2 Catalyst and Its Impact on Activity for CO Oxidation

An Au/ceria（0.44%, mass fraction） catalyst containing gold ions was prepared by a modified deposition precipitation method, and the evolution of gold ions in the catalyst and its influence on the catalysis of CO oxidation were investigated. It was found that the as-prepared catalyst containing gold ions with high valence could fully oxidize CO at -10 ℃ initially but was deactivated gradually at low temperatures during the reaction with CO or treatment by unpurified air. The deactivation of the catalyst during CO oxidation or treatment of it by unpurified air was independent and progressive at low temperatures while the activity of the catalyst at relatively high temperatures was maintained well. During the reaction with CO or treatment by unpurified air, the XPS results indicate that gold species evolved from high valence to low valence and the diffuse reflectance UV-Vis spectra show that high valence gold was reduced to charged gold clusters, gold clusters grew to small gold crystals and small gold crystals grew to large gold particles. Accordingly, the high valence gold corresponded to the activity at low temperatures and the metallic gold was active and relatively stable at high temperatures. The turnover frequencies（TOF） of the catalysts treated by different methods at 273 K decreased with the evolution of gold species from high valence to low valence, no maximum of TOF was observed although gold particles in the catalyst attained to about 2-3 nm during the treatment. An Au/ceria catalyst with a gold load of 0.87% （mass fraction） maintained a good activity for CO oxidation within 18 h at room temperature. The catalysts were characterized via transmitted electronic microscopy（TEM）, inductively coupled plasma optical emission spectrometry（ICP-OES）, X-ray diffraction（XRD） and BET specific surface area and UV-Vis DRS as well.

Bursting oscillation in CO oxidation with small excitation and the enveloping slow-fast analysis method

Based on the traditional scheme for a nonlinear system with multiple time scales, the enveloping slow-fast analysis method is developed in the paper, which can be employed to investigate the dynamics of nonlinear fields with multiple time scales with periodic excitation. Upon using the method, the behaviors of the kinetic model of CO oxidation on the platinum group metals have been explored in detail. Two typicM bursting phenomena such as Fold/Fold/Hopf bursting and Fold/Fold bursting, are presented, the bifurcation mechanisms of which have been obtained. Furthermore, the dynamic difference between the two cases corresponding to relatively large and small perturbation frequencies, respectively, has been presented, which can be used to describe the influence of the frequencies involving in the evolution on the bursting behaviors in the system.

Atmospheric-Pressure DBD Cold Plasma for Preparation of High Active Au/P25 Catalysts for Low-Temperature CO Oxidation

Cold plasma generated by dielectric barrier discharge （DBD） at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts （Au/P25- P） with the assistance of the deposition-precipitation procedure. The influences of the plasma reduction time and calcination on the performance of the Au/P25-P catalysts were investigated. CO oxidation was performed to investigate the catalytic activity of the Au/P25 catalysts. The results show that DBD cold plasma for the fabrication of Au/P25-P catalysts is a fast process, and Au/P25-P （4 min） exhibited the highest CO oxidation activity due to the complete reduction of Au compounds and less consumption of oxygen vacancies. In order to form more oxygen vacancies active species, Au/P25-P was calcined to obtain Au/P25-PC catalysts. Interestingly, Au/P25- PC exhibited the highest activity for CO oxidation among the Au/P25 samples. The results of transmission electron microscopy （TEM） indicated that the smaller size and high distribution of Au nanoparticles are the mean reasons for a high performance of Au/P25-PC. Atmospheric- pressure DBD cold plasma was proved to be of great efficiency in preparing high performance supported Au catalysts.

Synthesis of porous hematite nanorods loaded with CuO nanocrystals as catalysts for CO oxidation

Porous hematite （α-Fe2O3） nanorods with the diameter of 20-40 nm and the length of 80-300 nm were synthesized by a simple surfactant-assisted method in the presence of cetyltrimethylammonium bromide （CTAB）.The α-Fe2O3 nanorods possess a mesostructure with a pore size distribution in the range of 5-12 nm and high surface area,exhibiting high catalytic activity for CO oxidation.CuO nanocrystals were loaded on the surface of porous α-Fe2O3 nanorods by a deposition-precipitation method,and the catalysts exhibited superior activity for catalytic oxidation of CO,as compared with commercial α-Fe2O3 powders supported CuO catalyst.The enhanced catalytic activity was attributed to the strong interaction between the CuO nanocrystals and the support of porous α-Fe2O3 nanorods.

Simple Preparation of Crystal Co_3(BTC)_2·12H_2O and Its Catalytic Activity in CO Oxidation Reaction

Crystalline metal-organic framework cobalt （II） benzenetricarboxylate C%（BTC）2·12H2O （MOF-Co） has been prepared using solvothermal method. The reaction of cobalt （II） nitrate and 1,3,5-benzenetriearboxylic （BTC） acid in a mixed solution of N,N-dimethylformarnide （DMF）/C2H5OH/H2O （1：1：1, v/v） at low temperature for short reaction times produced this crystalline compound. Compared with traditional hydrothermal method, a mixed solution method for the synthesis of crystalline metal complex was found to be highly efficient. After water molecules were removed from this metal complex, its exposed nodes served as active sites. When this MOF-Co was employed in the oxidation of CO, it showed good catalytic properties causing 100% conversion of CO to CO2 at low temperature of 160 ℃.

Effects of preparation conditions of Au/FeO_x /Al_2O_3 catalysts prepared by a modified two-step method on the stability for CO oxidation

Composite oxide FeO x /Al 2 O 3 -supported gold catalysts were prepared by a modified two-step method. The effects of preparation conditions on the initial catalytic activity and long-time stability were studied for CO oxidation. XRD, XPS and in situ FTIR were employed to investigate the state of FeO x and the species on the catalyst surface. The results showed that Au/FeO x /Al 2 O 3 catalysts prepared by this method exhibited high activity and high stability in a wide pH value range. Calcination pretreatment was proved to be beneficial to improving the activity and stability. The beneficial effects of FeO x acting as a structural promoter could be ascribed to the ability to supply active oxygen species. As the precursor of FeO x , Fe（NO 3 ） 3 is superior to FeCl 3 for obtaining higher stability.

Effect of Addition of Base on Ceria and Reactivity of CuO/CeO_2 Catalysts for Low-Temperature CO Oxidation

In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction （XRD）, high resolution transmission electron microscopy （HRTEM）, and temperatureprogrammed reduction by H2 （H2-TPR）. The catalytic properties of the CuO/CeO2 catalysts for lowtemperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.

Doping Effect of CuO on CeO_2 for CO Oxidation

Cu-Ce-O catalysts, prepared by the amorphous citrate precursor (ACP) method, wereinvestigated by ICP, XRD and ndcro-reactor techniques. At low copper content of Cu-Ce-Ocatalysts, fluorite structures formed at low calcining temperatures, and Cuo doped into the CeO2matrix; at high copper content, in addition to the fluorite structure, crystalline monoclinic phaseCuO formed as well at high calcining temperatures. There was no other phase formed even calcinedat 1000℃. The results show that only a little CuO dopes into the CeO2 matrix to form complexoxide, which promotes the catalytic activity of CO oxidation greatly. The optimum Cu-Ce-Ocatalyst is composed of 15% copper by Cu/(Ce+Cu) atomic ratio, and calcined at 700℃ for 4h. Thephase compositions include the crystalline CuO and the active complex oxide with fluoritestructure. The formulation of the active complex oxide is Cu0.06Ce0. 94O1.94.

Ruthenium Catalyst Supported on Multi-Walled Carbon Nanotubes for CO Oxidation

This work proposes the synthesis of the 5%wt Ru on MWCNT catalyst and the influence of feed rate and testing variables for low-temperature oxidation affecting the CO2 yield. Morphology and incorporation of the nanoparticles in carbon nanotubes were investigated by specific surface area (BET method);thermogravimetric analyses (TGA);X-ray diffraction;Raman spectroscopy, transmission electron microscopy (TEM) and XPS. The conversions of CO and O2 were mostly 100% in groups C1 and C2 (temperature between 200 and 500°C with low WHSV). In order to assess the effect of mass on catalytic activity, condition C3 was tested at even lower temperatures. In the tested catalyst, high activity (100% CO and O2 conversion) was observed, keeping it active under reaction conditions, suggesting oxi-reduction of the RuO2 at surface without affecting the MWCNT but Lewis acid influencing the CO2 yield.

PREPARATION OF Au/SULFONATED POLYSTYRENE CATALYSTS FOR LOW-TEMPERATURE CO OXIDATION

Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (Cl). X-ray photoelectron spectroscopy (XPS) investigations indicated that the elemental gold in all the samples was in the metallic state, XRD measurements showed that the mean diameters of Au particles prepared by SMAI were smaller than those prepared by Cl with the same gold content. Catalytic tests showed that the SMAI catalyst had higher CO oxidation activity than the CI catalyst with the same compositions. Both SMAI and Cl catalysts exhibited high activity in low temperature CO oxidation. Full CO conversion was obtained at 323-383K.

Gold Catalysts Supported on Crystalline Fe_2O_3 and CeO_2/Fe_2O_3 for Low-temperature CO Oxidation

High active and stable gold catalysts supported on crystalline Fe203 and CeO2/Fe2O3 were prepared via the deposition-precipitation method. The catalyst with a Au load of 1.0% calcined at 180 ℃ showed a CO conversion of 100% at -8.9℃, while Au/CeO2/Fe2O3 converted CO completely at -16.1 ℃. Even having been calcined at 500 ℃, Au/Fe2O3 still exhibited significant catalytic activity, achieving full conversion of CO at 61.6℃. The catalyst with a low Au load of 0.5% could convert CO completely at room temperature and kept the activity unchanged for at least 150 h. N2 adsorption-desorption measurements show that the crystalline supports possessed a high specific surface area of about 200 m2/g. Characterizations of X-ray diffraction and transmission electron microscopy indicate that gold species were highly dispersed as nano or sub-nano particles on the supports. Even after the catalyst was calcined at 500 ℃, the Au particles remained in a nano-size of about 6--10 nm. X-ray photoelectron spectra reveal that the supported Au existed in metallic state Au0. The modification of Au/Fe2O3 by CeO2 proved to be beneficial to the inhibition of crystallization of Fe2O3 and the stabilization of gold particles in dispersed state, consequently promoting catalytic activity.