Single atom gold catalysts for low-temperature CO oxidation

Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The active sites are traditionally believed to be Au nanoclusters or nanoparticles in the size range of 0.5–5 nm. Only in the last few years have single‐atom Au catalysts been proved to be active for CO oxidation. Recent advances in both experimental and theoretical studies on single‐atom Au catalysts unambiguously demonstrated that when dispersed on suitable oxide supports the Au single atoms can be extremely active for CO oxidation. In this mini‐review, recent advances in the development of Au single‐atom catalysts are discussed, with the aim of illus‐trating their unique catalytic features during CO oxidation.

Low-temperature oxidation behavior of MoSi_2 powders

The oxidation behavior of molybdenum disilicide （MoSi2） powders at 400, 500, and 600℃ for 12 h in air were investigated by using X-ray diffraction （XRD） and transmission electron microscopic （TEM） techniques. Significant changes were observed in volume, mass, and color. Especially at 500℃, the volume expansion was found to be as high as 7-8 times, the color changed from black to yellow-white, and the mass gain was about 169.34% after 8 h, with SiO2 and MoO3 as main reaction products. The gains in volume and mass were less at 400 and 600℃ compared with those at 500℃, probably due to the less reaction rate at 400℃ and the formation of silica glass scale at 600℃, which would protect the matrix and restrain the diffusion of oxygen and molybdenum. Thus, the accelerated oxidation behavior of MoSi2 powder appeared at 500℃ and the volume expansion was the sign of accelerated oxidation.

In situ catalytic upgrading of heavy crude oil through low-temperature oxidation

The low-temperature catalytic oxidation of heavy crude oil（Xinjiang Oilfield,China） was studied using three types of catalysts including oil-soluble,watersoluble,and dispersed catalysts.According to primary screening,oil-soluble catalysts,copper naphthenate and manganese naphthenate,are more attractive,and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil.The heavy oil compositions and molecular structures were characterized by column chromatography,elemental analysis,and Fourier transform infrared spectrometry before and after reaction.An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity-temperature characteristics.Results show that the two oil-soluble catalysts can crack part of heavy components into light components,decrease the heteroatom content,and achieve the transition of reaction mode from oxygen addition to bond scission.The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil（oil viscosity and contents of heavy fractions）.It is found that the temperature,oil composition,and internal molecular structures are the main factors affecting its flow ability.Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.

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.

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.

Oxidation of Fe-Cr-Ni Alloys in a Low Oxygen Partial Pressure Atmosphere to Mitigate Coke Formation

Anti-coking oxide films were prepared on a 25Cr35Ni and 35Cr45Ni alloy surface under the low oxygen partialpressure atmosphere of a H2-H2O mixture. The composition and phase structure of the oxide films were analyzed by energydispersive spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The anti-cokingperformance of a mini tube made of a HP40 (25Cr35Ni) alloy was evaluated on a bench scale pyrolysis and coking test unit.The results showed that the surface Fe and Ni content decreased after the oxidation of the two alloys in a low oxygen partialpressure atmosphere. The oxide films were mainly composed of MnCr_(2)O_(4) and Cr_(2)O_(3). The average mass of coke in the minitube with oxide film decreased by 87% relative to that of a tube without an oxide film when the cracking temperature was 900℃. The ethylene, propylene, and butadiene yields in the pyrolysis tests were almost the same for the mini tubes withand without an oxide film. The oxide film on the alloy surface effectively inhibited catalytic filamentous coke formation.An industrial test showed that the run length of the cracking furnace with the in-situ coating technology was significantlyextended.

TiO_2-Supported Binary Metal Oxide Catalysts for Low-temperature Selective Catalytic Reduction of NO_x with NH_3

Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order：Mn-W/TiO2〉Mn-Fe/TiO2〉Mn-Cr/TiO2〉Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order：Mn-Fe/TiO2〉Mn-W/TiO2〉Mn-Mo/TiO2〉Mn-Cr/TiO2.In the presence of 0.01%SO2 and 6%H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8%and 94.2%, respectively,after 8 h at 120°C at GHSV 12600 h？ 1 .As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared（FTIR）spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.

Low CO content hydrogen production from oxidative steam reforming of ethanol over CuO-CeO_2 catalysts at low-temperature

CuO-CeO2 catalysts were prepared by a urea precipitation method for the oxidative steam reforming of ethanol at low-temperature.The catalytic performance was evaluated and the catalysts were characterized by inductively coupled plasma atomic emission spectroscopy,X-ray diffraction,temperature-programmed reduction,field emission scanning electron microscopy and thermo-gravimetric analysis.Over CuOCeO2 catalysts,H2 with low CO content was produced in the whole tested temperature range of 250–450 C.The non-noble metal catalyst 20CuCe showed higher H2production rate than 1%Rh/CeO2 catalyst at 300–400 C and the advantage was more obvious after 20 h testing at400 C.These results further confirmed that CuO-CeO2 catalysts may be suitable candidates for low temperature hydrogen production from ethanol.

Recent progress in CO oxidation over Pt-group-metal catalysts at low temperatures

CO oxidation is probably the most studied reaction in heterogeneous catalysis.This reaction has become a hot topic with the discovery of nanogold catalysts,which are active at low temperatures（at or below room temperature）.Au catalysts are the benchmark for judging the activities of other metals in CO oxidation.Pt-group metals（PGMs） that give comparable performances are of particular interest.In this mini-review,we summarize the advances in various PGM（Pt,Pd,Ir,Rh,Ru）catalysts that have high catalytic activities in low-temperature CO oxidation arising from reducible supports or the presence of OH species.The effects of the size of the metal species and the importance of the interface between the metal and the reducible support are covered and discussed in terms of their promotional role in CO oxidation at low temperatures.

Synthesis of Pd nanoparticles supported on CeO_2 nanotubes for CO oxidation at low temperatures

Developing efficient supported Pd catalysts and understanding their catalytic mechanism in CO oxidation are challenging research topics in recent years.This paper describes the synthesis of Pd nanoparticles supported on CeO2 nanotubes via an alcohol reduction method.The effect of the support morphology on the catalytic reaction was explored.Subsequently,the performance of the prepared catalysts was investigated toward CO oxidation reaction and characterized by Nitrogen sorption,X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,and CO-temperature-programmed desorption techniques.The results indicated that the catalyst of Pd on CeO2 nanotubes exhibits excellent activity in CO oxidation at low temperatures,due to its large surface area,the high dispersion of Pd species,the mesoporous and tubular structure of the CeO2-nanotube support,the abundant Ce3＋,formation of Pd–O–Ce bonding,and enhanced metal–support interaction on the catalyst surface.

Growth behaviour of low-energy plasma electrolytic oxidation coatings on a magnesium alloy

Plasma electrolytic oxidation(PEO),a promising surface treatment method to improve the corrosion and wear resistance of magnesium and its alloys,operates at high voltages,resulting in a relatively high energy cost.To make the PEO process more economically viable,its energy efficiency needs to be improved.This study investigates the growth behaviour and microstructural characteristics of low-energy PEO coatings on an AM50 magnesium alloy in a concentrated electrolyte containing sodium tetraborate.The surface morphology of the coatings was different from typical PEO coating morphologies and a large voltage oscillation was observed during treatment.Using different characterisation techniques,and based on a micro-discharge model,a correlation was made between the voltage-time behaviour,microdischarge characteristics and the composition and microstructure of the coated samples.The results suggest electrolyte chemistry can somewhat control discharge behaviour,which plays an important role in PEO coating growth.

An ionic liquid-assisted strategy for enhanced anticorrosion of low-energy PEO coatings on magnesium–lithium alloy

A low-energy plasma electrolytic oxidation(LePEO)technique is developed to simultaneously improve energy efficiency and anti-corrosion.Ionic liquids(1-butyl-3-methylimidazole tetrafluoroborate(BmimBF_(4)))as sustainable corrosion inhibitors are chosen to investigate the corrosion inhibition behavior of ionic liquid(ILs)during the LePEO process for LA91 magnesium-lithium(Mg-Li)alloy.Results show that the ionic liquid BmimBF_(4)participates in the LePEO coating formation process,causing an increment in coating thickness and surface roughness.The low conductivity of the ionic liquid is responsible for the voltage and breakdown voltage increases during the LePEO with IL process(LePEO-IL).After adding BmimBF_(4),corrosion current density decreases from 1.159×10^(−4)A·cm^(−2)to 8.143×10^(−6)A·cm^(−2).The impedance modulus increases to 1.048×10^(4)Ω·cm^(−2)and neutral salt spray remains intact for 24 h.The superior corrosion resistance of the LePEO coating assisted by ionic liquid could be mainly attributed to its compact and thick barrier layer and physical absorption of ionic liquid.The ionic liquid-assisted LePEO technique provides a promising approach to reducing energy consumption and improving film performance.

An experimental study of the effect of ionic liquids on the low temperature oxidation of coal

Fourier transform infrared spectroscopy(FTIR) and constant heating rate experiments were performed to study the low temperature oxidation of coal treated by an ionic liquid,1-allyl-3-methylimidazolium chloride.The inerting effect of the ionic liquid toward the low temperature oxidation process is discussed.The results show that:(1) The hydroxyl content associated with hydrogen bonds,the aliphatic methyl content,the methylene group content,and the ether oxygen bond content are reduced in the treated coal.At the same time the content of aromatic C@C bonds is constant but these chemical bonds weaken and some substituted aromatic hydrocarbon content increases while other types decrease.This demonstrates that(AMIm)Cl dissolves and destroys the coal surface microstructure;(2) The oxygen consumption of the treated coal is less than what is seen in raw coal.The CO,CO 2,C 2 H 4,and C 2 H 6 content from the treated coal is reduced compared to the untreated coal;(3) The apparent activation energy for the oxidizing reaction is different in the treated and raw coals.Micro-structural changes and macroscopic gas production allow us to conclude that(AMIm)Cl can effectively inhibit low temperature oxidation of coal.

Preparation and Properties of Anti-oxidation Inorganic Nano-coating for Low Carbon Steel at an Elevated Temperature

A new kind of anti-oxidation inorganic nano-coating for the common low carbon steel was prepared. It included magnesite mineral, metallurgic dust and silicate adhesive as the main raw materials. The nano-coating could be sprayed directly onto the low carbon steel slab even though with hot surface as far as under 1000 ℃ . And at the same time, a compact thin nano-film was formed, and the film would inhibit the oxygen into the interface of the steel body and decrease the loss of weight because of oxidation. The loss was decreased by about 60% or more. The properties and mechanism of oxidation resistance of the coating were discussed through XRD, TG-DTA and SEM. The experimental results show that many reactions would happen among the companents of the coating and then many microspheres with the size of 80- 100nm generated in the system. By using the heat of the steel body, the silicate adhesive would interact with the microspheres, and the other components of the coating would be soft and sintered so that when the coating was sprayed onto the suface of the steel slab , the intact and compact film could be formed and adhesive with the steel body. Besides the special properties of anti- oxidation, the coating could prevent the volatilization of microelement in the steel such as silicate and carbon at a high temperature. So it can improve the quality and output of steel with this new kind of nano-coating.

Investigation of low-temperature hydrothermal stability of Cu-SAPO-34 for selective catalytic reduction of NO_x with NH_3

The low‐temperature hydrothermal stabilities of Cu‐SAPO‐34samples with various Si contents and Cu loadings were systematically investigated.The NH3oxidation activities and NH3‐selective catalytic reduction(SCR)activities(mainly the low‐temperature activities)of all the Cu‐SAPO‐34catalysts declined after low‐temperature steam treatment(LTST).These results show that the texture and acid density of Cu‐SAPO‐34can be better preserved by increasing the Cu loading,although the hydrolysis of Si-O-Al bonds is inevitable.The stability of Cu ions and the stability of the SAPO framework were positively correlated at relatively low Cu loadings.However,a high Cu loading(e.g.,3.67wt%)resulted in a significant decrease in the number of isolated Cu ions.Aggregation of CuO particles also occurred during the LTST,which accounts for the decreasing NH3oxidation activities of the catalysts.Among the catalysts,Cu‐SAPO‐34with a high Si content and medium Cu content(1.37wt%)showed the lowest decrease in NH3‐SCR because its Cu2+content was well retained and its acid density was well preserved.

Oxidation of CO on Nanometer Metal Oxides at Low Temperatures

ＯｘｉｄａｔｉｏｎｏｆＣＯｏｎＮａｎｏｍｅｔｅｒＭｅｔａｌＯｘｉｄｅｓａｔＬｏｗＴｅｍｐｅｒａｔｕｒｅｓ＊ＺＨＡＮＧＷｅｎ－ｘｉａｎｇ＊＊，ＪＩＡＭｉｎｇ－ｊｕｎ，ＺＨＡＯＪｉｎｇ－ｚｈｅ，ＺＨＡＮＧＣｈｕｎ－ｌｅｉ，ＷＵＴｏｎｇ－ｈａｏ（Ｄｅｐａｒ...

La-doped Pt/TiO_2 as an efficient catalyst for room temperature oxidation of low concentration HCHO

Catalytic oxidation of formaldehyde (HCHO) is the most efficient way to purify indoor air of HCHO pollutant. This work investigated rare earth La‐doped Pt/TiO2 for low concentration HCHO oxidation at room temperature. La‐doped Pt/TiO2 had a dramatically promoted catalytic performance for HCHO oxidation. The reasons for the La promotion effect were investigated by N2 adsorption, X‐raydiffraction, CO chemisorption, X‐ray photoelectron spectroscopy, transmission electron microscopy(TEM) and high‐angle annular dark field scanning TEM. The Pt nanoparticle size was reduced to 1.7nm from 2.2 nm after modification by La, which led to higher Pt dispersion, more exposed activesites and enhanced metal‐support interaction. Thus a superior activity for indoor low concentrationHCHO oxidation was obtained. Moreover, the La‐doped TiO2 can be wash‐coated on a cordieritemonolith so that very low amounts of Pt (0.01 wt%) can be used. The catalyst was evaluated in asimulated indoor HCHO elimination environment and displayed high purifying efficiency and stability.It can be potentially used as a commercial catalyst for indoor HCHO elimination.

Preparation of Palladium Supported on Ferric Oxide Nano-catalysts for Carbon Monoxide Oxidation in Low Temperature

Catalytic property of Pd/Fe2O3 catalysts on carbon monoxide(CO) oxidation at low temperature were investigated in this paper. Both the as-prepared and H2-pretreated Pd/Fe2O3 catalysts show catalytic performances on CO oxidation. The CO was completely converted at 333 K for the as-prepared sample,whereas at 313 K for H2-pretreated Pd/Fe2O3-573 catalyst. The catalytic performance of the Pd/Fe2O3 catalyst decreases with increased calcination temperature. This may be due to the increased crystallinity of the support and decreased metal-support interaction. Progressive deactivation of the catalysts during long-time reaction was associated with the formation of carbonates on the catalyst surface that inhibits CO activation or intermediate transformation.

A Review on Complete Oxidation of Methane at Low Temperatures

This paper reviews recent developments in complete oxidation of methane atlow temperatures over noble metal catalysts in the past 20 years. The Pd/Al_2O_3 catalyst system isfully discussed. The review mainly focuses on the kinetic aspects of methane oxidation over thiscatalyst, and methane activation behavior over Pd and PdO phases (the form of PdO on the surface,transient behavior, the nature of the active sites, the influence of metal particle size and theirstructure sensitivities, and so on). Some Pd catalysts supported on other oxides besides the Al_2O_3support are briefly discussed. Possible routes of non-noble metal catalysts as substitutes for thePd catalyst are also proposed.

EFFECTS OF TRACE ELEMENTS ON THE OXIDATION OF LOW SEGREGATION Ni－Cr－Al BASED SUPERALLOYS

The oxidation behaviors of two kinds of low segregation Ht-Cr-Al based superalloys have been studied between 1000-1100℃, and compared with that of general Mt-Cr-Al based superalloys. The results indicated that the simultaneous additions of 0.1 wt% S and 0. 1 wt% Zr to low segregation alloys increase the oxidation rate of Al2O3-forming alloy and improve the scale adherence. The addition of 0.1 wt% Zr can ,minimize the negative effects of S on the adherence of Al2O3 scale. Low amounts of S(≤50 ppm wt) have no obviously negative effects on the adherence of Cr2O3 scale formed on one of the low segregation superalloys.