Direct observation of atomically-resolved silver species on a silver alumina catalyst active for selective catalytic reduction of nitrogen oxides

We characterize the size and state of the silver species in a 2 wt% silver alumina catalyst, which is highly active for the selective catalytic reduction of nitrogen oxides with ammonia or hydrocarbons as reductant. The silver alumina catalyst is prepared by a single-step sol-gel method and characterized with X-ray photoelectron and ultraviolet-visible spectroscopy, and high-resolution transmission electron microscopy. We show, for the first time, direct observations of atomically-resolved silver species and silver clusters on the silver alumina catalyst. The results determine the existence of these silver species on the alumina support, which corroborate previously reported indirect observations, and strengthen the hypothesis of small silver clusters as active sites for the selective catalytic reduction of nitrogen oxides

Plasmonic Temperature-Programmed Desorption

Temperature-programmed desorption (TPD) allows for the determination of the bonding strength and coverage of molecular mono- or multilayers on a surface and is widely used in surface science. In its traditional form using a mass spectrometric readout, this information is derived indirectly by analysis of resulting desorption peaks. This is problematic because the mass spectrometer signal not only originates from the sample surface but also potentially from other surfaces in the measurement chamber. As a complementary alternative, we introduce plasmonic TPD, which directly measures the surface coverage of molecular species adsorbed on metal nanoparticles at ultrahigh vacuum conditions. Using the examples of methanol and benzene on Au nanoparticle surfaces, the method can resolve all relevant features in the submonolayer and multilayer regimes. Furthermore, it enables the study of two types of nanoparticles simultaneously, which is challenging in a traditional TPD experiment, as we demonstrate specifically for Au and Ag

Synthesis and Characterization of Catalytically Active Au Core─Pd Shell Nanoparticles Supported on Alumina

A two-step seeded-growth method was refined to synthesize Au@Pd core@shell nanoparticles with thin Pd shells, which were then deposited onto alumina to obtain a supported Au@Pd/Al2O3 catalyst active for prototypical CO oxidation. By the strict control of temperature and Pd/Au molar ratio and the use of l-ascorbic acid for making both Au cores and Pd shells, a 1.5 nm Pd layer is formed around the Au core, as evidenced by transmission electron microscopy and energy-dispersive spectroscopy. The core@shell structure and the Pd shell remain intact upon deposition onto alumina and after being used for CO oxidation, as revealed by additional X-ray diffraction and X-ray photoemission spectroscopy before and after the reaction. The Pd shell surface was characterized with in situ infrared (IR) spectroscopy using CO as a chemical probe during CO adsorption-desorption. The IR bands for CO ad-species on the Pd shell suggest that the shell exposes mostly low-index surfaces, likely Pd(111) as the majority facet. Generally, the IR bands are blue-shifted as compared to conventional Pd/alumina catalysts, which may be due to the different support materials for Pd, Au versus Al2O3, and/or less strain of the Pd shell. Frequencies obtained from density functional calculations suggest the latter to be significant. Further, the catalytic CO oxidation ignition-extinction processes were followed by in situ IR, which shows the common CO poisoning and kinetic behavior associated with competitive adsorption of CO and O2 that is typically observed for noble metal catalysts

N2O Formation during NH3-SCR over Different Zeolite Frameworks: Effect of Framework Structure, Copper Species, and Water

The formation characteristics of N2O were investigated with respect to copper-functionalized zeolites, i.e., Cu/SSZ-13 (CHA), Cu/ZSM-5 (MFI), and Cu/BEA (BEA) and compared with the corresponding zeolites in the H form as references to elucidate the effect of the framework structure, copper addition, and water. Temperature-programmed reduction with hydrogen showed that the CHA framework has a higher concentration of Cu2+ (Z2Cu) compared to MFI and BEA. The characterizations and catalyst activity results highlight that CHA has a framework structure that favors high formation of ammonium nitrate (AN) in comparison with MFI and BEA. Moreover, AN formation and decomposition were found to be promoted in the presence of Cu species. On the contrary, lower N2O formation was observed from Cu/CHA during standard and fast SCR reactions, which is proposed to be due to highly stabilized AN inside the zeolite cages. On the other hand, significant amounts of N2O were released during heating due to decomposition of AN, implying pros and cons of AN stability for Cu/CHA with possible uncontrolled N2O formation during transient conditions. Additionally, important effects of water were found, where water hinders AN formation and increases the selectivity for decomposition to NO2 instead of N2O. Thus, less available AN forming N2O was observed in the presence of water. This was also observed in fast SCR conditions where all Cu/zeolites exhibited lower continuous N2O formation in the presence of water

Surface species and metal oxidation state during H2‐assisted NH3‐SCR of NOx over alumina‐supported silver and indium

Alumina‐supported silver and indium catalysts are investigated for the hydrogen‐assisted selective catalytic reduction (SCR) of NO x with ammonia. Particularly, we focus on the active phase of the catalyst and the formation of surface species, as a function of the gas environment. Diffuse reflectance ultraviolet‐visible (UV‐vis) spectroscopy was used to follow the oxidation state of the silver and indium phases, and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to elucidate the formation of surface species during SCR conditions. In addition, the NO x reduction efficiency of the materials was evaluated using H 2 ‐assisted NH 3 ‐SCR. The DRIFTS results show that the Ag/Al 2 O 3 sample forms NO‐containing surface species during SCR conditions to a higher extent compared to the In/Al 2 O 3 sample. The silver sample also appears to be more reduced by H 2 than the indium sample, as revealed by UV‐vis spectroscopic experiments. Addition of H 2 , however, may promote the formation of highly dispersed In 2 O 3 clusters, which previously have been suggested to be important for the SCR reaction. The affinity to adsorb NH 3 is confirmed by both temperature programmed desorption (NH 3 ‐TPD) and in situ DRIFTS to be higher for the In/Al 2 O 3 sample compared to Ag/Al 2 O 3 . The strong adsorption of NH 3 may inhibit (self‐poison) the NH 3 activation, thereby hindering further reaction over this catalyst, which is also shown by the lower SCR activity compared to Ag/Al 2 O 3

Selective Photocatalytic Reduction of CO2-to-CO in Water using a Polymeric Carbon Nitride Quantum Dot/Fe-Porphyrin Hybrid Assembly

Visible light-driven conversion of CO2 into more value-added products is a promising technology not only for diminution of CO2 emission but also for solar energy storage in the form of chemical energy. However, photocatalytic materials that can efficiently and selectively reduce CO2-to-CO in a fully aqueous solution typically involve precious metals that limit their suitability for large scale applications. Herein, a novel photocatalytic assembly is reported, consisting of polymeric carbon nitride quantum dots (CNQDs) as the visible light absorber and a Fe-porphyrin complex (Fe-p-TMA) as the catalyst for CO2-to-CO conversion. Both components were carefully selected to allow for excellent solubility in water as well as improved electronic communication through complementary electrostatic and π-π interactions. This CNQD ⋅ [Fe-p-TMA] hybrid assembly, at the optimized molar ratio, can produce CO with a turnover number (TON) exceeding 105 and selectivity ∼96 % after 10 hours of visible light irradiation (400–700 nm). It is postulated that the enhanced CO2-to-CO transformation performance is due to the convenience of a more direct charge transfer (CT) pathway between the CNQDs and [Fe-p-TMA] motif

Synthesis of highly monodisperse Pd nanoparticles using a binary surfactant combination and sodium oleate as a reductant

This study presents the synthesis of monodisperse Pd nanoparticles (NPs) stabilized by sodium oleate (NaOL) and hexadecyltrimethylammonium chloride (CTAC). The synthesis was conducted without traditional reductants and Pd-precursors are reduced by NaOL. It was confirmed that the alkyl double bond in NaOL is not the only explanation for the reduction of Pd-precursors since Pd NPs could be synthesized with CTAC and the saturated fatty acid sodium stearate (NaST). A quantitative evaluation of the reduction kinetics using UV-Vis spectroscopy shows that Pd NPs synthesized with both stabilizer combinations follow pseudo first-order reaction kinetics, where NaOL provides a faster and more effective reduction of Pd-precursors. The colloidal stabilization of the NP surface by CTAC and NaOL is confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) analysis

In situ DRIFT studies on N2O formation over Cu-functionalized zeolites during ammonia-SCR

The influence of the zeolite framework structure on the formation of N2O during ammonia-SCR of NOx was studied for three different copper-functionalized zeolite samples, namely Cu-SSZ-13 (CHA), Cu-ZSM-5 (MFI), and Cu-BEA (BEA). The evolution of surface species during the SCR reaction at different temperatures was monitored with step-response experiments using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) at different reaction conditions. Also, density functional theory (DFT) calculations were performed to assist the interpretation of the experimental results. The DRIFTS results indicate that NO+ and nitrate species are the main products formed during NO oxidation, and NO appears to adsorb on both Cu-Lewis and Al-Lewis acid sites. The DFT calculations for NO adsorption on the SSZ-13 sample reveal adsorption at Bronsted acid sites with similar adsorption energies but with a slight difference in NO+ stretching vibrations in the DRIFT spectra. Within the standard SCR reaction, in the O-H stretching region, the number of NH3 molecules adsorbed on the Bronsted acid sites is higher for the small-pore size sample compared to the medium- and large-pore zeolites. The obtained DRIFTS results for nitrate species are supported by DFT calculations by simulating the IR spectra of mobile and framework bound nitrate species, which both have a signature at 1604 cm(-1) associated with the O-N bond on NO3-. It is revealed that N2O is produced in a higher amount at lower temperatures for all three samples irrespective of the NO/NO2 ratio. Furthermore, the obtained results from both DRIFTS studies and flow reactor experiments show the higher formation of N2O for the large-pore zeolite compared to the medium- and small-pore zeolite

Methane Adsorption and Methanol Desorption for Copper Modified Boron Silicate

Boron silicate (BS) with a chabazite framework structure was synthesised using a direct route and rigorously characterized before it was ion-exchanged with copper to form Cu-BS. Employing in situ infrared spectroscopy, we show that Cu-BS is capable of oxidising methane to methoxy species and methanol interacts with the boron sites without deprotonation