A5049133522- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Electrocatalysts for Energy Conversion
- Catalytic Processes in Materials Science
- Catalytic Cross-Coupling Reactions
- Organometallic Complex Synthesis and Catalysis
- CO2 Reduction Techniques and Catalysts
- Asymmetric Hydrogenation and Catalysis
- Fuel Cells and Related Materials
- Coordination Chemistry and Organometallics
- Ammonia Synthesis and Nitrogen Reduction
- Electrochemical Analysis and Applications
- Advanced Photocatalysis Techniques
- Carbon dioxide utilization in catalysis
- Advanced battery technologies research
- Machine Learning in Materials Science
- Catalytic C–H Functionalization Methods
- Catalysis and Oxidation Reactions
- Metal-Organic Frameworks: Synthesis and Applications
- Metal-Catalyzed Oxygenation Mechanisms
- Nanomaterials for catalytic reactions
- Chemistry and Stereochemistry Studies
- History and advancements in chemistry
- Chemical Reactions and Isotopes
- Nanocluster Synthesis and Applications
CIC energiGUNE
2024-2025
Trinity College Dublin
2017-2025
Ikerbasque
2024-2025
Advanced Materials and BioEngineering Research
2019-2025
22q11 Ireland
2018-2021
Greenville College
2018-2021
Trinity College
2019
Stanford University
2016-2018
Interface (United States)
2016-2018
SLAC National Accelerator Laboratory
2015-2018
Earth-abundant first-row (3d) transition metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials substantially above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies OER intermediates. We a room-temperature synthesis to produce gelled oxyhydroxides materials with an atomically homogeneous...
Palladium-catalyzed C-C cross-coupling reactions (Suzuki-Miyaura, Negishi, Stille, Sonogashira, etc.) are among the most useful in modern organic synthesis because of their wide scope and selectivity under mild conditions. The many steps involved availability competing pathways with similar energy barriers cause mechanism to be quite complicated. In addition, short-lived intermediates difficult detect, making it challenging fully characterize these using purely experimental techniques....
Co3O4 is an attractive earth-abundant catalyst for CO oxidation, and its high catalytic activity has been attributed to Co3+ cations surrounded by Co2+ ions. Hence, the majority of efforts enhancing have focused on exposing more surface. Herein, we enhance replacing ions in lattice with Cu2+. Polycrystalline nanowires which substituted Cu2+ are synthesized using a modified hydrothermal method. The Cu-substituted Co3O4_Cux polycrystalline exhibit much higher oxidation than pure similar those...
A major roadblock in realizing large-scale production of hydrogen via electrochemical water splitting is the cost and inefficiency current catalysts for oxygen evolution reaction (OER). Computational research has driven important developments understanding designing heterogeneous OER using linear scaling relationships derived from computed binding energies. Herein, we interrogate 17 most active molecular catalysts, based on different transition metals (Ru, Mn, Fe, Co, Ni, Cu), show they obey...
Mechanisms for H2 dissociation on metal oxides have been typically inferred from the infrared spectra of reaction products basis presence or lack M–H fingerprints. Here, we demonstrate by means density functional theory that with polar M–O bonds might favor heterolytic dissociation. Moreover, report resulting product can further evolve to homolytic one provided ions are reducible. Hence, it follows redox capacity determines outcome. This finding sheds light why both and O–H bands appear in...
The preferential CO oxidation (CO-PROX) reaction is paramount for the purification of reformate H2-rich streams, where CuO/CeO2 catalysts show promising opportunities. This work sheds light on lattice oxygen recovery mechanism during CO-PROX reaction, which critical to guarantee both good activity and selectivity, but that yet be well understood. Particularly, in situ Raman spectroscopy reveals vacancies ceria do not form significant amounts until advanced degrees, whereas pulse O2 isotopic...
During their lifetime, the electrocatalytically active NiFe LDH platelets show impressive, but unstable water-splitting capabilities due largely to compositional degradation.
Abstract The increase in anthropogenic carbon dioxide (CO 2 ) emissions has exacerbated the deterioration of global environment, which should be controlled to achieve neutrality. Central core goal achieving neutrality is utilization CO under economic and sustainable conditions. Recently, strong need for led a proliferation studies on direct conversion into carboxylic acids, can effectively alleviate create high‐value chemicals. purpose this review present application prospects acids basic...
Cyclohexanone oxime is an important precursor for Nylon-6 and typically synthesized via the nucleophilic addition–elimination of hydroxylamine with cyclohexanone. Current technologies production are, however, not environment-friendly due to requirement harsh reaction conditions. Here, we report electrochemical method one-pot synthesis cyclohexanone under ambient conditions aqueous nitrate as nitrogen source. A series Zn–Cu alloy catalysts are developed drive reduction nitrate, where...
A DFT study of R−R reductive elimination (R = Me, Ph, vinyl) in plausible intermediates Pd-catalyzed processes is reported. These include the square-planar tetracoordinated systems cis-[PdR2(PMe3)2] themselves, possible cis-[PdR2(PMe3)L] formed solution or upon addition coupling promoters (L acetonitrile, ethylene, maleic anhydride (ma)), and tricoordinated cis-[PdR2(PMe3)] (represented as L empty). The activation energy ranges from 0.6 to 28.6 kcal/mol gas phase, increasing order...
Abstract Transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress development of highly active oxide nanostructures is hampered by a lack knowledge location and nature sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy computational modelling, how hydroxyls form from dissociation at under coordinated cobalt edge sites nanoislands. Surprisingly, find...
While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This often been aided through the use of transition state (TS) scaling relationships, which estimate activation TS energies as linear function easily calculated descriptor, such final energy, thus avoiding tedious calculations. It shown that can be activated via radical or surface-stabilized pathway, both possess unique...
Metal-free carbon electrodes with well-defined composition and smooth topography are prepared via sputter deposition followed by thermal treatment inert reactive gases. X-ray photoelectron spectroscopy (XPS) Raman show that three carbons of similar N/C content differ in N-site thus prepared: an electrode consisting almost exclusively graphitic-N (NG ), predominantly pyridinic-N (NP one ≈1:1 NG :NP composition. These materials used as model systems to investigate the activity N-doped oxygen...
Abstract Elastic strain is being increasingly employed to enhance the catalytic properties of mixed ion–electron conducting oxides. However, its effect on oxygen storage capacity not well established. Here, we fabricate ultrathin, coherently strained films CeO 2-δ between 5.6% biaxial compression and 2.1% tension. In situ ambient pressure X-ray photoelectron spectroscopy reveals up a fourfold enhancement in equilibrium under both This non-monotonic variation with departs from conventional...
Chiroptically active fluorescent semiconductor nanocrystals, quantum dots (QDs), are of high interest from a theoretical and technological point view, because they promising candidates for range potential applications. Optical activity can be induced in QDs by capping them with chiral molecules, resulting circular dichroism (CD) signals the QD ultraviolet–visible (UV-vis) absorption. However, effects ligand concentration binding modes on chiroptical properties still poorly understood. In...
Abstract In alkaline water electrolysis and anion exchange membrane technologies, the hydrogen evolution reaction (HER) at cathode is significantly constrained by a high energy barrier during dissociation step. This study employs phase engineering strategy to construct heterostructures composed of crystalline Ni 4 W amorphous WO x aiming enhance catalytic performance in HER under conditions. work systematically modulates oxidation states within heterostructure adjust electronic boundary,...
This study reports a method for the selective reduction of NO3– and NO2– to N2 or NH3, extending prior work in our lab where was reduced NO by [N(afaCy)3Fe]OTf2 (N(afaCy)3 = tris(5-cyclohexyl-amineazafulvene-2-methyl)amine, OTf triflate). The first pathway involves N2, generated initial step is transformed N2O PPh3 further complex. An alternative showcases bound complex, [N(afaCy)3Fe(NO)]2+, NH3 using chemical reductants, albeit with modest yield 29%. Confirmation nitrogen source as...
The reaction mechanism for the Pd-catalyzed Cu-free Sonogashira is analyzed by means of density functional theory (DFT) calculations on a model system. most common routes proposed in literature this reaction, namely, carbopalladation and deprotonation, are considered. In agreement with experiment, clearly demonstrate that route can be discarded. For case deprotonation route, however, pathway may take place via several alternatives; suggest all them feasible. Moreover, an additional where...
The role of trivalent (La, Sm, Gd, and Y) tetravalent (Hf, Zr, Ti) dopants in the catalytic, structural, electronic properties ceria was investigated. Promoted catalysts were synthesized by coprecipitation with ammonia tested HCl CO oxidation. Ceria exhibit a medium high reactivity excellent stability intrinsic oxidation can be improved factor 2 when doping Hf Zr appropriate quantities, whereas are detrimental. Although both reactions rely on existence oxygen vacancies, order is not...
Rare-earth oxides (REOs) possess a remarkable intrinsic hydrophobicity, making them candidates for myriad of applications. Although the superhydrophobicity REOs has been explored experimentally, atomistic details structure at oxide–water interface are still not well understood. In this work, we report density functional theory study interaction between water and CeO2, Nd2O3, α-Al2O3 to explain their different wettability. The wetting metal oxide surface is controlled by geometric electronic...