Article
Engineering, Electrical & Electronic
Katharina C. L. Bauerfeind, Joachim Laun, Marvin Frisch, Ralph Kraehnert, Thomas Bredow
Summary: State-of-the-art catalysts for the acidic oxygen evolution reaction are mainly based on mixed oxides of titanium and iridium or ruthenium. In this study, the stability and electronic properties of substituted rutile-phase titania were theoretically examined, with tantalum and niobium identified as the most promising candidates to improve the electronic properties of titania. Experimentally, favorable and unfavorable elements were synthesized with 25% foreign metal concentration.
JOURNAL OF ELECTRONIC MATERIALS
(2022)
Review
Chemistry, Physical
Yuting Li, Daniel Bahamon, Mutasem Sinnokrot, Khalid Al-Ali, Giovanni Palmisano, Lourdes F. Vega
Summary: Hydrogen is crucial for a clean and sustainable energy future, with the photocatalytic splitting of H2S being a considered sustainable method to meet energy demands. Improving solar light utilization and splitting efficiency to design effective photocatalysts is essential for enhancing hydrogen generation efficiency.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY C-PHOTOCHEMISTRY REVIEWS
(2021)
Article
Chemistry, Physical
Gerhard R. Wittreich, Geun Ho Gu, Daniel J. Robinson, Markos A. Katsoulakis, Dionisios G. Vlachos
Summary: This study develops a framework to estimate correlations in parameters of kinetic models and quantify uncertainty for thermochemistry, reaction barriers, reaction paths, and ultimately reaction rates, while also considering the contribution of entropic uncertainty. The approach is illustrated on propane combustion and ethane oxidative dehydrogenation reactions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Physical
Lukas Cvitkovich, Dominic Waldhoer, Al-Moatassem El-Sayed, Markus Jech, Christoph Wilhelmer, Tibor Grasser
Summary: This paper presents a theoretical assessment of the thermal oxidation process of the Si(100) surface in the ultra-thin layer regime below 2 nm using a first-principles approach. The study reveals the amorphization of the oxide surface layer as a direct consequence of lattice vibrations and provides insights into the complex interplay between different oxidation mechanisms. The method used in this study can also be extended to other material systems for the generation of realistic interface structures.
APPLIED SURFACE SCIENCE
(2023)
Article
Nanoscience & Nanotechnology
Farahnaz Maleki, Giovanni Di Liberto, Gianfranco Pacchioni
Summary: In this work, the pH- and facet-dependent surface chemistry of TiO2/water interfaces was studied using ab initio molecular dynamics simulations. Acid-base equilibrium constants were determined at the interface, allowing for estimation of the pH at the point of zero charge, an important experimental observable. The amount of H+, OH-, and adsorbed H2O species on the surfaces was predicted based on simulated equilibrium constants, providing insights into water splitting semi-reactions. The complex morphology of TiO2 particles was approximated by considering different surfaces.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Materials Science, Ceramics
V. B. Sulimov, D. C. Kutov, A. Sulimov, F. Grigoriev, A. Tikhonravov
Summary: Ab initio molecular dynamics modeling is used to obtain amorphous states of SiO2, ZrO2, and HfO2 crystals under different temperature conditions. The structural characteristics of the obtained amorphous states are analyzed and discussed. The findings show that the amorphous state features vary with different materials and temperature conditions.
JOURNAL OF NON-CRYSTALLINE SOLIDS
(2022)
Article
Chemistry, Physical
Zachary K. Goldsmith, Annabella Selloni, Zhutian Ding
Summary: In this study, hole states at the aqueous interface of Zn-doped hematite (0001) were characterized using density functional theory. A hole state within the band gap of hematite, localized on a Fe-O moiety, was observed. The interfacial hydration structure and hydrogen bonding dynamics were minimally affected by Zn doping.
Article
Engineering, Chemical
Li-Jun Jing, Wei-Qi Yan, Han-Jie Xiao, Ming Lei, Yue-Qiang Cao, Zhi-Jun Sui, Jing-Hong Zhou, Xing-Gui Zhou, De Chen, Yi-An Zhu
Summary: The electronic structures of Cu-TiO2 and Au-TiO2 were investigated, and it was found that metal clusters mainly coordinate with O2c ions on the TiO2 surface. The defective surface of TiO2 provides additional sites for anchoring Cu6 and Au6 clusters. The Cu-TiO2 catalyst exhibits higher turnover frequency for DMO hydrogenation and has the potential for selective production of methyl glycolate.
CHEMICAL ENGINEERING SCIENCE
(2023)
Article
Materials Science, Multidisciplinary
A. C. Martinez-Olguin, R. Ponce-Perez, Leonardo Morales De la Garza, Maria G. Moreno-Armenta, Gregorio H. Cocoletzi
Summary: The study investigates the structural, electronic, and magnetic properties of cobalt adsorption and incorporation on the AlN surface, showing different magnetic behaviors depending on coverage and configuration.
JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Peiwei You, Chao Lian, Daqiang Chen, Jiyu Xu, Cui Zhang, Sheng Meng, Enge Wang
Summary: In this study, a polymeric semiconductor-graphitic carbon nitride was chosen as a prototype substrate to investigate light-driven photocatalytic water splitting. The research reveals the transport channel of photogenerated charge carriers at the interface, proposes a three-step photoreaction mechanism, and presents insights for further development of efficient water-splitting photocatalysts from a dynamic perspective.
Article
Chemistry, Physical
Kohei Tada, Hiroyuki Ozaki, Koji Fujimaru, Yasutaka Kitagawa, Takashi Kawakami, Mitsutaka Okumura
Summary: The study found that surface interactions can tune chemical indices and that weak adsorption onto ionic solids with charge-dipole interactions can enhance diradical character.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Review
Multidisciplinary Sciences
Ajin Rajan, Anoop P. Pushkar, Balaji C. Dharmalingam, Jithin John Varghese
Summary: Modern heterogeneous catalysis benefits greatly from computational predictions of catalyst structure and its evolution, first-principles mechanistic investigations, and detailed kinetic modeling. This article presents operando catalyst structure prediction techniques using density functional theory simulations and ab initio thermodynamics calculations, as well as surface structure characterization and hierarchical approaches in kinetic parameter estimation. In addition, a bottom-up hierarchical and closed loop modeling framework is proposed.
Review
Chemistry, Multidisciplinary
Zirui Yan, Yaofang Zhang, Weimin Kang, Nanping Deng, Yingwen Pan, Wei Sun, Jian Ni, Xiaoying Kang
Summary: Gas sensors are vital in industry and daily life, and different types of sensors are developed for various situations. Titanium dioxide, with its outstanding properties and wide applications in fields such as dyes and photocatalysis, plays a significant role. Researchers are using modern computers to simulate and study sensors, opening up new possibilities for research. The combination of simulation and calculation helps to understand reaction mechanisms, improve gas sensor material design, and respond to different gas environments. This paper reviews the experimental and computational aspects of TiO2 and describes future research directions.
Article
Chemistry, Physical
Lang Xu, Eric E. Stangland, James A. Dumesic, Manos Mavrikakis
Summary: Catalytic hydrodechlorination of 1,2-dichloroethane using Pt catalysts was studied through a synergistic approach of DFT calculations, reaction kinetics experiments, and microkinetic modeling. The reaction on Pt(111) involves multiple steps leading to the formation of ethane. Adjustments to model parameters were made to achieve good agreement between theoretical predictions and experimental results, highlighting the importance of coverage effects in catalytic reactions. Overall, the study provides valuable mechanistic insights for improving catalysts in this chemistry.
Article
Materials Science, Multidisciplinary
Andrew C. Burgess, Edward Linscott, David D. O'Regan
Summary: A DFT+U-type corrective functional is proposed to enforce the flat plane condition on localized subspaces, eliminating the need for deriving from the Hubbard model. The functional shows low relative errors in total energy for dissociated s-block dimers and the challenging dissociated H+5 ring system. In comparison, bare PBE and PBE+U yield much higher energetic errors.
Article
Chemistry, Physical
Hui Zhou, Xin-Ping Wu, Xue-Qing Gong
Summary: In this study, density functional theory calculations were used to investigate the catalytic performances of CeO4-terminated and Ca-doped surfaces. It was found that the Ca-doped surface exhibits lower-coordinated Ce sites which facilitate reduction of Ce4+ to Ce3+ and enhance the selective oxidation of CH4 to CH3OH. The isolated nature and strong electron-reservoir character of the low-coordinated Ce sites on the Ca-doped surface play a crucial role in the high activity and selectivity towards CH4 oxidation.
Article
Chemistry, Physical
Cong Fu, Fei Li, Jianlong Yang, Jijia Xie, Yunshang Zhang, Xiao Sun, Xusheng Zheng, Yuanxu Liu, Junfa Zhu, Junwang Tang, Xue-Qing Gong, Weixin Huang
Summary: It is found that uniform anatase TiO2 nanocrystals predominantly enclosed with the {001} facets exhibit high activity in photocatalytic catalyzing methane combustion. The valence band maximum and conduction band minimum were found to locate separately for TiO2-{001} nanocrystals terminated with the reconstructed (001)-(1 x 4) surface, at the surface and in the bulk, respectively. The photocatalytic methane reaction rate is about 6 and 7 times higher compared to TiO2 nanocrystals predominantly enclosed with the {100} facets or with the {101} facets. This high activity is mainly attributed to the spontaneous bulk-surface charge separation and subsequent facile interfacial hole transfer from TiO2(001) surface to adsorbed methane.
Article
Chemistry, Physical
Tao Tong, Mark Douthwaite, Lu Chen, Rebecca Engel, Matthew B. Conway, Wanjun Guo, Xin-Ping Wu, Xue-Qing Gong, Yanqin Wang, David J. Morgan, Thomas Davies, Christopher J. Kiely, Liwei Chen, Xi Liu, Graham J. Hutchings
Summary: The physicochemical properties of Pt/CeO2 catalysts were varied to investigate their impact on the hydrogen-borrowing amination of alcohols. It was found that the Pt precursor and CeO2 support properties strongly influenced catalytic performance. The most active catalyst exhibited linearly structured Pt species, which were more effective for the rate-determining step of cyclopentanol dehydrogenation compared to Pt clusters and nanoparticles. This study not only provides insights into desirable catalytic properties for hydrogen-borrowing amination but also has broader relevance to related fields.
Article
Chemistry, Physical
Hui Zhou, Dong Wang, Xue-Qing Gong
Summary: By performing density functional theory calculations, it was found that the composite catalysts of inverse CeOx/Cu(111) can produce more active hydride species compared to CeO2 or Cu alone. This is mainly due to the efficient combination of the unique structural feature of CeOx islands and the electronic promotion from Cu. Additionally, modifying the Cu(111) surface with pyridine molecules can enhance the thermo- and dynamical stabilities of the hydride species.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Yan-Ping Zhang, Zi-Xiang Su, He-He Wei, Zhi-Qiang Wang, Xue-Qing Gong
Summary: In this study, the researchers systematically investigated the oxygen reduction reaction (ORR) on various Pt-Bi surfaces using density functional theory calculations. They found that the introduction of Bi changes the determining step of ORR and identified the hydroxy adsorption free energy (GOH*) as a descriptor for ORR activity. The researchers also discovered that the combination of tensile strain introduced by Bi and electron transfer between Pt and Bi affects the d-band position of Pt, leading to the highest ORR activity on PtBi(100), even exceeding that of Pt(111).
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Zheng Huang, Dongsheng Ma, Pei Nian, Yu Zhou, Dong Wang, Xueqing Gong, Zheng Wang, Qin Yue
Summary: A novel 2D mesoporous N-doped carbon nanosheet with confined bimetallic CoNi nanoparticles sandwiched graphene has been successfully fabricated as a host material for lithium-sulfur batteries. This material exhibits high reversible capacity, superior rate capability, and excellent cycling stability. The remarkable performance is attributed to the ordered mesoporous N-doped carbon framework and the adsorption and catalytic conversion abilities of bimetallic CoNi nanoparticles.
Article
Multidisciplinary Sciences
Bin Shao, Zhi-Qiang Wang, Xue-Qing Gong, Honglai Liu, Feng Qian, P. Hu, Jun Hu
Summary: The integrated CO2 capture and conversion (iCCC) technology is a promising cost-effective approach for Carbon Neutrality. The lack of molecular consensus about the synergistic effect between adsorption and in-situ catalytic reaction hampers its development. In this study, the synergies between CO2 capture and in-situ conversion are illustrated through high-temperature Calcium-looping and dry reforming of methane processes.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Cong Fu, Fei Li, Zongfang Wu, Feng Xiong, Junfa Zhu, Xue-Qing Gong, Weixin Huang
Summary: A trace amount of potassium dopant is found to restructure the surface of anatase TiO2(001) single crystal, changing the termination from molecule termination to oxygen termination. The molecule-terminated surface shows (photo)catalytic activity, while the oxygen-terminated surface is inert.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Renjie Zhou, Lipeng Yang, Zhengda Chen, Li Jiang, Tuan Liu, Zhiqiang Wang, Xinyi Huang, Qiuning Lin, Xueqing Gong, Yi Yang, Linyong Zhu
Summary: Photoactivated fluorophores (PAFs) have great potential as imaging tools for subcellular structures and dynamic biological processes. However, the current photoremovable protecting groups (PPGs) used in PAF construction have limitations in terms of excitation wavelength and efficiency. In this study, a new class of coumarin-based PPGs with electron-rich thiophene derived substitutions was developed to address these limitations. The modified PPGs showed redshifted absorption and increased photolysis efficiency, enabling efficient photolysis even under weak blue light. The resulting PAF exhibited fast photoactivation, low background signal, and high signal-to-noise ratio in fluorescence imaging. It is anticipated that these superior photolysis properties make the PPGs a novel platform for constructing photoresponsive systems in various applications.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yan-Ping Zhang, Zi-Xiang Su, He-He Wei, Zhi-Qiang Wang, Xue-Qing Gong
Summary: Reducing the use of Pt in proton exchange membrane fuel cells is a significant interest for both academia and industry. This study investigated the oxygen reduction reaction (ORR) on various Pt-Bi surfaces using density functional theory calculations. The introduction of Bi altered the determining step of ORR and the hydroxy adsorption free energy (GOH*) was found to be an indicator of ORR activity, with 0.74 eV being the optimal GOH* value. It was also discovered that the strain induced by Bi and electron transfer between Pt and Bi influenced the d-band of Pt, resulting in PtBi(100) having superior ORR activity compared to Pt(111).
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Xiang-Peng Tao, Xue-Qing Gong, Dong Wang
Summary: The study reveals the reaction mechanism of photocatalytic formaldehyde degradation and proposes an optimal degradation mechanism that harnesses the advantages of photogenerated holes and (OH)-O-center dot radicals. Additionally, the research also discovers the correlation between the catalytic and thermocatalytic reaction barriers of C-H bond activation and the polarity of C-H bonds.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Jing Hao, Jie Hou, Hehe Wei, Zixiang Su, Hui Li, Longtao Zhang, Xueqing Gong
Summary: An amorphous 1.1 nm Ir/C catalyst shows ultralow overpotentials, high mass activity, and outstanding long-term durability for the hydrogen evolution reaction, surpassing the commercial Pt/C catalyst.
CHEMICAL COMMUNICATIONS
(2022)
