Article
Engineering, Environmental
Thanapha Numpilai, Chin Kui Cheng, Jumras Limtrakul, Thongthai Witoon
Summary: The increasing concerns over global warming due to rising CO2 levels have prompted activities and research into reducing CO2 emissions. The industrial sector is a major emitter of CO2, emphasizing the need for efficient processes to reduce emissions. Utilizing CO2 for the production of high value-added chemicals, such as light olefins, has shown promise in addressing these issues.
PROCESS SAFETY AND ENVIRONMENTAL PROTECTION
(2021)
Article
Chemistry, Physical
Renjie Liu, Denis Leshchev, Eli Stavitski, Mitchell Juneau, Jane N. Agwara, Marc D. Porosoff
Summary: Research on utilizing CO2 as a C-1 feedstock for the synthesis of chemicals and fuels shows that the selectivity of catalysts is strongly linked to the Si/Al ratio and the method of introducing the K promoter.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Review
Chemistry, Multidisciplinary
Tesfalem Aregawi Atsbha, Taeksang Yoon, Park Seongho, Chul-Jin Lee
Summary: Replacing fossil fuels with renewable energy sources plays a fundamental role in creating a sustainable and carbon-free economy. Recent attention has been focused on the catalytic hydrogenation of CO2, emphasizing the development of efficient, selective, and stable catalysts. This review summarizes the current developments and improvements in catalytic conversion of CO2 towards the synthesis of CO, methanol, and hydrocarbons.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Chemistry, Physical
Qian Jiang, Wen Luo, Yuang Piao, Hiroaki Matsumoto, Xi Liu, Andreas Zuttel, Ksenia Parkhomenko, Cuong Pham-Huu, Yuefeng Liu
Summary: This study investigates the metal-support interaction in TiC-SiC supported cobalt catalyst in Fischer-Tropsch synthesis, revealing the significant impact of surface oxides on metal-carbide interactions and catalytic activity. Surface TiOx species and Co-TiOx overlayer were identified as key factors modulating the metal-support interaction in the Co/TiC-SiC system.
Article
Chemistry, Multidisciplinary
Iris C. ten Have, Robin Y. van den Brink, Stephane C. Marie-Rose, Florian Meirer, Bert M. Weckhuysen
Summary: Gasification is a process that converts solid waste into gaseous feedstock. This study investigates the possibility of using waste gasification solid residue as a catalyst for producing light olefins. Experimental results show that the catalyst can convert biomass-derived syngas into methane and olefins.
Article
Chemistry, Physical
Mikhail Shipilin, David Degerman, Patrick Lomker, Christopher M. Goodwin, Gabriel L. S. Rodrigues, Michael Wagsta, Joergen Gladh, Hsin-Yi Wang, Andreas Stierle, Christoph Schlueter, Lars G. M. Pettersson, Anders Nilsson, Peter Amann
Summary: In this study, the effect of pressure, temperature, time, and gas feed composition on the growth dynamics of iron-carbon phases was investigated. The details of iron surface carburization and product formation under realistic conditions were revealed using a combination of experimental and theoretical approaches. This research provides important insights into the relationship between the catalyst's surface and the reaction.
Article
Chemistry, Physical
Mikhail Shipilin, David Degerman, Patrick Loemker, Christopher M. Goodwin, Gabriel L. S. Rodrigues, Michael Wagstaffe, Jorgen Gladh, Hsin-Yi Wang, Andreas Stierle, Christoph Schlueter, Lars G. M. Pettersson, Anders Nilsson, Peter Amann
Summary: This study investigates the detailed mechanism of carbide formation on iron-based catalysts and the effect of reaction conditions on the catalyst surface state through experiments and theoretical calculations.
Article
Chemistry, Physical
Yuzhen Ge, Tangsheng Zou, Antonio J. Martin, Javier Perez-Ramirez
Summary: This study investigates the impact of highly dispersed metal oxides of Co-Cu, Cu-Fe, and Co-Fe m-FTS systems on the direct synthesis of higher alcohols (HA) and demonstrates the viability of ZrO2 as a promoter. The addition of ZrO2 significantly increases HA productivity, with the Cu(1)Co(4)@ZrO2-5 catalyst exhibiting a 2.5-fold increase compared to its ZrO2-free counterpart. The Co1Fe4@ZrO2-10 catalyst shows the most productive performance among similar systems.
Article
Chemistry, Physical
Yajing Duan, Huijuan Sun, Wencai Lu
Summary: This study investigated the adsorption and activation of CO on the h-Fe7C3 (111) surface using density functional theory calculations. The results showed that the B5 site on the h-Fe7C3 (111) surface exhibited excellent intrinsic activity for CO adsorption and activation. The preferred CO activation pathway on the B5 site was identified and the influences of carbon vacancy on the CO adsorption and activation were studied. It was found that the vacancy surface was more conducive to the elementary reactions of CO adsorbed on the B5 site, especially on the VC2 surface.
MOLECULAR CATALYSIS
(2022)
Article
Energy & Fuels
Dalia Liuzzi, Francisco J. Perez-Alonso, Sergio Rojas
Summary: Ru-Co/Al2O3 and Ru-Fe/Al2O3 catalysts prepared by reduction-deposition method exhibit high activity in Fischer-Tropsch Synthesis, showing different conversion rates and product selectivity. The interaction between Ru and Co in Ru-Co/Al2O3 enhances the activity, while Ru-Fe/Al2O3 displays superior initial performance but declines over time, with less enriched products compared to Ru/Al2O3.
Article
Chemistry, Applied
Nothando C. Shiba, Yali Yao, Roy P. Forbes, Chike G. Okoye-Chine, Xinying Liu, Diane Hildebrandt
Summary: The study showed that mixed CoO-Co nanoparticles dispersed on a SiO2 support exhibit high activity for Fischer-Tropsch synthesis reactions, with a synergistic effect between CoO and Co degrees. This research provides valuable information for the design of commercial Fischer-Tropsch cobalt-based catalysts.
FUEL PROCESSING TECHNOLOGY
(2021)
Article
Chemistry, Physical
Yanbing Li, Yingluo He, Kensei Fujihara, Chengwei Wang, Xu Sun, Weizhe Gao, Xiaoyu Guo, Shuhei Yasuda, Guohui Yang, Noritatsu Tsubaki
Summary: In this study, a core-shell structured Na/Fe@Co bimetallic catalyst was developed to enhance CO2 conversion and selectivity of light hydrocarbons, while inhibiting CO selectivity. Characterization analyses revealed that the introduction of CoCo Prussian Blue Analog (CoCo PBA) increased the reducibility of iron oxide, accelerated the formation of iron carbide, and adjusted the surface basic properties of the catalyst. Additionally, trace Co atoms acted as a second active center in the CO2 Fischer-Tropsch synthesis process for increasing the synthesis of light hydrocarbons from CO hydrogenation. This work provides a novel core-shell structured bimetallic catalyst system for the production of light hydrocarbons, particularly light olefins, from CO2 hydrogenation.
Article
Chemistry, Physical
Tshepo Molefe, Dean Barrett, Beatriz Diaz, Roy Forbes, Neil J. Coville
Summary: This study reports on the synthesis and application of osmium nanoparticles supported on and/or encapsulated in hollow carbon spheres for Fischer-Tropsch Synthesis (FTS). It is demonstrated that the interaction between osmium and cobalt has a significant effect on the catalyst activity when loaded together. Proximity of osmium and cobalt leads to higher FTS activity and C5+ production through the primary spillover effect. This study reveals the effect of osmium on FTS catalysts for the first time.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Chide Chen, Xiaoting Wu, Shuxian Zhang, Ming Qing, Mengying La, Jifan Li, Chun-Ling Liu, Wen-Sheng Dong
Summary: Ga-modified CuFeO(2) as a catalyst for CO2 hydrogenation to heavy olefins achieves a high heavy olefin selectivity of 53.5% at a single pass CO2 conversion of 41.5%, which is among the highest reported catalysts. It also demonstrates excellent long-term stability over 100 hours, showing promising potential for industrial applications.
CHEMICAL COMMUNICATIONS
(2023)
Article
Energy & Fuels
Lisheng Guo, Song Sun, Jie Li, Weizhe Gao, Heng Zhao, Baizhang Zhang, Yingluo He, Peipei Zhang, Guohui Yang, Noritatsu Tsubaki
Summary: A bifunctional catalyst composed of K-Fe/C and zeolite efficiently produces liquid fuels by tuning the microenvironment properties of ZSM-5 zeolite. K-Fe/C catalyst is responsible for olefin formation, while ZSM-5 catalyst is responsible for olefin secondary reactions. Surface acid properties of ZSM-5 can be regulated through different ion-exchange strategies to improve C5+ selectivity.
Review
Chemistry, Physical
Hua Guo, Wenyu Hu, Duowen Yang, Dan Wan, Hao Xu, Wei Yan, Xiaoliang Jin
Summary: Electrochemical characterization is crucial for understanding the degradation and properties of electrodes. In the field of anodic oxidation (AO) for wastewater treatment, electrochemical characterization mainly focuses on qualitative comparison of catalytic activity and electrode stability. However, the influence of reaction environment and the need for horizontal comparison should be considered. Common electrochemical indexes obtained from cyclic voltammetry, linear sweep voltammetry, electrochemical impedance spectroscopy, and other methods should be carefully tested according to the requirements of AO. Monitoring and predicting system performance can be achieved by observing the variation of these indexes before and after the degradation process.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Chemistry, Physical
Dandan Lu, Rodrigo Urzua-Leiva, Otoniel Denis-Alpizar, Hua Guo
Summary: The hyperthermal dynamics and kinetics of the title reaction, which plays an important role in hypersonic chemistry for atmospheric entry vehicles, are investigated using quasi-classical trajectory methods on a recently developed ground electronic state potential energy surface. The dynamics calculations indicated that the reaction follows a complex-forming mechanism, despite its large endoergicity. The calculated differential cross section is forward-backward symmetric, consistent with a long-lived reaction intermediate supported by the NCN potential well . The lifetime of the reaction complex is sufficiently long that the vibrational distribution of the CN product can be predicted by the phase space theory. The calculated vibrational state specific and thermal rate coefficients follow the Arrhenius behavior, and the agreement with existing low-temperature experimental thermal rate coefficients is satisfactory. Extrapolations to high temperatures relev a n t to hypersonic conditions are provided.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Dandan Lu, Hua Guo
Summary: The dynamics and kinetics of nonadiabatic excitation of C(3P) to C(1D) induced by hyperthermal collisions with N2 molecules were investigated using quantum mechanical and two semiclassical nonadiabatic methods. The interaction potential energy surfaces and spin-orbit coupling were represented by a diabatic potential energy matrix, which facilitated the spin-forbidden process. Quantum dynamics calculations showed small transition probabilities due to weak spin-orbit coupling, with the most favored spin-flip transition near the threshold. The results also revealed strong oscillations and vibrational state-specified rate coefficients, with the N2 collision partner increasing the excitation rate at low temperatures but reversing the trend at high temperatures. The semiclassical methods qualitatively reproduced the quantum rate coefficients.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Brendan C. Sweeny, Bryan A. Long, Dominique Maffucci, Junxiang Zuo, Hua Guo, Albert A. Viggiano, Shaun G. Ard, Nicholas S. Shuman
Summary: The kinetics of the reaction between Zr+ and CH4 were investigated over a range of temperatures and pressures using a selected-ion flow tube apparatus. The measured rate constants were found to be small, indicating that the reaction is not very efficient. Two products, ZrCH4+ and ZrCH2+, were observed. A statistical modeling approach was used to fit the experimental data and revealed important information about the reaction mechanism and energetics. The results showed that the formation of the bimolecular product is favored over competing processes, and the energy of the products and reaction depend on various factors.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
James F. E. Croft, Pablo G. Jambrina, F. Javier Aoiz, Hua Guo, N. Balakrishnan
Summary: This study focuses on the collisions of two D2 molecules prepared in the v = 2 vibrational level and j = 2 rotational level. Quantum calculations were performed to identify key resonance features that contribute to the angular distribution in the experimental results.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Hua Guo, Yingqi Wang
Summary: As shown by a recent scanning tunneling microscopy study, the dissociation of N-2 impinging on Ru(0001) produces spherical N atoms that can travel significant distances from the impact site. In this work, the hot nitrogen atom dynamics following N-2 dissociation is investigated theoretically using a neural network representation of density functional theory data. Quasi-classical trajectory simulations reveal that typically only one N atom undergoes significant migration, while the other is often trapped near the impact site. The relatively short migration distance of the hot N atom found in the simulations is attributed to a high diffusion barrier and fast energy dissipation to surface phonons.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Liang Zhang, Junxiang Zuo, Yury V. V. Suleimanov, Hua Guo
Summary: A ring polymer molecular dynamics (RPMD) method is proposed for calculating the dissociative chemisorption rate coefficient on surfaces. The RPMD rate theory considers quantum effects such as zero-point energy and tunneling, while using classical trajectories for simulation. The method is applied to H-2 dissociative chemisorption and shows deviations from Arrhenius behavior at low temperatures due to tunneling. On Pt(111), where dissociation has a barrierless pathway, the RPMD rate coefficient agrees with the experimentally derived thermal sticking coefficient within a factor of 2 over a wide temperature range. Significant quantum effects are also observed.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Fenfei Wei, Sen Lin, Hua Guo
Summary: This paper presents a theoretical investigation of methane dissociation on a Pt(110)-(2 x 1) surface using a machine-learned potential energy surface. The simulations show good agreement with experimental results at high incidence energies and provide an explanation for negative activation at low incidence energies.
Article
Chemistry, Physical
Hongwei Song, Hua Guo
Summary: This Perspective focuses on the dynamics of gas-phase bimolecular reactions with submerged barriers, which are prevalent in combustion, atmospheric chemistry, astrochemistry, and plasma chemistry. The temperature dependence of the rate coefficients for such reactions is often non-Arrhenius and complex, and the corresponding dynamics may also be quite different from those with significant barriers or those completely dominated by capture. Recent experimental and theoretical studies have revealed interesting dynamical behaviors, particularly at relatively low temperatures or collision energies, enriching our understanding of these unusual reactions.
ACS PHYSICAL CHEMISTRY AU
(2023)
Correction
Chemistry, Physical
Humberto da Silva, Qian Yao, Masato Morita, Brian K. Kendrick, Hua Guo, Naduvalath Balakrishnan
Summary: This article corrects the errors in the investigation of the Li + CaF reaction under cold conditions and provides accurate results and explanations.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Dandan Lu, Breno R. L. Galvao, Antonio J. C. Varandas, Hua Guo
Summary: The dynamics and kinetics of spin-forbidden transitions between N(D-2) and N(S-4) mediated by collisions with N-2 molecules were investigated using quantum wave packet (WP) method and semi-classical coherent switches with decay of mixing (CSDM) method. These transitions compete with exchange reaction channels on both doublet and quartet potential energy surfaces. The WP and CSDM quenching rate coefficients were in reasonable agreement with each other, reproducing previous theoretical results. For the excitation process, the agreement between the two approaches depended on the treatment of zero-point energy (ZPE) in the product, as the high endoergicity of this process led to severe violation of vibrational ZPE. The Gaussian-binning (GB) method improved the agreement with the quantum result. The excitation rate coefficients were two orders of magnitude smaller than those of the adiabatic exchange reaction, indicating inefficient intersystem crossing due to weak spin-orbit coupling between the two spin manifolds of the N-3 system.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Reed Nieman, Michael Sands, Yingqi Wang, Timothy K. Minton, Erin E. Mussoni, Jeffrey Engerer, Hua Guo
Summary: In order to investigate the gas-surface chemistry on the thermal protection system of a hypersonic vehicle, extensive periodic density functional theory (DFT) calculations are conducted to study the interaction between atomic oxygen/nitrogen and highly oriented pyrolytic graphite (HOPG) surfaces. The calculated reaction energies and barriers provide important information for adsorption, desorption, diffusion, recombination, and other reactions. The results are compared with a finite-rate model and suggest that some model parameters may need further refinement. These calculations contribute to the development of a predictive kinetic model for the complex reaction network under hypersonic flight conditions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Humberto da Silva Jr, Qian Yao, Masato Morita, Brian K. Kendrick, Hua Guo, Naduvalath Balakrishnan
Summary: This paper reports the ab initio electronic structure and full-dimensional quantum dynamical calculations of the Li + CaF -> LiF + Ca chemical reaction. The results show that the Li + CaF reaction populates several low-lying vibrational levels and many rotational levels of the product LiF molecule, and the reaction is inefficient in the 1-100 mK regime, allowing sympathetic cooling of CaF by collisions with cold Li atoms.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yingqi Wang, Hua Guo
Summary: A recent study using scanning tunneling microscopy showed that N2 dissociation on Ru(0001) generates N atoms with high exoergicity, which can migrate away from the impact site. In this work, theoretical investigation based on a high-dimensional potential energy surface and neural network representation was conducted to study the dynamics of these hot nitrogen atoms. Simulation results revealed that typically only one N atom undergoes significant migration while the other remains near the impact site. The average final separation between the two N atoms is much smaller than the experimental report, mainly attributed to high diffusion barrier and fast energy dissipation to surface phonons.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Marcio O. Alves, Vinicius C. Mota, Joao P. Braga, Antonio J. C. Varandas, Hua Guo, Breno R. L. Galvao
Summary: In this study, an accurate potential energy surface (PES) for the lowest lying (4 )A '' state of the CNO system is presented. The energy terms are fitted using a theoretical framework, incorporating long-range interactions. The results show improved accuracy in predicting rate coefficients and highlight the importance of long-range interactions for low-temperature reactions.
JOURNAL OF CHEMICAL PHYSICS
(2023)