scholarly journals Cold Plasma Synthesis and Testing of NiOX-Based Thin-Film Catalysts for CO2 Methanation

Catalysts ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 905
Author(s):  
Martyna Smolarek ◽  
Hanna Kierzkowska-Pawlak ◽  
Ryszard Kapica ◽  
Maciej Fronczak ◽  
Maciej Sitarz ◽  
...  

An essential problem in managing CO2 and transforming it into methane as a useful fuel is the quest for adequately efficient and cheap catalysts. Another condition is imposed by the new designs of structured reactors, which require catalysts in the form of the thinnest possible films. The aim of this work was to produce Ni-based thin-film catalysts by the cold plasma deposition method (PECVD) from a volatile metal complex (Ni(CO)4) and to study their structure and catalytic properties in the CO2 methanation process. We tested three basic types of films: as-deposited, calcined in Ar, and calcined in air. The nanostructure and molecular structure of the films were investigated by electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The catalytic activity was evaluated in the methanation process (CO2 + H2), which was performed in a tubular reactor operating in the temperature range of 300–400 °C. The films calcined in air showed the highest activity in this process but behaved unstably. However, their regeneration by recalcination in air restored the initial catalytic activity. An important conclusion emerged from the obtained results, namely that the active phase in the tested films is Ni3+ (most likely in the form of Ni2O3), contrary to the common opinion that this phase is metallic Ni0. In our case, Ni0 quenches the catalytic activity.

Nanomaterials ◽  
2019 ◽  
Vol 9 (10) ◽  
pp. 1432 ◽  
Author(s):  
Weiwei Xu ◽  
Mengyue Dong ◽  
Lanbo Di ◽  
Xiuling Zhang

With increasing applications of metal-organic frameworks (MOFs) in the field of gas separation and catalysis, the preparation and performance research of encapsulating metal nanoparticles (NPs) into MOFs (M@MOF) have attracted extensive attention recently. Herein, an Ru@UiO-66 catalyst is prepared by a one-step method. Ru NPs are encapsulated in situ in the UiO-66 skeleton structure during the synthesis of UiO-66 metal-organic framework via a solvothermal method, and its catalytic activity for CO2 methanation with the synergy of cold plasma is studied. The crystallinity and structural integrity of UiO-66 is maintained after encapsulating Ru NPs according to the X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). As illustrated by X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), and mapping analysis, the Ru species of the hydration ruthenium trichloride precursor are reduced to metallic Ru NPs without additional reducing processes during the synthesis of Ru@UiO-66, and the Ru NPs are uniformly distributed inside the Ru@UiO-66. Thermogravimetric analysis (TGA) and N2 sorption analysis show that the specific surface area and thermal stability of Ru@UiO-66 decrease slightly compared with that of UiO-66 and was ascribed to the encapsulation of Ru NPs in the UiO-66 skeleton. The results of plasma-assisted catalytic CO2 methanation indicate that Ru@UiO-66 exhibits excellent catalytic activity. CO2 conversion and CH4 selectivity over Ru@UiO-66 reached 72.2% and 95.4% under 13.0 W of discharge power and a 30 mL·min−1 gas flow rate ( V H 2 : V C O 2 = 4 : 1 ), respectively. Both values are significantly higher than pure UiO-66 with plasma and Ru/Al2O3 with plasma. The enhanced performance of Ru@UiO-66 is attributed to its unique framework structure and excellent dispersion of Ru NPs.


Polymers ◽  
2021 ◽  
Vol 13 (3) ◽  
pp. 478
Author(s):  
Wan Mohd Ebtisyam Mustaqim Mohd Daniyal ◽  
Yap Wing Fen ◽  
Silvan Saleviter ◽  
Narong Chanlek ◽  
Hideki Nakajima ◽  
...  

In this study, X-ray photoelectron spectroscopy (XPS) was used to study chitosan–graphene oxide (chitosan–GO) incorporated with 4-(2-pyridylazo)resorcinol (PAR) and cadmium sulfide quantum dot (CdS QD) composite thin films for the potential optical sensing of cobalt ions (Co2+). From the XPS results, it was confirmed that carbon, oxygen, and nitrogen elements existed on the PAR–chitosan–GO thin film, while for CdS QD–chitosan–GO, the existence of carbon, oxygen, cadmium, nitrogen, and sulfur were confirmed. Further deconvolution of each element using the Gaussian–Lorentzian curve fitting program revealed the sub-peak component of each element and hence the corresponding functional group was identified. Next, investigation using surface plasmon resonance (SPR) optical sensor proved that both chitosan–GO-based thin films were able to detect Co2+ as low as 0.01 ppm for both composite thin films, while the PAR had the higher binding affinity. The interaction of the Co2+ with the thin films was characterized again using XPS to confirm the functional group involved during the reaction. The XPS results proved that primary amino in the PAR–chitosan–GO thin film contributed more important role for the reaction with Co2+, as in agreement with the SPR results.


2011 ◽  
Vol 2 ◽  
pp. 593-606 ◽  
Author(s):  
Matthias Roos ◽  
Dominique Böcking ◽  
Kwabena Offeh Gyimah ◽  
Gabriela Kucerova ◽  
Joachim Bansmann ◽  
...  

Aiming at model systems with close-to-realistic transport properties, we have prepared and studied planar Au/TiO2 thin-film model catalysts consisting of a thin mesoporous TiO2 film of 200–400 nm thickness with Au nanoparticles, with a mean particle size of ~2 nm diameter, homogeneously distributed therein. The systems were prepared by spin-coating of a mesoporous TiO2 film from solutions of ethanolic titanium tetraisopropoxide and Pluronic P123 on planar Si(100) substrates, calcination at 350 °C and subsequent Au loading by a deposition–precipitation procedure, followed by a final calcination step for catalyst activation. The structural and chemical properties of these model systems were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption, inductively coupled plasma ionization spectroscopy (ICP–OES) and X-ray photoelectron spectroscopy (XPS). The catalytic properties were evaluated through the oxidation of CO as a test reaction, and reactivities were measured directly above the film with a scanning mass spectrometer. We can demonstrate that the thin-film model catalysts closely resemble dispersed Au/TiO2 supported catalysts in their characteristic structural and catalytic properties, and hence can be considered as suitable for catalytic model studies. The linear increase of the catalytic activity with film thickness indicates that transport limitations inside the Au/TiO2 film catalyst are negligible, i.e., below the detection limit.


2016 ◽  
Vol 73 (11) ◽  
pp. 2747-2753 ◽  
Author(s):  
Wusong Kong ◽  
Hongxia Qu ◽  
Peng Chen ◽  
Weihua Ma ◽  
Huifang Xie

In this study, Cu2O-CuO/ZSM-5 nanocomposite was synthesized by the impregnation method, and its catalytic performance for the destruction of AO7 in aqueous solutions was investigated. The morphology, structure and surface element valence state of Cu2O-CuO/ZSM-5 were characterized by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The operating conditions on the degradation of AO7 by Cu2O-CuO/ZSM-5, such as initial pH values, concentration of AO7 and catalyst dosage were investigated and optimized. The results showed that the sample had good catalytic activity for destruction of AO7 in the absence of a sacrificial agent (e.g. H2O2): it could degrade 91% AO7 in 140 min at 25 °C and was not restricted by the initial pH of the AO7 aqueous solutions. Cu2O-CuO/ZSM-5 exhibited stable catalytic activity with little loss after three successive runs. The total organic carbon and chemical oxygen demand removal efficiencies increased rapidly to 69.36% and 67.3% after 120 min of treatment by Cu2O-CuO/ZSM-5, respectively.


2019 ◽  
Vol 26 (5) ◽  
pp. 1600-1611 ◽  
Author(s):  
Gihan Kwon ◽  
Yeong-Ho Cho ◽  
Ki-Bum Kim ◽  
Jonathan D. Emery ◽  
In Soo Kim ◽  
...  

Porous, high-surface-area electrode architectures are described that allow structural characterization of interfacial amorphous thin films with high spatial resolution under device-relevant functional electrochemical conditions using high-energy X-ray (>50 keV) scattering and pair distribution function (PDF) analysis. Porous electrodes were fabricated from glass-capillary array membranes coated with conformal transparent conductive oxide layers, consisting of either a 40 nm–50 nm crystalline indium tin oxide or a 100 nm–150 nm-thick amorphous indium zinc oxide deposited by atomic layer deposition. These porous electrodes solve the problem of insufficient interaction volumes for catalyst thin films in two-dimensional working electrode designs and provide sufficiently low scattering backgrounds to enable high-resolution signal collection from interfacial thin-film catalysts. For example, PDF measurements were readily obtained with 0.2 Å spatial resolution for amorphous cobalt oxide films with thicknesses down to 60 nm when deposited on a porous electrode with 40 µm-diameter pores. This level of resolution resolves the cobaltate domain size and structure, the presence of defect sites assigned to the domain edges, and the changes in fine structure upon redox state change that are relevant to quantitative structure–function modeling. The results suggest the opportunity to leverage the porous, electrode architectures for PDF analysis of nanometre-scale surface-supported molecular catalysts. In addition, a compact 3D-printed electrochemical cell in a three-electrode configuration is described which is designed to allow for simultaneous X-ray transmission and electrolyte flow through the porous working electrode.


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