GaPt Supported Catalytically Active Liquid Metal Solution Catalysis for Propane Dehydrogenation–Support Influence and Coking Studies
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ABSTRACT:
SUBMITTER: Raman N
PROVIDER: S-EPMC8576810 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Our contribution demonstrates that rhodium, an element that has barely been reported as an active metal for selective dehydrogenation of alkanes becomes a very active, selective, and robust dehydrogenation catalyst when exposed to propane in the form of single atoms at the interface of a solid-supported, highly dynamic liquid Ga-Rh mixture. We demonstrate that the transition to a fully liquid supported alloy droplet at Ga/Rh ratios above 80, results in a drastic increase in catalyst activity with high propylene selectivity. The combining results from catalytic studies, X-ray photoelectron spectroscopy, IR-spectroscopy under reaction conditions, microscopy, and density-functional theory calculations, we obtained a comprehensive microscopy picture of the working principle of the Ga-Rh supported catalytically active liquid metal solution.
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Project description:Supported Catalytically Active Liquid Metal Solutions (SCALMS) were recently described as a new class of heterogeneous catalysts, where the catalytic transformation takes place at the highly dynamic interface of a liquid alloy. Their application in alkane dehydrogenation has been claimed to be superior to classical heterogeneous catalysts, because the single atom nature of Rh dissolved in liquid Ga hinders the formation of significant amounts of coke, e.?g. by oligomerisation of carbon fragments and excessive dehydrogenation. In the present study, we investigate the coking behaviour of Ga-Rh SCALMS during dehydrogenation of propane in detail by means of high-resolution thermogravimetry. We report that the application of Ga-Rh SCALMS indeed limits the formation of coke when compared to the Ga-free Rh catalyst, in particular when relating coke formation to the catalytic performance. Furthermore, the formed coke has been shown to be highly reactive during temperature programmed oxidation in 21?% O2/He with onset temperatures of approx. 150?°C enabling a regeneration of the Ga-Rh SCALMS system under mild conditions. The activation energy of the oxidation lies in the lower range of values reported for spent cracking catalysts. Monitoring the formation of coke and performance of SCALMS in?situ via thermogravimetry coupled with mass spectrometry revealed the continuous formation of coke, which becomes the only process affecting the net weight change after a certain time on stream.
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Project description:Zr-based metal-organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in the two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.
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Project description:Non-precious metal supported catalytically active liquid metal solutions exhibit attractive performance in ethylene oligomerization. It is found for the Ga-Ni system on silica that the performance depends strongly on the applied Ga/Ni ratio. Ga-rich systems forming liquid alloys exhibit a far higher Ni-based catalytic activity than solid intermetallic compounds or Ni nanoparticles.
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Project description:Gallium-rich supported catalytically active liquid metal solutions (SCALMS) were recently introduced as a new way towards heterogeneous single atom catalysis. SCALMS were demonstrated to exhibit a certain resistance against coking during the dehydrogenation of alkanes using Ga-rich alloys of noble metals. Here, the conceptual catalytic application of SCALMS in dry reforming of methane (DRM) is tested with non-noble metal (Co, Cu, Fe, Ni) atoms in the gallium-rich liquid alloy. This study introduces SCALMS to high-temperature applications and an oxidative reaction environment. Most catalysts were shown to undergo severe oxidation during DRM, while Ga-Ni SCALMS retained a certain level of activity. This observation is explained by a kinetically controlled redox process, namely oxidation to gallium oxide species and re-reduction via H2 activation over Ni. Consequentially, this redox process can be shifted to the metallic side when using increasing concentrations of Ni in Ga, which strongly suppresses coke formation. Density-functional theory (DFT) based ab initio molecular dynamics (AIMD) simulations were performed to confirm the increased availability of Ni at the liquid alloy-gas interface. However, leaching of gallium via the formation of volatile oxidic species during the hypothesised redox cycles was identified indicating a critical instability of Ga-Ni SCALMS for prolonged test durations.
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Project description:Propane Dehydrogenation is a key technology, where Pt-based catalysts have widely been investigated in industry and academia, with development exploring the use of promoters (Sn, Zn, Ga, etc.) and additives (Na, K, Ca, Si, etc.) towards improved catalytic performances. Recent studies have focused on the role of Ga promotion: while computations suggest that Ga plays a key role in enhancing catalytic selectivity and stability of PtGa catalysts through Pt-site isolation as well as morphological changes, experimental evidence are lacking because of the use of oxide supports that prevent more detailed investigation. Here, we develop a methodology to generate Pt and PtGa nanoparticles with tailored interfaces on carbon supports by combining surface organometallic chemistry (SOMC) and specific thermolytic molecular precursors containing or not siloxide ligands. This approach enables the preparation of supported nanoparticles, exhibiting or not an oxide interface, suitable for state-of-the art electron microscopy and XANES characterization. We show that the introduction of Ga enables the formation of homogenously alloyed, amorphous PtGa nanoparticles, in sharp contrast to highly crystalline monometallic Pt nanoparticles. Furthermore, the presence of an oxide interface is shown to stabilize the formation of small particles, at the expense of propene selectivity loss (formation of cracking side-products, methane/ethene), explaining the use of additives such as Na, K and Ca in industrial catalysts.
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Project description:Supported catalytically active liquid metal solutions (SCALMS) represent a class of catalytic materials that have only recently been developed, but have already proven to be highly active, e.g., for dehydrogenation reactions. Previous studies attributed the catalytic activity to isolated noble metal atoms at the surface of a liquid and inert Ga matrix. In this study, we apply diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with CO as a probe molecule to Ga/Al2O3, Pt/Al2O3, and Ga37Pt/Al2O3 catalysts, to investigate in detail the nature of the active Pt species. Comparison of CO adsorption on Pt/Al2O3 and Ga37Pt/Al2O3 shows that isolated Pt atoms are, indeed, present at the surface of the liquid SCALMS. Combining DRIFTS with online gas chromatography (GC), we investigated the Ga/Al2O3, Pt/Al2O3, and Ga37Pt/Al2O3 systems under operando conditions during propane dehydrogenation in CO/propane and in Ar/propane. We find that the Pt/Al2O3 sample is rapidly poisoned by CO adsorption and coke, whereas propane dehydrogenation over Ga37Pt/Al2O3 SCALMS leads to higher conversion with no indication of poisoning effects. We show under operando conditions that isolated Pt atoms are present at the surface of SCALMS during the dehydrogenation reaction. IR spectra and density-functional theory (DFT) suggest that both the Ga matrix and the presence of coadsorbates alter the electronic properties of the surface Pt species.
| S-EPMC7252903 | biostudies-literature
Project description:A novel GaPt-based supported catalytically active liquid metal solution (SCALMS) material is developed by exploiting the suprabead concept: Supraparticles, i.e. micrometer-sized particles composed of nanoparticles assembled by spray-drying, are bonded to millimeter-sized beads. The suprabeads combine macroscale size with catalytic properties of nanoscale GaPt particles entrapped in their silica framework.
| S-EPMC10615327 | biostudies-literature
Project description:PtCu single-atom alloys (SAAs) open an extensive prospect for heterogeneous catalysis. However, as the host of SAAs, Cu suffers from severe sintering at elevated temperature, resulting in poor stability of catalysts. This paper describes the suppression of the agglomeration of Cu nanoparticles under high temperature conditions using copper phyllosilicate (CuSiO3) as the support of PtCu SAAs. Based on quasi in situ XPS, in situ CO-DRIFTS, in situ Raman spectroscopy and in situ XRD, we demonstrated that the interfacial Cu+-O-Si formed upon reduction at 680 °C serves as the adhesive between Cu nanoparticles and the silicon dioxide matrix, strengthening the metal-support interaction. Consequently, the resistance to sintering of PtCu SAAs was improved, leading to high catalytic stability during propane dehydrogenation without sacrificing conversion and selectivity. The optimized PtCu SAA catalyst achieved more than 42% propane conversion and 93% propylene selectivity at 580 °C for at least 30 hours. It paves a way for the design and development of highly active supported single-atom alloy catalysts with excellent thermal stability.
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Project description:Single-site gallium centers on the surface of silica are prepared via grafting of [Ga(OSi(OtBu)3)3(THF)] on SiO2-700 followed by a thermolysis step. The resulting surface species corresponds to well-defined tetra-coordinate gallium single-sites, [([triple bond, length as m-dash]SiO)3Ga(XOSi[triple bond, length as m-dash])] (X = -H or [triple bond, length as m-dash]Si) according to IR, X-ray absorption near-edge structure and extended X-ray absorption fine structure analysis. These gallium sites show high activity, selectivity and stability for propane dehydrogenation with an initial turnover frequency of 20 per h per gallium center, propylene selectivity of ≥93% and remarkable stability over 20 h. The stability of the catalyst probably results from site-isolation of the active site on a non-reducible support such as silica, diminishing facile reduction typical of Ga2O3-based catalysts.
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