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1. Nanoshaped CeO2 and SiO2 Supported Ru catalyst for Plasma Catalysis Chemical Looping Reactions

   Rajagopalan, Ranganathan; Zhongqi, Liu; Harigovind, Menon; Shaon, Talukdar; Ruigang, Wang; Mruthunjaya, Uddi (November 2020, International journal of energy engineering)

   null (Ed.)

   Chemical Looping Reaction is a key strategy to achieve both emission reduction and carbon utilization while producing various value-added chemicals, through redox reactions. Here we study the effect of nanoshape ceria supported Ru catalysts for plasma assisted Chemical Looping Reforming reduction step coupled with water splitting oxidation step reactions in the temperature range 150 ⁰C to 400 ⁰C at 1 atm pressure. The oxygen carrier/catalyst combination materials used are Ru/CeO2 nanorods (NR), Ru/CeO2 nanocubes (NC), Ru/SiO2 nanospheres (NS), and Ni-based perovskite mixed with CeO2. NRs and NCs showed the best catalytic performance followed by Ni-based perovskite and NS. Differences in the selectivity and reactivity for the NRs and NCs were noticed. The NCs showed slightly higher selectivity towards H2 formation during reduction step and lesser carbon deposition. From the analysis of data and literature, it is proposed that the spillover of species such as H adatoms and CHx radicals after activation at Ru sites into the CeO2 supports and lattice O mobility may be slightly faster in the case of NCs. During the oxidation step, the NR and NC materials showed increased H2 production by a factor of more than 4 when compared to Ni based perovskite material. 

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2. Acetylene hydrogenation catalyzed by bare and Ni doped CeO ₂ (110): the role of frustrated Lewis pairs

   https://doi.org/10.1039/D2CP00925K  

   Zhou, Shulan; Wan, Qiang; Lin, Sen; Guo, Hua (May 2022, Physical Chemistry Chemical Physics)

   Ceria (CeO 2 ) has recently been found to catalyze the selective hydrogenation of alkynes, which has stimulated much discussion on the catalytic mechanism on various facets of reducible oxides. In this work, H 2 dissociation and acetylene hydrogenation on bare and Ni doped CeO 2 (110) surfaces are investigated using density functional theory (DFT). Similar to that on the CeO 2 (111) surface, our results suggest that catalysis is facilitated by frustrated Lewis pairs (FLPs) formed by oxygen vacancies (O v s) on the oxide surfaces. On bare CeO 2 (110) with a single O v (CeO 2 (110)–O v ), two surface Ce cations with one non-adjacent O anion are shown to form (Ce 3+ –Ce 4+ )/O quasi-FLPs, while for the Ni doped CeO 2 (110) surface with one (Ni–CeO 2 (110)–O v ) or two (Ni–CeO 2 (110)–2O v ) O v s, one Ce and a non-adjacent O counterions are found to form a mono-Ce/O FLP. DFT calculations indicate that Ce/O FLPs facilitate the H 2 dissociation via a heterolytic mechanism, while the resulting surface O–H and Ce–H species catalyze the subsequent acetylene hydrogenation. With CeO 2 (110)–O v and Ni–CeO 2 (110)–2O v , our DFT calculations suggest that the first hydrogenation step is the rate-determining step with a barrier of 0.43 and 0.40 eV, respectively. For Ni–CeO 2 (110)–O v , the reaction is shown to be controlled by the H 2 dissociation with a barrier of 0.41 eV. These barriers are significantly lower than that (about 0.7 eV) on CeO 2 (111), explaining the experimentally observed higher catalytic efficiency of the (110) facet of ceria. The change of the rate-determining step is attributed to the different electronic properties of Ce in the Ce/O FLPs – the Ce f states closer to the Fermi level not only facilitate the heterolytic dissociation of H 2 but also lead to a higher barrier of acetylene hydrogenation. 

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3. First-principles microkinetic modeling of partial methane oxidation over graphene-stabilized single-atom Fe-catalysts

   https://doi.org/10.1039/D3CY01335A  

   Hong, Sungil; Kauppinen, Minttu M.; Miu, Evan V.; Mpourmpakis, Giannis; Grönbeck, Henrik (December 2023, Catalysis Science & Technology)

   Catalytic conversion of CH4 to transportable liquid hydrocarbons via partial oxidation is a promising avenue towards efficient utilization of natural gas. Single Fe atoms on N-functionalized graphene (FeN4/GN) have recently been shown to be active for partial CH4 oxidation with H2O2 at room temperature. Here, density functional theory (DFT) calculations combined with mean-field microkinetic modeling (MKM) have been applied to obtain kinetic understanding of partial CH4 oxidation with H2O2 to CH3OH and CH3OOH over FeN4/GN. CH3OH and CH3OOH are found to be minor and major reaction products, respectively, with a selectivity in agreement with reported experimental data. The kinetic modeling reveals two pathways for CH3OH production together with a dominant catalytic cycle for CH3OOH formation. The selectivity is found to be sensitive to the temperature and H2O2 concentration, with the CH3OH selectivity increasing with increasing temperature and decreasing H2O2 concentration. Turnover frequencies of both CH3OH and CH3OOH are found to decrease over time, due to a change in the Fe formal oxidation state from +6 to +4; Fe(+6) is more active, but less stable than Fe(+4). The present work unravels the detailed reaction mechanism for partial oxidation of methane by FeN4/GN, rationalizes experimental observations and provides guidance for efficient room-temperature methane conversion by single-atom Fe-catalysts. 

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4. Redox-couple investigations in Si-doped Li-rich cathode materials

   https://doi.org/10.1039/D0CP05737A  

   Nation, Leah; Wu, Yan; Liu, Xiaoming; Chi, Miaofang; Wu, Yuqin; Qi, Yue; Sheldon, Brian W. (February 2021, Physical Chemistry Chemical Physics)

   null (Ed.)

   In this investigation, the improved electrochemical behavior in Si-doped Li-rich cathodes is studied with scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). Z-contrast images show a layered structure that develops a thin, spinel-like surface layer after the first charge cycle. Si-doping increases discharge capacity by ∼25% and appears to retard the surface phase transformation. Based on electron energy loss spectra, the surface layer in the doped material has an altered oxygen electronic environment, which supports the STEM findings. Furthermore, Si-doping changes the redox behavior during the activation cycle. Density functional theory calculations indicate that Si-doping can increase oxygen vacancy formation, and change the sequence of the redox couples by introducing more oxygen vacancies before or during the typical high voltage activation process. The results of this work indicate that the type of doping employed here is an effective strategy for controlling the complex charge compensation mechanisms in lithium-rich cathodes. 

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5. “Single Pd Atom–In2O3 Catalyzes Production of CH3CH2OH from Atom-Economic C–C Coupling of HCHO and CH4.”,

   Zhao, Y; Fontillas, N; Wang, H; Zhu, X; Mei, D; Ge, Q (January 2024, ACS catalysis)

   Using methane as a reagent to synthesize high-value chemicals and high-energy density fuels through C−C coupling has attracted intense attention in recent decades, as it avoids completely breaking all C−H bonds in CH4. In the present study, we demonstrated that the coupling of HCHO with the CH3 species from CH4 activation to produce ethanol can be accomplished on the single Pd atom−In2O3 catalyst based on the results of density functional theory (DFT) calculations. The results show that the supported single Pd atom stabilizes the CH3 species following the activation of one C−H bond of CH4, while HCHO adsorbs on the neighboring In site. Facile C−C coupling of HCHO with the methyl species is achieved with an activation barrier of 0.56 eV. We further examined the C−C coupling on other single metal atoms, including Ni, Rh, Pt, and Ag, supported on In2O3 by following a similar pathway and found that a balance of the three key steps for ethanol formation, i.e., CH4 activation, C−C coupling, and ethoxy hydrogenation, was achieved on Pd/In2O3. Taking the production of acetaldehyde and ethylene on the Pd/In2O3 catalyst into consideration, the DFT-based microkinetic analysis indicates that ethanol is the dominant product on the Pd/In2O3 catalyst. The facile C−C coupling between HCHO and dissociated CH4 makes formaldehyde a potential C1 source in the conversion and utilization of methane through an energy- and atom-efficient process. 

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