Spectroscopic Identification of Adsorbed Intermediates Derived from the CO+H(2)O Reaction on Zeolite-Encapsulated Gold Catalysts

Identification of reaction intermediates in the water-gas shift reaction (WGSR: H(2)O+CO-->H(2)+CO(2)) on Au(n+) (1相似文献   

An infrared study of co-adsorption of N2O and CO on ZnO

The absorption of N(2)O and CO at room temperature on finely divided ZnO surfaces gives reversible absorption bands from surface N(2)O species in the 2237-2245, 2265-2285 and 1245-1255 cm(-1) regions. The growth of the first band is at the expense of the second while its intensity and position depends on the extent of the surface carbonate, formed by the oxidation of CO by N(2)O. The order of introduction of CO and N(2)O, and whether the ZnO surface is oxidised or reduced, gave significantly different results in terms of carbonate formation. The strongest carbonate formation and implied decomposition of N(2)O, occurs at room temperature when CO is added to preadsorbed N(2)O on an oxidised ZnO surface. A single bidentate carbonate is formed under these conditions but on heating in the gas mixture to 200 degrees C an additional, possibly monodentate, carbonate occurs together with a surface formate species.     

Cu_2O(111)催化水煤气变换反应机理的理论研究

采用密度泛函理论结合周期平板模型方法系统地研究了水煤气变换反应在Cu_2O(111)表面上的反应机理,包括氧化还原机理、羧基机理和甲酸根机理.结果表明,在Cu_2O(111)表面,羧基机理和甲酸根机理均可行,且甲酸根机理更为有利,其最佳反应途径为H_2O~*→H~*+OH~*;CO(g)+H~*+OH~*→trans-HCOOH~*(1)→cis-HCOOH~*→CO_2~*+H_2(g).其中trans-HCOOH~*(1)→cis-HCOOH~*为其决速步,该基元反应的能垒仅为59 kJ·mol~(-1).羧基机理的最优反应路径同样是以H_2O的解离反应开始,随后CO(g)+OH~*→cis-COOH~*→trans-COOH~*→CO_2(g)+H~*,最后产生的两个吸附的H原子先迁移再结合生成H_2,整个反应的控速步骤为H原子的迁移,迁移能垒为96 kJ·mol~(-1).氧化还原机理则由于OH解离需要越过一个很高的能垒(254 vs.187 kJ·mol~(-1))而不可行.     

CO2 template synthesis of metal formates with a ReO3 net

The serendipitous discovery of CO2 as a template in the fabrication of ferric formate (1) has led to the preparation of serial metal(III) formates [MIII(HCOO)3.3/4CO2.1/4H2O.1/4HCOOH ]infinity (M = Fe(1), Al (2), Ga (3), and In(4)). The X-ray single-crystal determinations showed that the metals have octahedral geometries and are linked by HCOO- in the anti-anti style into a 3D ReO3 net, where CO2 molecules exist in cages of mmm symmetry and are hydrogen bonded to the formic CH groups. An X-ray powder diffraction (XRD) study revealed that 2 is identical to the documented [Al(HCOO)3.xH2O]. Further synthetic experiments and 13C NMR spectroscopy eventually confirmed that 2 should be formulated as [Al(HCOO)3.3/4CO2.1/4H2O.1/4HCOOH ]infinity, which for decades had been mistakenly given as [AlIII(HCOO)3.xH2O].     

Influence of H2 on the gas-phase decomposition of formic acid: a theoretical study

Gas-phase decomposition of formic acid results in final products CO + H2O and CO2 + H2. Experimentally, the CO/CO2 ratio tends to be large, in contradiction with mechanism studies, which show almost equal activation energies for dehydration and decarboxylation. In this work, the influence of H2 on the decomposition mechanism of HCOOH was explored using ab initio calculations at the CCSD(T)/6-311++G**//MP2/6-311++G** level. It was found that, in the presence of H2, the reaction channels leading to CO + H2O are more than those leading to CO2 + H2. With competitive energy, H2 addition to HCOOH can reduce the latter into HCHO, which then dissociates into CO + H2 catalyzed by H2O. Compared to trans-HCOOH, cis-HCOOH and cis-C(OH)2, conformers required for decarboxylation, are less populated due to interactions with H2.     

Surface chemistry of Cu in the presence of CO2 and H2O

The chemical nature of copper and copper oxide (Cu 2O) surfaces in the presence of CO 2 and H 2O at room temperature was investigated using ambient pressure X-ray photoelectron spectroscopy. The studies reveal that in the presence of 0.1 torr CO 2 several species form on the initially clean Cu, including carbonate CO 3 (2) (-), CO 2 (delta-) and C (0), while no modifications occur on an oxidized surface. The addition of 0.1 ML Zn to the Cu results in the complete conversion of CO 2 (delta-) to carbonate. In a mixture of 0.1 torr H 2O and 0.1 torr CO 2, new species are formed, including hydroxyl, formate and methoxy, with H 2O providing the hydrogen needed for the formation of hydrogenated species.     

Formation of nonclassical carbonyls of Au3+ in zeolite NaY: characterization by infrared spectroscopy

Adsorption of CO on gold supported in zeolite NaY at 85 K led to the formation of (i) various carbonyls and isocarbonyls typical of the zeolite and (ii) carbonyls formed at cationic gold sites (observed in the 2186-2171 cm(-1) region). Analysis of the behavior of the bands allows their assignment to carbonyls of Au(3+) ions. At temperatures higher than 220 K, CO adsorption led to the formation of a new type of Au(3+)-CO species (2207 cm(-1)). Once formed, these complexes could be transformed into the dicarbonyls Au(3+)(CO)(2) when the sample was cooled to 85 K in the presence of CO. The results are explained by migration of Au(3+) ions to more accessible positions within the zeolite at increasing temperatures. When a CO molecule is already adsorbed, it stabilizes the Au(3+) ion in the new position, and a second CO molecule can be coordinated, thus forming a geminal species. These results are the first evidence of Au(3+)(CO)(2) complexes.     

A kinetic study of the reactions of Fe+ with N2O, N2, O2, CO2 and H2O, and the ligand-switching reactions Fe+.X + Y --> Fe+.Y + X (X = N2, O2, CO2; Y = O2, H2O)

A series of reactions involving Fe(+) ions were studied by the pulsed laser ablation of an iron target, with detection of ions by quadrupole mass spectrometry at the downstream end of a fast flow tube. The reactions of Fe(+) with N(2)O, N(2) and O(2) were studied in order to benchmark this new technique. Extending measurements of the rate coefficient for Fe(+) + N(2)O from 773 K to 185 K shows that the reaction exhibits marked non-Arrhenius behaviour, which appears to be explained by excitation of the N(2)O bending vibrational modes. The recombination of Fe(+) with CO(2) and H(2)O in He was then studied over a range of pressure and temperature. The data were fitted by RRKM theory combined with ab initio quantum calculations on Fe(+).CO(2) and Fe(+).H(2)O, yielding the following results (120-400 K and 0-10(3) Torr). For Fe(+) + CO(2): k(rec,0) = 1.0 x 10(-29) (T/300 K)(-2.31) cm(6) molecule(-2) s(-1); k(rec,infinity) = 8.1 x 10(-10) cm(3) molecule(-1) s(-1). For Fe(+) + H(2)O: k(rec,0) = 5.3 x 10(-29) (T/300 K)(-2.02) cm(6) molecule(-2) s(-1); k(rec,infinity) = 2.1 x 10(-9) (T/300 K)(-0.41) cm(3) molecule(-1) s(-1). The uncertainty in these rate coefficients is determined using a Monte Carlo procedure. A series of exothermic ligand-switching reactions were also studied at 294 K: k(Fe(+).N(2) + O(2)) = (3.17 +/- 0.41) x 10(-10), k(Fe(+).CO(2) + O(2)) = (2.16 +/- 0.35) x 10(-10), k(Fe(+).N(2) + H(2)O) = (1.25 +/- 0.14) x 10(-9) and k(Fe(+).O(2) + H(2)O) = (8.79 +/- 1.30) x 10(-10) cm(3) molecule(-1) s(-1), which are all between 36 and 52% of their theoretical upper limits calculated from long-range capture theory. Finally, the role of these reactions in the chemistry of meteor-ablated iron in the upper atmosphere is discussed. The removal rates of Fe(+) by N(2), O(2), CO(2) and H(2)O at 90 km altitude are approximately 0.1, 0.07, 3 x 10(-4) and 1 x 10(-6) s(-1), respectively. The initially formed Fe(+).N(2) and Fe(+).O(2) are converted into the H(2)O complex at approximately 0.05 s(-1). Fe(+).H(2)O should therefore be the most abundant single-ligand Fe(+) complex in the mesosphere below 90 km.     

Infrared absorption spectra of the CO(2)/H(2)O complex in a cryogenic nitrogen matrix--detection of a new bending frequency

Infrared absorption spectra have been measured for the mixture of CO(2) and H(2)O in a cryogenic nitrogen matrix. The 1:1 CO(2)/H(2)O complex has been observed. Each structure of this complex should have two bending frequencies corresponding to the CO(2) fundamental bending mode (ν(2)). In this work, three bending frequencies corresponding to the CO(2) fundamental bending mode (ν(2)) have been detected; one of them at 660.3 cm(-1) is reported here for the first time. This finding helps confirm the existence of two structures for this complex. A new feature attributed to a CO(2) and H(2)O complex is observed at 3604.4 cm(-1) and is tentatively assigned to the CO(2)/H(2)O complex band corresponding to the CO(2) combination mode (ν(3) + 2ν(2)). In addition, a band that belongs to a CO(2) and H(2)O complex is detected at 3623.8 cm(-1) for the first time and is tentatively assigned to the (CO(2))(2)/H(2)O complex band corresponding to the symmetric stretching mode (ν(1)) of H(2)O.     

Reaction mechanism of CO oxidation on Cu(2)O(111): A density functional study

The possible reaction mechanisms for CO oxidation on the perfect Cu(2)O(111) surface have been investigated by performing periodic density functional theoretical calculations. We find that Cu(2)O(111) is able to facilitate the CO oxidation with different mechanisms. Four possible mechanisms are explored (denoted as M(ER1), M(ER2), M(LH1), and M(LH2), respectively): M(ER1) is CO((gas))+O(2(ads))→CO(2(gas)); M(ER2) is CO((gas))+O(2(ads))→CO(3(ads))→O((ads))+CO(2(gas)); M(LH1) refers to CO((ads))+O(2(ads))→O((ads))+CO(2(ads)); and M(LH2) refers to CO((ads))+O(2(ads))→OOCO((ads))→O((ads))+CO(2(ads)). Our transition state calculations clearly reveal that M(ER1) and M(LH2) are both viable; but M(ER1) mechanism preferentially operates, in which only a moderate energy barrier (60.22 kJ/mol) needs to be overcome. When CO oxidation takes place along M(ER2) path, it is facile for CO(3) formation, but is difficult for its decomposition, thereby CO(3) species can stably exist on Cu(2)O(111). Of course, the reaction of CO with lattice O of Cu(2)O(111) is also considered. However, the calculated barrier is 600.00 kJ/mol, which is too large to make the path feasible. So, we believe that on Cu(2)O(111), CO reacts with adsorbed O, rather than lattice O, to form CO(2). This is different from the usual Mars-van Krevene mechanism. The present results enrich our understanding of the catalytic oxidation of CO by copper-based and metal-oxide catalysts.     

Insights into the oxidation and decomposition of CO on Au/alpha-Fe2O3 and on alpha-Fe2O3 by coupled TG-FTIR

CO oxidation and decomposition behaviors over nanosized 3% Au/alpha-Fe2O3 catalyst and over the alpha-Fe2O3 support were studied in situ via thermogravimetry coupled to on-line FTIR spectroscopy (TG-FTIR), which was used to obtain temperature-programmed reduction (TPR) curves and evolved gas analysis. The catalyst was prepared by a sonication-assisted Au colloid based method and had a Au particle size in the range of 2-5 nm. Carburization studies of H 2-prereduced samples were also made in CO gas. According to gravimetry, for the 3% Au/alpha-Fe2O3 catalyst, there were three distinct stages of CO interaction with the Au catalyst but only two stages for the catalyst support. At low temperatures (相似文献   

Adsorption of CO and O2 on W2C(0001)

CO, O(2), and H(2) adsorption on a clean W(2)C(0001)√13×√13 R ± 13.9° reconstructed surface at room temperature (RT) were investigated using high-resolution electron energy loss spectroscopy (HREELS). The W(2)C(0001) adsorbs CO molecularly and adsorbs O(2) dissociatively, but does not adsorb H(2) at RT. In the CO adsorption system, two C-O stretching (antisymmetric CCO stretching) modes were found at 242.3 meV (1954 cm(-1)) and at 253.0 meV (2041 cm(-1)). The low-frequency site is occupied at first with subsequent conversion to the high-frequency site with increasing coverage. Additionally, a small peak was apparent at 104.5 meV (843 cm(-1)), and a middle peak at 50-51 meV (400-410 cm(-1)), which are assignable to a symmetric stretching mode and a hindered translational mode, respectively, of a CCO (ketenylidene) species. These observations are consistent with the CO adsorption model on top of the surface carbon. For oxygen adsorption, two adsorption states were found at 65.2-68.1 meV (526-549 cm(-1)) and 73.6 meV (594 cm(-1)): typical frequencies to oxygen adsorption on metal surfaces. Results suggest that atomic oxygen adsorption occurred on a threefold hollow site of the second W layer.     

H(2) and CO(2) coadsorption effects in CO adsorption over nanosized Au/gamma-Al(2)O(3) catalysts

The present study is focused on the kinetic investigation of the effects of H(2) and CO(2) on the rates related to the elementary steps of CO sorption over Au/gamma-Al(2)O(3). The kinetic study was carried out in a wide temperature range (50-300 degrees C) by the novel methodology of reversed flow gas chromatography (RF-GC). The findings of preliminary coadsorption studies of CO with H(2), O(2) and O(2)+H(2) indicate that a reductive pre-treatment of the Au catalyst with a mixture of CO in excess of H(2) can be more beneficial concerning CO oxidation activity at low temperatures, compared to the usual reduction in a diluted hydrogen atmosphere, most probably due to the easier activation of oxygen molecules. At high temperatures the rate of reversed water gas shift reaction becomes significant resulting in H(2) and CO(2) consumption. The kinetic findings indicate that hydrogen strongly influences the adsorption of CO over Au/gamma-Al(2)O(3), by enhancing CO adsorption at lower temperatures and weakening the strength CO binding. On the other hand, CO(2) adsorption competes that of CO under hydrogen-rich conditions. However, the strength of CO(2) bonding is higher compared to that of CO and it further increases at higher temperatures, in agreement with the observed deactivation of the selective CO oxidation in the presence of CO(2).     

First-principles study of interaction of cluster Au32 with CO, H2, and O2

First-principles calculations are performed to study the interaction of cluster Au(32) with small molecules, such as CO, H(2), and O(2). The cagelike Au(32)(I(h)) shows a higher chemical inertness than the amorphous Au(32)(C(1)) with respect to the interaction with small molecules CO, H(2), and O(2). H(2) can only be physically adsorbed on Au(32)(I(h)), while it can be dissociatively chemisorbed on Au(32)(C(1)). Although CO can be chemically adsorbed on Au(32)(I(h)) and Au(32)(C(1)) with one electron transferred from Au(32) to the antibonding pi* orbit of CO, it is bound more strongly on Au(32)(C(1)) than on Au(32)(I(h)). Spin polarized and spin nonpolarized calculations result almost identical ground state structures of Au(32)(I(h))-O(2) and Au(32)(C(1))-O(2), in which O(2) is dissociatively chemisorbed.     

Vibrational distributions of the CO(v) products of the C2H2 + O(3P) and HCCO + O(3P) reactions studied by FTIR emission

The C2H2 + O(3P) and HCCO + O(3P) reactions are investigated using Fourier transform infrared (FTIR) emission spectroscopy. The O(3P) radicals are produced by 193 nm photolysis of an SO2 precursor or microwave discharge in O2. The HCCO radical is either formed in the first step of the C2H2 + O(3P) reaction or by 193 nm photodissociation of ethyl ethynyl ether. Vibrationally excited CO and CO2 products are observed. The microwave discharge experiment [C2H2 + O(3P)] shows a bimodal distribution of the CO(v) product, which is due to the sequential C2H2 + O(3P) and HCCO + O(3P) reactions. The vibrational distribution of CO(v) from the HCCO + O(3P) reaction also shows its own bimodal shape. The vibrational distribution of CO(v) from C2H2 + O(3P) can be characterized by a Boltzmann plot with a vibrational temperature of approximately 2400 +/- 100 K, in agreement with previous results. The CO distribution from the HCCO + O(3P) reaction, when studied under conditions to minimize other processes, shows very little contamination from other reactions, and the distribution can be characterized by a linear combination of Boltzmann plots with two vibrational temperatures: 2320 +/- 40 and 10 300 +/- 600 K. From the experimental results and previous theoretical work, the bimodal CO(v) distribution for the HCCO + O(3P) reaction suggests a sequential dissociation process of the HC(O)CO++ --> CO + HCO; HCO --> H + CO.     

Chemical properties of the Pd4(dppm)4(H)2(2+) cluster and the homogeneous electrocatalytical behavior of hydrogen evolution and formate decomposition

Two new reductive electrochemical (CO2 + H2O + 2e-; HCO2H + 2e-) and two new chemical methods (Al(CH3)3 + proton donor; NaO2CH) to prepare the title compound from Pd2(dppm)2Cl2 are reported. For the latter method, an intermediate species formulated as Pd2(dppm)4(O2CH)2(2+) is identified spectroscopically (1H NMR, 31P NMR, IR, and FAB-MS). Limited stability of the title compound in the presence of Cl- and Br- as counteranions is noticed and is due to sensitivity of the cluster toward nucleophilic attack of the halide ions. This result is corroborated by the rapid decomposition of these clusters in the presence of CN- to form the binuclear species Pd2(dppm)2(CN)4 and by the preparation of the stable salts [Pd4(dppm)4(H)2](X)2(X- = BF4-, PF6-, BPh4-). Upon a two-electron electrochemical reduction of this cluster to the neutral species (E1/2 = -1.42 V vs SCE in DMF) in the presence of 1 equiv of HCO2H, a highly reactive species formulated as [Pd4(dppm)4(H)3]+ is generated and characterized by 1H NMR, 31P NMR, and cyclic voltammetry. Subsequent addition of H+ (via RCO2H; R = H, CH3, CF3, C6H5) under the same reducing conditions, induces the homogeneous catalysis of H2 evolution. The turnover number is found to be 134 in 2 h, with no evidence for catalyst decomposition. This same species also exhibits a one-electron oxidation process (E1/2 = -0.61 V vs SCE in DMF) that induces the catalytical decomposition of formate (HCO2- --> CO2 + 1/2H2 + 1e-). This double catalysis from the same cluster intermediate is unprecedented.     

Coadsorption properties of CO(2) and H(2)O on TiO(2) rutile (110): A dispersion-corrected DFT study

Adsorption and reactions of CO(2) in the presence of H(2)O and OH species on the TiO(2) rutile (110)-(1×1) surface were investigated using dispersion-corrected density functional theory and scanning tunneling microscopy. The coadsorbed H(2)O (OH) species slightly increase the CO(2) adsorption energies, primarily through formation of hydrogen bonds, and create new binding configurations that are not present on the anhydrous surface. Proton transfer reactions to CO(2) with formation of bicarbonate and carbonic acid species were investigated and found to have barriers in the range 6.1-12.8 kcal∕mol, with reactions involving participation of two or more water molecules or OH groups having lower barriers than reactions involving a single adsorbed water molecule or OH group. The reactions to form the most stable adsorbed formate and bicarbonate species are exothermic relative to the unreacted adsorbed CO(2) and H(2)O (OH) species, with formation of the bicarbonate species being favored. These results are consistent with single crystal measurements which have identified formation of bicarbonate-type species following coadsorption of CO(2) and water on rutile (110).     

Surface photochemistry of Rh(CO)2 on zeolite Y-production of a stable coordinatively unsaturated rhodium monocarbonyl surface species at room temperature

The photochemical production and chemical reactivity of a new coordinatively unsaturated rhodium monocarbonyl species on the surface of dealuminated zeolite Y over a temperature range of 300-420 K and a pressure range from 10(-5) to 20 Torr has been studied. Using high vacuum techniques and transmission infrared spectroscopy, ultraviolet irradiation (350 +/- 50 nm) of supported Rh(CO)(2) surface species led to the production of stable, but reactive, =Rh(CO) surface species, characterized by an infrared band at 2023 cm(-1). The coordinatively unsaturated =Rh(CO) species convert to less reactive and coordinatively saturated Rh(CO) by thermal treatment above 370 K. The Rh(CO) species were characterized by an infrared band at 2013 cm(-1). An explanation of the mode of bonding of the rhodium monocarbonyl species to the zeolite surface is provided. Coordinatively unsaturated =Rh(CO) species captured N(2), H(2), and O(2) gas molecules near room temperature to produce a variety of mixed ligand rhodium surface complexes of the form Rh(CO)(N(2)), Rh(CO)(H(2)), Rh(CO)(H)(2), Rh(CO)(H), Rh(CO)(O), and Rh(O). Infrared band assignments for the new species are provided. The work provides new insight into the photochemical behavior of Rh(CO)(2) species supported on high-area zeolite materials and may improve our understanding of the role of active rhodium monocarbonyl species in the development of heterogeneous photocatalysts.     

DFT法研究HCOOH在Pd/WC(0001)上的分解机理（英文）

作为便携式电子设备的动力源,直接甲酸燃料电池(DFAFC)具有燃料跨界范围小、电动势大、甲酸无毒、低温下功率密度大等优点,因而引起了人们的极大兴趣.DFAFC商业化的主要挑战之一是阳极电催化剂材料的高成本和低CO耐受性.阳极通常需要高负载的贵金属电催化剂(Pt或Pd)氧化甲酸(HCOOH)以获得所需的电能.完全电氧化甲酸在Pt和Pd表面上会产生强吸附的CO,从而降低了Pt或Pd催化剂的活性.Pt和Pd储量少且价格昂贵,减少Pt和Pd含量且保持催化性能的燃料电池催化剂一直是研究者的奋斗目标.本文用周期性密度泛函理论(DFT)系统地研究了WC负载的单分子层Pd(Pd/WC(0001))催化剂对甲酸的分解机理,这可为所需的反应路径设计、筛选催化剂提供指导.Trans-HCOOH通过C-H,O-H,C-O键的活化发生分解.关于吸附,确定了可能反应中间体的最稳定吸附构型.trans-HCOOH,HCOO,mHCOO,cis-COOH,trans-COOH,CO,H2O,OH和H的吸附过程是化学吸附,而cis-HCOOH和CO2与Pd/WC(0001)表面的相互作用较弱,是物理吸附.此外,提出了trans-HCOOH分解的不同途径来探索分解机理.trans-HCOOH中O-H,C-H和C-O键的活化能垒分别为0.61,0.77和1.05 eV,O-H键断裂的能垒最小,则trans-HCOOH优先通过O-H键断裂生成HCOO.双齿HCOO是HCOOH分解的主要中间体,它可以转变为单齿HCOO,这条路线生成CO2的能垒比双齿HCOO的低0.04 eV.CO2是HCOO主要解离产物,这一步是总反应的决速步骤.对于cis-COOH和trans-COOH,CO是其主要解离产物.此外,trans-HCOOH也能直接生成CO,但克服的能垒较大.在Pd/WC(0001)表面上分解trans-HCOOH的最有利途径是HCOOH→HCOO→CO2,其中HCOO脱氢形成CO2的步骤是速率决定步骤.本文提供了HCOOH在Pd/WC(0001)表面上分解的活性中间体、能垒和机理的推测,CO形成主要是通过cis-COOH、trans-COOH及HCO的分解,CO2的形成主要是通过HCOO的分解,CO2占主导.该结论与Pd(111)面上甲酸分解结果一致,说明WC作为Pd载体没有改变Pd对甲酸的催化性能,但降低了Pd的使用量.综上,本文阐明了WC负载单分子层Pd催化剂上甲酸催化分解机理,得出甲酸分解的最佳反应路径,为直接甲酸燃料电池设计低贵金属含量、高活性的负载型Pd催化剂提供了理论指导;可用于预测不同载体负载Pd催化剂的性能,大大减少实验成本,以验证提出的实验假设.     

Heats of adsorption of linear CO species adsorbed on the Au degrees and Ti+delta sites of a 1% Au/TiO2 catalyst using in situ FTIR spectroscopy under adsorption equilibrium

The heats of adsorption of two linear CO species adsorbed on the Au degrees particles (denoted L(Au degrees)) and on the Ti(+delta) sites (denoted L(Ti+delta)) of a 1% Au/TiO(2) catalyst are determined as the function of their respective coverage by using the AEIR procedure (adsorption equilibrium infrared spectroscopy) previously developed. Mainly, the evolutions of the IR band area of each adsorbed species (2184 cm(-1) for L(Ti+delta) and at 2110 cm(-1) for L(Au degrees)) as a function of the adsorption temperature T(a), at a constant CO adsorption pressure P(CO), provide the evolutions of the coverages theta(LTi+delta) and theta(LAu degrees ) of each adsorbed CO species with T(a) in isobar conditions that give the individual heats of adsorption. It is shown that they linearly vary from 74 to 47 kJ/mol for L(Au degrees ) and from 50 to 40 kJ/mol for L(Ti+delta) at coverages 0 and 1, respectively. These values are consistent with literature data on model Au particles and TiO(2). In particular, it is shown that the mathematical formalism supporting the AEIR procedure can be applied to literature data on Au-containing solids (single crystals and model particles).