Hydrogen Atoms Research Articles

Proton Conduction via Water and Ammonia Coordinated Metal Cationic Species in MOF and MHOF Platforms.

Although metal-organic frameworks (MOFs) and metalo hydrogen-bonded organic frameworks (MHOFs) are designed as promising solid-state proton conductors by incorporating various protonic species intrinsically or extrinsically, design and development of such materials by employing the concept of proton conduction through coordinated polar protic solvent is largely unexplored. Herein, we have constructed two proton-conducting materials having different solvent coordinated metal cationic species: In-H2O-MOF, ({[In(H2O)6][In3(Pzdc)6] ⋅ 15H2O}n; H2Pzdc: pyrazine-2,3-dicarboxylic acid) with coordinated water molecules from hexaaquaindium cationic species, and MHOF-4, ([{Co(NH3)6}2(2,6-NDS)2(H2O)2]n; 2,6-H2NDS: 2,6-naphthalenedisulfonic acid) with coordinated ammonia from hexaammoniacobalt cationic species. Interestingly, higher proton conductivity was achieved for In-H2O-MOF (1.5×10-5 S cm-1) than MHOF-4 (6.3×10-6 S cm-1) under the extreme conditions (80 °C and 95 % RH), which could be attributed to enhanced acidity of coordinated water molecules having much lower pKa value than that of coordinated ammonia. Greater charge polarization on hydrogen atoms of In3+-coordinated water molecules than that of Co2+-coordinated ammonia led to the high conductivity of In-H2O-MOF, as evident by quantum chemical studies. Such a comparative study on metal-coordinated protic polar solvents in achieving proton conduction in crystalline solids is yet to be made.

Revisiting the Vertical Distribution of H i Absorbing Clouds in the Solar Neighborhood. II. Constraints from a Large Catalog of 21 cm Absorption Observations at High Galactic Latitudes

The cold neutral medium (CNM) is where neutral atomic hydrogen (H i) is converted into molecular clouds, so the structure and kinematics of the CNM are key drivers of galaxy evolution. Here we provide new constraints on the vertical distribution of the CNM using the recently developed kinematic_scaleheight software package and a large catalog of sensitive H i absorption observations. We estimate the thickness of the CNM in the solar neighborhood to be σ z ∼ 50–90 pc, assuming a Gaussian vertical distribution. This is a factor of ∼2 smaller than typically assumed, indicating that the thickness of the CNM in the solar neighborhood is similar to that found in the inner Galaxy, consistent with recent simulation results. If we consider only structures with H i optical depths τ > 0.1 or column densities N(H i) > 1019.5 cm−2, which recent work suggests are thresholds for molecule formation, we find σ z ∼ 50 pc. Meanwhile, for structures with τ < 0.1 or column densities N(H i) < 1019.5 cm−2, we find σ z ∼ 120 pc. These thicknesses are similar to those derived for the thin- and thick-disk molecular cloud populations traced by CO emission, possibly suggesting that cold H i and CO are well mixed. Approximately 20% of CNM structures are identified as outliers, with kinematics that are not well explained by Galactic rotation. We show that some of these CNM structures—perhaps representing intermediate-velocity clouds—are associated with the Local Bubble wall. We compare our results to recent observations and simulations, and we discuss their implications for the multiphase structure of the Milky Way’s interstellar medium.

Inelastic resonant scattering of electrons on hydrogen-like ions

Abstract The inelastic electron scattering is one of the processes that must be understood in detail for the correct interpretation of astrophysical data. We suggest ab initio QED treatment of the inelastic scattering of quasi-free electrons on hydrogen-like ions with possible formation and subsequent decay of intermediate autoionizing states. We calculate the doubly differential cross sections for scattering on F8+, Ca19+ and Kr35+ in the range of energies where doubly excited 3 l 3 l ′ states are involved. The energies and widths of these states are presented.

Selective monodeuteration enabled by bisphosphonium catalyzed ring opening processes

The selective incorporation of a deuterium atom into small molecules with high selectivity is highly valuable for medical and chemical research. Unfortunately, this remains challenging due to the complete deuteration caused by commonly used hydrogen isotope exchange strategies. We report the development of a photocatalytic selective monodeuteration protocol utilizing C–C bond as the unconventional functional handle. The synergistic combination of radical-mediated C–C bond scission and deuterium atom transfer processes enables the effective constructions of benzylic CDH moieties with high selectivity for monodeuteration. The combinational use of a bisphosphonium photocatalyst, thiol catalyst, and CH3OD deuteration agent provides operationally simple conditions for photocatalytic monodeuteration. Moreover, the photoinduced electron transfer process of the bisphosphonium photocatalyst is elucidated through a series of spectroscopy experiments, identifying a peculiar back electron transfer process that can be regulated by subsequent nucleophilic additions.

Shuttle HAT for mild alkene transfer hydrofunctionalization.

Hydrogen atom transfer (HAT) from a metal-hydride is a reliable and powerful method for functionalizing unsaturated C-C bonds in organic synthesis. Cobalt hydrides (Co-H) have garnered significant attention in this field, where the weak Co-H bonds are most commonly generated in a catalytic fashion through a mixture of stoichiometric amounts of peroxide oxidant and silane reductant. Here we show that the reverse process of HAT to an alkene, i.e. hydrogen atom abstraction of a C-H adjacent to a radical, can be leveraged to generate catalytically active Co-H species in an application of shuttle catalysis coined shuttle HAT. This method obviates the need for stoichiometric reductant/oxidant mixtures thereby greatly simplifying the generation of Co-H. To demonstrate the generality of this shuttle HAT platform, five different reaction manifolds are shown, and the reaction can easily be scaled up to 100 mmol.

Synthesis of Alkyl Bis(trifluoromethyl)carbinols via Fe-LMCT-Enabled Hydrobis(trifluoromethyl)carbinolation of Alkenes.

Bis(trifluoromethyl)carbinols are valuable pharmacophores, yet their synthesis is challenging, largely due to a scarcity of safe and effective bis(trifluoromethyl)carbinolation reagents. Here, we realized the hydrobis(trifluoromethyl)carbinolation of alkenes, utilizing stable and readily accessible 2,2-bis(trifluoromethyl)glycolic acid as a source of both the bis(trifluoromethyl)carbinol unit and a hydrogen atom. This process leverages a photoinduced Fe-LMCT-enabled radical decarboxylation process that generates a key bis(trifluoromethyl)carbinol radical intermediate. Our mild protocol facilitates the synthesis of a diverse range of alkyl bis(trifluoromethyl)carbinols, including structurally complex molecules with pharmaceutical relevance.

Ab Initio Molecular Dynamics Studies of Stacked Adenine–Thymine and Guanine–Cytosine Nucleic Acid Base Pairs in Aqueous Solution

Ab initio MD studies have been performed on stacked adenine–thymine (A–T) and guanine–cytosine (G–C) nucleobase pairs solvated in water using Born–Oppenheimer molecular dynamics. These two systems have been analyzed using RDF, SDF, angle–distance CDF (combined distribution functions), plane projection analysis, hydrogen bond analysis, and non–covalent interaction (NCI) plots. The stacking property studies have shown that the molecular orientation of the A–T pair is completely opposite to that of the G–C pair though the center of mass distance between the two molecules is similar. The G–C pair shows significantly more stability in water than the A–T system does. RDF analyses show that the –NH– group and carbonyl groups show predominant interaction with water molecules. Water molecules are found to be most in numbers around the cytosine molecule and least around the adenine molecule. Hydrogen bonding studies show that the guanine molecule forms the highest number of hydrogen bonds with water molecules. On the other hand, the hydrogen atom attached to the –NH– group of adenine molecule shows the longest mean H–bond lifetime with water oxygen atoms. NCI interactions calculated through the ab initio method help us to visualize the [Formula: see text]-electron stacking and H–bonding between aromatic nucleobases and water molecules. A great shift in bond polarity and interaction intensity in different functional groups is observed for the nucleobases going from individually solvated molecules to paired states.

Diastereoselective Access to Ester-Substituted cis-Phenanthridinones via Hydrogen Atom Transfer-Involved 1,7-Enyne Bicyclization.

An organophotoredox-catalyzed 1,7-enyne bicyclization for the cis-diastereoselective synthesis of ester-substituted phenanthridinones has been achieved through radical cascade cyclization involving 1,6-hydrogen atom transfer. This transition-metal- and oxidant-free one-pot protocol generates three distinct C-C bonds and two quaternary carbon centers.

Determination of atomic hydrogen density and fluorescence decay time by 1D resolved, picosecond TALIF in the RAID linear device

Abstract We report on the first 1D resolved two-photon absorption laser-induced fluorescence (TALIF) measurements of atomic hydrogen (H) performed in the Resonant Antenna Ion Device using a picosecond laser system. The results are obtained across a cylindrical plasma column with peak electron density 10 18 m − 3 and temperature 1 eV on axis, which decrease monotonically to 2 ⋅ 10 17 m − 3 and 0.75 eV over a scale of a few cm away from the axis. TALIF results in these conditions are compatible with a uniform H density profile across the observed region, with a mean dissociation degree close to 3%. The small variation of H density across regions covering a wide range of plasma parameters suggests that transport processes and wall interactions play an important role in determining the H density profile. The fluorescence decay time is close to 10 ns at all observed locations, a result compatible with complete substate mixing of the n = 3 states of H.

Taming CO2•- via Synergistic Triple Catalysis in Anti-Markovnikov Hydrocarboxylation of Alkenes.

The direct utilization of carbon dioxide as an ideal one-carbon source in value-added chemical synthesis has garnered significant attention from the standpoint of global sustainability. In this regard, the photo/electrochemical reduction of CO2 into useful fuels and chemical feedstocks could offer a great promise for the transition to a carbon-neutral economy. However, challenges in product selectivity continue to limit the practical application of these systems. A robust and general method for the conversion of CO2 to the polarity-reversed carbon dioxide radical anion, a C1 synthon, is critical for the successful valorization of CO2 to selective carboxylation reactions. We demonstrate herein a hydride and hydrogen atom transfer synergy driven general catalytic platform involving CO2•- for highly selective anti-Markovnikov hydrocarboxylation of alkenes via triple photoredox, hydride, and hydrogen atom transfer catalysis. Mechanistic studies suggest that the synergistic operation of the triple catalytic cycle ensures a low-steady-state concentration of CO2•- in the reaction medium. This method using a renewable light energy source is mild, robust, selective, and capable of accommodating a wide range of activated and unactivated alkenes. The highly selective nature of the transformation has been revealed through the synthesis of hydrocarboxylic acids from the substrates bearing a hydrogen atom available for intramolecular 1,n-HAT process as well as diastereoselective synthesis. This technology represents a general strategy for the merger of in situ formate generation with a synergistic photoredox and HAA catalytic cycle to provide CO2•- for selective chemical transformations.

Photooxidation of Polyolefins to Produce Materials with In-Chain Ketones and Improved Materials Properties.

Herein, we report a selective photooxidation of commodity postconsumer polyolefins to produce polymers with in-chain ketones. The reaction does not involve the use of catalyst, metals, or expensive oxidants, and selectively introduces ketone functional groups. Under mild and operationally simple conditions, yields up to 1.23 mol % of in-chain ketones were achieved. Installation of in-chain ketones resulted in materials with improved adhesion of the materials and miscibility of mixed plastics relative to the unfunctionalized plastics. The introduction of ketone groups into the polymer backbone allows these materials to react with diamines, forming dynamic covalent polyolefin networks. This strategy allows for the upcycling of mixed plastic waste into reprocessable materials with enhanced performance properties compared to polyolefin blends. Mechanistic studies support the involvement of photoexcited nitroaromatics in consecutive hydrogen and oxygen atom transfer reactions.

Induced magnetic effects on intrinsic properties of edge-passivated triangular zigzag phosphorene quantum dots using spin-polarized density functional theory

The electrical and magnetic characteristics of edge-passivated triangular zigzag phosphorene quantum dots, saturated with hydrogen and oxygen atoms, have been investigated using spin-polarized density functional theory. The findings indicate that oxygen passivation alters the bond lengths, cohesive energies, and bandgaps of the quantum dots, leading to increased stability and magnetism due to unbonded single electrons in the oxygen atoms. The study also explored the impact of an external electric field on the energy gap, molecular orbital distribution, and local spin density of selected quantum dots. Our results show significant changes in the energy spectra and magnetic moments of the magnetized structures. The tunability of the magnetic and electronic attributes of triangular phosphorene quantum dots can be exploited in designing electronic and spintronic devices.

Pt12H24 -: A Cuboctahedral Platinum Hydride Cluster Cage.

The platinum hydride cluster Pt12H24 - is studied in gas phase by a combination of trapped ion electron diffraction and density functional theory computations. We find a cuboctahedral platinum cage with bridge bound hydrogen atoms. This unusual structure is stabilized by Pt-H-Pt multicenter bonds and shows characteristics of spherical aromaticity.

A Strongly Coupled Metal/Hydroxide Heterostructure Cascades Carbon Dioxide and Nitrate Reduction Reactions toward Efficient Urea Electrosynthesis.

The direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch-Meiser process in industry. The simultaneous activation of carbon dioxide and nitrate, however, as well as efficient C-N coupling on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based on synthesizing an Ag-CuNi(OH)2 composite to cascade carbon dioxide and nitrate reduction reactions for urea electrosynthesis. The strongly coupled metal/hydroxide heterostructure interface integrates two distinct sites for carbon dioxide and nitrate activation, and facilitates the coupling of *CO (on silver, where * denotes an active site) and *NH2 (on hydroxide) for urea formation. Moreover, the strongly coupled interface optimizes the water splitting process and facilitates the supply of active hydrogen atoms, thereby expediting the deoxyreduction processes essential for urea formation. Consequently, our Ag-CuNi(OH)2 composite delivers a high urea yield rate of 25.6 mmol gcat. -1 h-1 and high urea Faradaic efficiency of 46.1 %, as well as excellent cycling stability. This work provides new insights into the design of dual-site catalysts for C-N coupling, considering their role on the interface.

A Strongly Coupled Metal/Hydroxide Heterostructure Cascades Carbon Dioxide and Nitrate Reduction Reactions toward Efficient Urea Electrosynthesis

AbstractThe direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch–Meiser process in industry. The simultaneous activation of carbon dioxide and nitrate, however, as well as efficient C−N coupling on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based on synthesizing an Ag−CuNi(OH)2 composite to cascade carbon dioxide and nitrate reduction reactions for urea electrosynthesis. The strongly coupled metal/hydroxide heterostructure interface integrates two distinct sites for carbon dioxide and nitrate activation, and facilitates the coupling of *CO (on silver, where * denotes an active site) and *NH2 (on hydroxide) for urea formation. Moreover, the strongly coupled interface optimizes the water splitting process and facilitates the supply of active hydrogen atoms, thereby expediting the deoxyreduction processes essential for urea formation. Consequently, our Ag−CuNi(OH)2 composite delivers a high urea yield rate of 25.6 mmol gcat.−1 h−1 and high urea Faradaic efficiency of 46.1 %, as well as excellent cycling stability. This work provides new insights into the design of dual‐site catalysts for C−N coupling, considering their role on the interface.

Entropy Considerations in Stochastic Electrodynamics

The use of entropy concepts in the field of stochastic electrodynamics is briefly reviewed here. Entropy calculations that have been fully carried out to date are discussed in two main cases: first, where electric dipole oscillators interact with zero-point, or zero-point plus Planckian, or Rayleigh–Jeans radiation; and second, where only these radiation fields exist within a cavity. The emphasis here is on the first, more complicated, case, where both charged particles and radiation fields are present and interacting. Unlike the usual exposition on entropy in classical statistical mechanics, involving probabilistic notions of phase-space occupation, the calculations to date for both particles and fields, or for fields alone, follow the caloric entropy method, where the notions of heat flow, adiabatic surfaces, and isothermal conditions are utilized. Probability notions certainly still enter into the calculations, as the fields and charged particles interact stochastically together, following Maxwellian electrodynamics. Examples of phase-space calculations for harmonic oscillators and classical hydrogen atoms are carried out, emphasizing how much farther caloric entropy calculations have successfully gone.

Semitransparent Cu2O Films Based on CuO Back Layer for Photoelectrochemical Water Splitting and Photovoltaic Applications.

Cuprous oxide (Cu2O) as an intrinsic p-type semiconductor is promising for solar energy conversion. The major challenge in fabricating Cu2O lies in achieving both high transparency and high performance in a tandem device. The Cu2O photocathodes often employ gold as the back contact layer. However, it is not an optimal choice in tandem device due to its poor transmission, scarcity, and electron-hole recombination at the interface of Au and Cu2O. Here, we presented a facile method that utilizes the earth-abundant material copper oxide (CuO) to fabricate highly transparent Cu2O devices. The maximum transmittance of the Cu2O film on CuO (FTO/CuO/Cu2O) increased from 42 % to 58 % compared with Cu2O film on Au (FTO/Au (3 nm)/Cu2O) in 550-800 nm. After coating atomic layer deposition (ALD) layers and hydrogen evolution reaction (HER) catalyst, the photocurrent density at 0 V (versus RHE) of the semitransparent Cu2O photocathode with CuO as the back layer for photoelectrochemical (PEC) water splitting reached -4.9 mA cm-2, which showed a 24.5 % improvement compared with FTO/Au/Cu2O photocathode. Moreover, expanding the CuO layer strategy to the field of solar cells enables Cu2O solar cells to achieve a PCE of 2.37 %.

Plasmagestützter Prozess mit Einzelatom‐Katalysatoren zur Nachhaltigen Umwandlung von Kunststoffabfällen

AbstractDie stetig steigende Menge an Kunststoffabfällen erfordert effektive Lösungen zur Bewältigung dieser Herausforderung. In dieser Studie stellen wir eine neuartige plasmagestützte Strategie zur schnellen Zersetzung verschiedener Plastikabfälle, einschließlich Mischungen, in hochwertige Kohlenstoffnanomaterialien und Wasserstoff vor. Die H2‐Ausbeute und die H2‐Selektivität, die durch die katalysatorfreien plasmagestützten Prozesse erzielt wurden, sind 14,2‐ bzw. 5,9‐mal höher als bisher unter ähnlichen Bedingungen mit konventioneller thermischer Pyrolyse erreicht wurde. Bemerkenswert ist, dass dieser katalysatorfreie Plasmaprozess einen signifikant höheren Energieertrag an H2 (gH2/kWh) im Vergleich zu anderen Pyrolyseprozessen liefert. Durch die Kopplung von Plasmapyrolyse mit thermischer Katalyse durch den Einsatz von atomar dispergierten Katalysatoren 1 Gew.‐ % M/CeO2 (M=Fe, Co und Ni) kann die Wasserstoffproduktion weiter gesteigert werden. Insbesondere der 1 Gew.– %Co/CeO2 Katalysator zeigte eine hervorragende katalytische Leistung über 10 Zyklen der Kunststoffabfallzersetzung hinweg und erreichte die höchste H2‐Ausbeute von 46,7 mmol/gplastic (entsprechend 64,4 % der theoretischen H2‐Ausbeute) und nahezu 100 % Wasserstoffatom‐Rückgewinnungseffizienz im 7. Zyklus. Atomar dispergiertes Fe auf der CeO2‐Oberfläche (1 Gew.– % Fe/CeO2) konnte im integrierten plasma‐thermischen Katalyseprozess eine H2‐Ausbeute erzielen wie sie sonst nur mit deutlich höheren Beladungen von Fe‐Partikeln auf der CeO2‐Oberfläche (10 Gew.– % Fe/CeO2) erreicht wird. Daher wurde demonstriert, dass Einzelatom‐Katalysatoren einen vielversprechenden Weg für ein kostengünstiges und effizientes chemisches Kunststoffrecycling darstellen. Durch eine Kombination aus Experiment und Modellierung haben wir ein tiefgehendes Verständnis der katalytischen Mechanismen der untersuchten Einzelatom‐Katalysatoren im entwickelten plasmagestützten Prozess erzielt. Dieser innovative und unkomplizierte Ansatz bietet eine vielversprechende und schnelle Strategie zur kontinuierlichen Umwandlung verschiedener Kunststoffabfallströme, einschließlich gemischter und kontaminierter Quellen, in hochwertige Produkte, die eine Kreislaufwirtschaft für Kunststoffe unterstützen.

Integral Equation Approach for a Hydrogen Atom in a Strong Magnetic Field

Integral Equation Approach for a Hydrogen Atom in a Strong Magnetic Field

Transition-Metal-Free Radical Relay Cascade Annulation of Amides: Access to Antitumor Active Benzo[b]azepine and Oxindole Derivatives.

Efficient transition-metal-free synthesis of benzo[b]azepines and oxindoles is achieved via a radical relay cascade strategy employing halogen atom transfer (XAT) for aryl radical generation followed by intramolecular hydrogen atom transfer (HAT). Optimization yielded moderate to substantial yields under visible light irradiation. Preliminary biological assessments revealed promising anti-tumor activity for select compounds. This study underscores the potential of XAT-mediated radical relay cascades in medicinal chemistry and anticancer drug discovery.