Optimized Pt-Co Alloy Nanoparticles for Reverse Water-Gas Shift Activation of CO2.

Different Co contents were used to tune bimetallic Pt-Co nanoparticles with a diameter of 8 nm, resulting in Pt:Co ratios of 3.54, 1.51, and 0.96. These nanoparticles were then applied to the MCF-17 mesoporous silica support. The synthesized materials were characterized with HR-TEM, HAADF-TEM, EDX, XRD, BET, ICP-MS, in situ DRIFTS, and quasi in situ XPS techniques. The catalysts were tested in a thermally induced reverse water-gas shift reaction (CO2:H2 = 1:4) at atmospheric pressure in the 200-700 °C temperature range. All bimetallic Pt-Co particles outperformed the pure Pt benchmark catalyst. The nanoparticles with a Pt:Co ratio of 1.51 exhibited 2.6 times higher activity and increased CO selectivity by 4% at 500 °C. Experiments proved that the electron accumulation and alloying effect on the Pt-Co particles are stronger with higher Co ratios. The production of CO followed the formate reaction pathway on all catalysts due to the face-centered-cubic structure, which is similar to the Pt benchmark. It is concluded that the enhanced properties of Co culminate at a Pt:Co ratio of 1.51 because decreasing the ratio to 0.96 results in lower activity despite having more Co atoms available for the electronic interaction, resulting in the lack of electron-rich Pt sites.

Pt/MnO Interface Induced Defects for High Reverse Water Gas Shift Activity.

The implementation of supported metal catalysts heavily relies on the synergistic interactions between metal nanoparticles and the material they are dispersed on. It is clear that interfacial perimeter sites have outstanding skills for turning catalytic reactions over, however, high activity and selectivity of the designed interface-induced metal distortion can also obtain catalysts for the most crucial industrial processes as evidenced in this paper. Herein, the beneficial synergy established between designed Pt nanoparticles and MnO in the course of the reverse water gas shift (RWGS) reaction resulted in a Pt/MnO catalyst having ≈10 times higher activity compared to the reference Pt/SBA-15 catalyst with >99 % CO selectivity. Under activation, a crystal assembly through the metallic Pt (110) and MnO evolved, where the plane distance differences caused a mismatched-row structure in softer Pt nanoparticles, which was identified by microscopic and surface-sensitive spectroscopic characterizations combined with density functional theory simulations. The generated edge dislocations caused the Pt lattice expansion which led to the weakening of the Pt-CO bond. Even though MnO also exhibited an adverse effect on Pt by lowering the number of exposed metal sites, rapid desorption of the linearly adsorbed CO species governed the performance of the Pt/MnO in the RWGS.

CO2 Conversion on N-Doped Carbon Catalysts via Thermo- and Electrocatalysis: Role of C-NO x Moieties.

N-doped carbon (N-C) materials are increasingly popular in different electrochemical and catalytic applications. Due to the structural and stoichiometric diversity of these materials, however, the role of different functional moieties is still controversial. We have synthesized a set of N-C catalysts, with identical morphologies (∼27 nm pore size). By systematically changing the precursors, we have varied the amount and chemical nature of N-functions on the catalyst surface. The CO2 reduction (CO2R) properties of these catalysts were tested in both electrochemical (EC) and thermal catalytic (TC) experiments (i.e., CO2 + H2 reaction). CO was the major CO2R product in all cases, while CH4 appeared as a minor product. Importantly, the CO2R activity changed with the chemical composition, and the activity trend was similar in the EC and TC scenarios. The activity was correlated with the amount of different N-functions, and a correlation was found for the -NO x species. Interestingly, the amount of this species decreased radically during EC CO2R, which was coupled with the performance decrease. The observations were rationalized by the adsorption/desorption properties of the samples, while theoretical insights indicated a similarity between the EC and TC paths.

M(II)Al4 Type Layered Double Hydroxides-Preparation Using Mechanochemical Route, Structural Characterization and Catalytic Application.

The synthesis of the copper-poor and aluminum-rich layered double hydroxides (LDHs) of the CuAl4 type was optimized in detail in this work, by applying an intense mechanochemical treatment to activate the gibbsite starting reagent. The phase-pure forms of these LDHs were prepared for the first time; using copper nitrate and perchlorate salts during the syntheses turned out to be the key to avoiding the formation of copper hydroxide sideproducts. Based on the use of the optimized syntheses parameters, the preparation of layered triple and multiple hydroxides was also attempted using Ni(II), Co(II), Zn(II) and even Mg(II) ions. These studies let us identify the relative positions of the incorporating cations in the well-known selectivity series as Ni2+ >> Cu2+ >> Zn2+ > Co2+ >> Mg2+. The solids formed were characterized by using powder X-ray diffractometry, UV-Vis diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. The catalytic potential of the samples was investigated in carbon monoxide oxidation reactions at atmospheric pressure, supported by an in situ diffuse reflectance infrared spectroscopy probe. All solids proved to be active and the combination of the nickel and cobalt incorporation (which resulted in a NiCoAl8 layered triple hydroxide) brought outstanding benefits regarding low-temperature oxidation and increased carbon monoxide conversion values.

The Effect of the Reducing Sugars in the Synthesis of Visible-Light-Active Copper(I) Oxide Photocatalyst.

In the present work, shape tailored Cu2O microparticles were synthesized by changing the nature of the reducing agent and studied subsequently. d-(+)-glucose, d-(+)-fructose, d-(+)xylose, d-(+)-galactose, and d-(+)-arabinose were chosen as reducing agents due to their different reducing abilities. The morpho-structural characteristics were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS), while their photocatalytic activity was evaluated by methyl orange degradation under visible light (120 min). The results show that the number of carbon atoms in the sugars affect the morphology and particle size (from 250 nm to 1.2 µm), and differences in their degree of crystallinity and photocatalytic activity were also found. The highest activity was observed when glucose was used as the reducing agent.

Mechanistic insight of structural and optical properties of BiOCl in the presence of CNTs and investigating photodegradation of phenol by BiOCl/CNT composites.

In this work, we have synthesized composites of BiOCl with carbon nanotubes (CNTs) via a hydrothermal method. Different compositions of CNTs were used to study their influence on the physicochemical properties of BiOCl. Based on the interesting results obtained, various significant correlations were made. This study explored how use of CNTs and different hydrothermal crystallization conditions can influence the photocatalytic activity of composites. The CNTs have an impact on the primary crystallite size and morphology of BiOCl. Also, a higher degree of crystallization was obtained in the case of samples containing CNTs. However, in some cases, the synthesis parameters such as high temperature and longer duration also promoted crystallinity in BiOCl/CNT samples. Further, the samples were investigated for their photocatalytic activity to study the photodegradation of RhB and phenol, as model pollutants, under visible and UV light, respectively. The maximum degradation efficiency of 83% for RhB under visible light and almost 40% for phenol under UV light was obtained using BiOCl/CNT composites. Surprisingly, pure BiOCl showed higher performance for the removal of both the pollutants. This is why some comparisons and correlations between the structural and optical properties of BiOCl and CNTs were made. Finally, this study illustrates how a nanostructure like conductive multiwalled carbon nanotubes can sometimes have detrimental effects on the overall photocatalytic properties of a photocatalyst like BiOCl under certain conditions. Therefore, understanding the synergy between physico-chemical properties of BiOCl and nanostructured-modifiers like CNTs could help in designing a photocatalyst system which could benefit wastewater treatment.

Utilization of Carbon Nanospheres in Photocatalyst Production: From Composites to Highly Active Hollow Structures.

Titanium dioxide-carbon sphere (TiO2-CS) composites were constructed via using prefabricated carbon spheres as templates. By the removal of template from the TiO2-CS, TiO2 hollow structures (HS) were synthesized. The CS templates were prepared by the hydrothermal treatment of ordinary table sugar (sucrose). TiO2-HSs were obtained by removing CSs with calcination. Our own sensitized TiO2 was used for coating the CSs. The structure of the CSs, TiO2-CS composites, and TiO2-HSs were characterized by scanning electron microscopy (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectroscopy (DRS). The effect of various synthesis parameters (purification method of CSs, precursor quantity, and applied furnace) on the morphology was investigated. The photocatalytic activity was investigated by phenol model pollutant degradation under visible light irradiation (λ > 400 nm). It was established that the composite samples possess lower crystallinity and photocatalytic activity compared to TiO2 hollow structures. Based on XPS measurements, the carbon content on the surface of the TiO2-HS exerts an adverse effect on the photocatalytic performance. The synthesis parameters were optimized and the TiO2-HS specimen having the best absolute and surface normalized photocatalytic efficiency was identified. The superior properties were explained in terms of its unique morphology and surface properties. The stability of this TiO2-HS was investigated via XRD and SEM measurements after three consecutive phenol degradation tests, and it was found to be highly stable as it entirely retained its crystal phase composition, morphology and photocatalytic activity.

Gold Size Effect in the Thermal-Induced Reaction of CO2 and H2 on Titania- and Titanate Nanotube-Supported Gold Catalysts.

In this paper, we study the thermal activation of CO2 on the surface of small Au nanoparticles supported on TiO2 and titanate nanotube. We characterize the catalysts with high resolution transmission electron microscopy (HR-TEM) and total gold content measurement. We performed catalytic test in flow reactors then we investigate the surface of the catalysts during the adsorption and reaction processes by diffuse reflectance infrared spectroscopy (DRIFTS). The size of gold nanoparticles on the surface has been found to have the most important effect on the final activity of the studied catalysts. Significantly higher TOF values were obtained when the size of Au were smaller on both TiO2 and titanate nanotube supports. The size of the Au nanoparticles with the method of their preparation was controlled. The gold adatom promotes the adsorption and scission of CO2, but the nature of the support has got important effect, too. The explored reaction schemes may pave the way towards novel catalytic materials that can solve challenges associated with the activation of CO2 and thus contribute to a greener chemistry related to it.

Stability and Temperature-Induced Agglomeration of Rh Nanoparticles Supported by CeO2.

The effects of reduction by H2 and by heat treatment in vacuum and in O2 flow on Rh particle size changes of Rh/CeO2 samples were studied by X-ray photoelectron spectroscopy (XPS), high-resolution electron microscopy (HRTEM), and CO adsorption followed by diffuse reflectance infrared spectroscopy (DRIFTS). Low-temperature (373-423 K) reduction of Rh without agglomeration is demonstrated. An average particle size of 2.3 ± 1.1 nm was measured by HRTEM regardless of the metal loading (1-5%). On Rh/CeO2, a significant particle size increase of the Rh particles was detected on heating (773 K). In this work, we suggest that the temperature-induced surface decrease resulting from the sintering of Rh is favored only for well-dispersed particles. XP spectra revealed that the mobile oxygens of CeO2 fundamentally determine the oxidation state of the supported metals. At elevated temperature, the oxidation of the reduced support surface as well as the metal component takes place because of the segregation of ceria oxygens. When the aggregated particles were reoxidized, the redispersion of Rh was observed probably because of the formation of Rh-O-Ce bonds.