Dissociation Of Molecules Research Articles

Efficient and Durable Oxidation Removal of Formaldehyde over Layered Double Hydroxide Catalysts at Room Temperature.

Room temperature catalytic oxidation (RTCO) using non-noble metals has emerged as a highly promising technique for removal of formaldehyde (HCHO) under ambient conditions; however, non-noble catalysts still face the challenges related to poor water resistance and low stability under harsh conditions. In this study, we synthesized a series of layered double hydroxides (LDHs) incorporating various dual metals (MgAl, ZnAl, NiAl, NiFe, and NiTi) for formaldehyde oxidation at ambient temperature. Among the synthesized catalysts, the NiTi-LDH catalyst showed an HCHO removal efficiency and CO2 yield close to 100.0%, and exceptional water resistance and chemical stability on running 1300 min. The abundant hydroxyl groups in LDHs directly bonded with HCHO, leading to the production of CO2 and H2O, thus inhibiting the formation of CO, even in the absence of O2 and H2O. The coexistence of O2 effectively reduced the reaction barrier for H2O molecule dissociation, facilitating the formation of hydroxyl groups and their subsequent backfill on the catalyst surface. The mechanisms underlying the involvement and regeneration of hydroxyl groups in room temperature oxidation of formaldehyde were elucidated with the combined in situ DRIFTS, HCHO-TPD-MS, and DFT calculations. This work not only demonstrates the potential of LDH catalysts in environmental applications but also advances the understanding of the fundamental processes involved in room temperature oxidation of formaldehyde.

Stable CO2 reduction under natural air on Ni–Sn hydroxide photocatalyst with dynamic renewable oxygen vacancies

Advanced photocatalysts are highly desired to activate the photocatalytic CO2 reduction reaction (CO2RR) with low concentration. Herein, the NiSn(OH)6 with rich surface lattice hydroxyls was synthesized to boost the activity directly under the natural air. Results showed that terminal Ni–OH could serve as donors to feed protons and generate oxygen vacancies (VO), thus beneficial to convert the activated CO2 (HCO3 −) mainly into CO (5.60 μmol g−1) in the atmosphere. It was flexible and widely applicable for a stable CO2RR from high pure to air level free of additionally adding H2O reactant, and higher than the traditional gas–liquid–solid (1.58 μmol g−1) and gas–solid (4.07 μmol g−1) reaction system both using high pure CO2 and plenty of H2O. The strong hydrophilia by the rich surface hydroxyls allowed robust H2O molecule adsorption and dissociation at VO sites to achieve the Ni–OH regeneration, leading to a stable CO yield (11.61 μmol g−1) with the enriched renewable VO regardless of the poor CO2 and H2O in air. This work opens up new possibilities for the practical application of natural photosynthesis.

Nucleation behaviors of p-coumaric acid in four solvents from induction time and metastable zone width: experiments and simulations

The study of nucleation behaviors during crystallization is important for understanding the drug crystallization process. The induction time of p-coumaric acid (p-CA) was measured in four solvents at various levels of supersaturation. The kinetic parameters of nucleation (interfacial energy, critical nucleation radius, and critical Gibbs free energy) were estimated using the classical nucleation theory (CNT). The results showed that the nucleation difficulty of p-CA in the four solvents was in the order of ethyl acetate > acetone > ethanol > methanol. In addition, the metastable zone width (MSZW) of p-CA was determined in four solvents. The nucleation behaviors of p-CA were further expounded using self-consistent Nývlt-like model and modified Sangwal’s model. The results were consistent with those of CNT. To further reveal the impact of interactions between solvent and solute molecules on the nucleation behaviors of p-CA, molecular electrostatic potential surfaces (MEPs), Hirshfeld Surfaces (HS), and the radial distribution function (RDF) were performed. The investigation revealed that the intensity of solvent–solute interactions depended primarily on the strength of hydrogen bonding interactions. The RDF results showed that the magnitude of hydrogen bonding interactions of p-CA in the four solvents was in the following order: ethyl acetate > acetone > ethanol > methanol. As the hydrogen bonding interactions between p-CA and solvent molecules became stronger, the dissociation of solute molecules from solvent molecules became more difficult, leading to a wider MSZW and a lower nucleation rate.

First-principles study of hydrogen sulfide decomposition on Sc-Ti3C2O2 single-atom catalyst.

Hydrogen sulfide gas poses significant risks to both human health and the environment, with the potential to induce respiratory and neurological effects, and a heightened fatality risk at elevated concentrations. This article investigates the catalytic decomposition of H2S on a Sc-Ti3C2O2 single-atom catalyst(SAC) using the density functional theory-based first-principles calculation approach. Initially, the adsorption behavior of H2S on Ti3C2O2-MXene was examined, revealing weak physical adsorption between them. Subsequently, the transition metal atom Sc was introduced to the Ti3C2O2 surface, and its stability was studied, demonstrating high stability. Further exploration of H2S adsorption on Sc-Ti3C2O2 revealed direct dissociation of H2S gas molecules into HS* and H*, with HS* binding to Sc and H* binding to O on the Ti3C2O2 surface, resulting in OH groups. Using the transition state search method, the dissociation of H2S molecules on the SAC's surface was investigated, revealing a potential barrier of 2.45eV for HS* dissociation. This indicates that the H2S molecule can be dissociated into H2 and S with the action of the Sc-Ti3C2O2 SAC. Moreover, the S atom left on the catalyst surface can aggregate to produce elemental S8, desorbing on the catalyst surface, completing the catalytic cycle. Consequently, the Sc-Ti3C2O2 SAC is poised to be an efficient catalyst for the catalytic decomposition of H2S. The Dmol3 module in Materials Studio software based on density functional theory is used in this study. The generalized gradient approximation method GGA-PBE is used for the exchange-correlation function. The complete LST/QST and the NEB methods in the Dmol3 module were used to study the minimum energy path of the dissociation of hydrogen sulfide molecules on the catalyst surface.

Interfacial electronic structure modulations of Au@CuS with defective Ni-doped CoS2 facilitates the electroreduction of N2 into NH3

The nitrogen reduction reaction (NRR) offers a sustainable pathway for ammonia production. However, its effectiveness is hindered by the selective adsorption of nitrogen and the subsequent occurrence of the hydrogen evolution reaction. In this work, a novel and efficient NRR catalyst, Au@CuS heterostructured nanoparticles supported on carbon-coated Ni-doped CoS2 hollow nanocages (Au@CuS/Ni-CoS2/C), was designed and synthesized to enhance the conversion of N2 to NH3 under ambient conditions. The defective Ni-CoS2@C nanocages not only provide a larger surface area for the loading of Au@CuS nanoparticles but also improve conductivity and promote synergistic effects among different components within catalyst. Both experimental investigations and density functional theory (DFT) calculations reveal that the integration of Au and CuS leads to unique inorganic donor–acceptor couplings with electron enriched in Au nanoparticles due to the higher work function of Au compared to CuS. This electron enrichment expedites the adsorption and dissociation of N2 molecules over the electron-rich Au active sites, thereby significantly optimizing the adsorption of intermediates and catalyzing subsequent hydrogenation reduction processes. Benefiting from these synergistic advantages, the resulting Au@CuS/Ni-CoS2/C catalyst exhibited high NRR electrocatalytic activity with a maximum NH3 yield of 25.61 µg h−1 mg−1cat. and a Faraday efficiency of 14.99 % at –0.3 V (vs. reversible hydrogen electrode, RHE), surpassing those of Au@CuS, Ni-CoS2/C, and Au/Ni-CoS2/C. This work presents a new strategy for precisely adjusting the valence state of Au species, thereby facilitating the production of valuable ammonia through NRR.

Promoting Electrochemical CO2 Reduction to Formate via Sulfur‐Assisted Electrolysis

AbstractElectrochemical CO2 reduction reaction (CO2RR) provides a renewable approach to transform CO2 to produce chemicals and fuels. Unfortunately, it faces the challenges of sluggish CO2 activation and slow water dissociation. This study reports the modification of Bi‐based electrocatalyst by S, which leads to a remarkable enhancement in activity and selectivity during electrochemical CO2 reduction to formate. Based on comprehensive in situ examinations and kinetic evaluations, it is observed that the presence of S species over Bi catalyst can significantly enhance its interaction with K+(H2O)n, facilitating fast dissociation of water molecules to generate protons. Further in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) and in situ Raman spectroscopy measurements reveal that S modification is able to decrease the oxidation state of Bi active site, which can effectively enhance CO2 activation and facilitate HCOO* intermediate formation while suppressing competing hydrogen evolution reaction. Consequently, the S‐modified Bi catalyst achieves impressive electrochemical CO2RR performance, reaching a formate Faradaic efficiency (FEformate) of 91.2% at a formate partial current density of ≈135 mA cm−2 and a potential of −0.8 V versus RHE in an alkaline electrolyte.

Selected Nonorthogonal Configuration Interaction with Compressed Single and Double Excitations.

Addressing both dynamic and static correlations accurately is a primary goal in electronic structure theory. Nonorthogonal configuration interaction (NOCI) is a versatile tool for treating static correlation, offering chemical insights by combining diverse reference states. Nevertheless, achieving quantitative accuracy requires the inclusion of the missing dynamic correlation. This work introduces a framework for compressing orthogonal single and double excitations into a NOCI of a much smaller dimension. This compression is repeated with each Slater determinant in a reference NOCI, resulting in another NOCI that includes all of its single and double excitations (NOCISD), effectively recovering the missing dynamic correlations from the reference. This compressed NOCISD is further refined through a selection process using metric and energy tests (SNOCISD). We validate the effectiveness of SNOCISD through its application to the dissociation of the nitrogen molecule and the hole-doped two-dimensional Hubbard model at various interaction strengths.

Effects of sulfur‐ and Fe‐deficient defects on the decomposition of hydrogen peroxide H2O2 on pyrite surface

AbstractThere is still a lack of research on the effect of the S and Fe vacancy on the adsorption mechanism of peroxide (H2O2) on the pyrite surface. In this work, the adsorption of H2O2 molecules on the perfect and defective pyrite surface is simulated based on density functional theory (DFT). The results indicated that the adsorption energy of H2O2 molecules on the S‐vacancy surface is relatively lower than that on the perfect surface and dissociative adsorption entirely occurs, while the adsorption behavior of H2O2 molecules on the S‐rich pyrite surface has not occurred. When the H2O2 molecules are adsorbed on the Fe‐rich pyrite surface, two products appear, one with two OH− species and the other with an H2O molecule and an O atom. The analysis of the transition state (TS) found that the dissociation of the H2O2 molecule producing two OH− species that bond with two Fe atoms is more likely to occur. In addition, based on the coordination chemistry, it is demonstrated that Fe atoms are more reactive around an S vacancy than on a perfect surface.

Surface-Assisted Laser Desorption/Ionization Mass Spectrometry with a Two-Dimensional Au Nanoparticle Array for Soft Ionization.

Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) is a valuable technique for detecting small molecules in environmental and medicinal studies. We investigated dot-like and 2D-array gold nanoparticle-based SALDI-MS substrates that excite surface plasmons and enhance the desorption/ionization of sample molecules via charge transfer between the substrate and sample molecules. We aimed to optimize the nondissociative detection of sample molecules by efficiently transferring energy while suppressing excess internal energy. SALDI-MS measurements using crystal violet (CV) molecules revealed ion intensity and spectral pattern differences between the dot-like and 2D-array substrates. SALDI-MS measurements using dot-like substrates suggested two desorption/ionization processes: internal energy supply and charge transfer between the substrate and sample molecules. However, SALDI-MS measurements using 2D-array substrates suggested that the internal energy supply was suppressed. As a result, the dot-like substrate provided higher desorption/ionization efficiency but increased fragmentation, whereas the 2D-array substrate was suitable for highly sensitive and nondissociative SALDI-MS measurements. This study contributes to the optimization of SALDI-MS measurements and advances our understanding of energy transfer and sample molecule dissociation.

Regulating the d-band center of Cu nanoparticles for efficient photo-driven catalytic CO2 reduction

The conversion of CO2 into solar fuels via photo-driven catalytic reduction presents a promising avenue toward achieving carbon neutrality. Herein, copper-based catalysts are prepared and explored for photo-driven photothermal CO2 reduction reaction. The optimized catalyst exhibits a consistent CO production rate of 165.9 mmol g−1 h−1 and 100% CO selectivity at ambient pressure. We unveil the intricate adsorption dynamics at play: H2 molecules predominantly interact with and activate at Cu sites, while CO2 molecules preferentially adsorb and activate at interfacial sites within the composites. Furthermore, we elucidate how the positive shift of the d-band center (εd) for Cu 3d orbitals significantly enhances H2 adsorption and activation. Crucially, the subsequent dissociation of H2 molecules at Cu sites drives the efficient conversion of adsorbed CO2 molecules at interfacial sites into CO. Overall, our findings not only advance the theoretical understanding but also offer practical insights for realizing photothermal catalytic CO2 reduction reactions.

Initiation and Carbene Induced Radical Chain Reactions in CH2F2 Pyrolysis.

High temperature dissociations of organic molecules typically involve a competition between radical and molecular processes. In this work, we use a modeling, experiment, theory (MET) framework to characterize the high temperature thermal dissociation of CH2F2, a flammable hydrofluorocarbon (HFC) that finds widespread use as a refrigerant. Initiation in CH2F2 proceeds via a molecular elimination channel; CH2F2→CHF+HF. Here we show that the subsequent self-reactions of the singlet carbene, CHF, are fast multichannel processes and a facile source of radicals that initiate rapid chain propagation reactions. These have a marked influence on the decomposition kinetics of CH2F2. The inclusion of these reactions brings the simulations into better agreement with the present and literature experiments. Additionally, flame simulations indicate that inclusion of the CHF+CHF multichannel reaction leads to a noticeable enhancement in predictions of laminar flame speeds, a key parameter that is used to determine the flammability of a refrigerant.

Numerical investigations on flow and heat transfer characteristics of a high-enthalpy double-cone in thermal and chemical non-equilibrium for hypersonic propulsion

There are strong interests in hypersonic propulsion communities in predicting the flow and heat transfer characteristics over a hypersonic vehicle. However, this is quite challenging due to the emergence of thermal and chemical out-of-equilibrium effects as prominent in a high-temperature flow. In this work, we conduct 2D numerical investigations on the hypersonic double cone flow in a surrounding of the stagnation enthalpy of 15.23 MJ/kg by solving the laminar Navier–Stokes equation systems with the vibrational non-equilibrium processes and seven species air reactions. We then conduct the sensitivities analyses on the flow and heat transfer features, as different transport models and different thermochemical models are applied. It is shown that the aerodynamic heat is more sensitive to the transport models than the flow, and the transport coefficients computed by the Gupta-Yos model are more suitable for predicting the double cone flow at the high enthalpy. On the other hand, the flow field of the high enthalpy double cone is more sensitive to the thermochemical models than the heat transfer on the wall excluding the peak position. Behind the detached shock, chemical reactions are found to enhance thermal or vibrational out-of-equilibrium effects. However, vibrational non-equilibrium effects are revealed to weaken the degree of molecule dissociation reactions. Two flow separations occur in the flow field computed by using the thermal non-equilibrium gas models, but the flows of thermal equilibrium gas models separate only once. The maximum values of wall parameters without chemical reactions are found to deviate greatly from the experimental measurements. The thermochemical out-of-equilibrium gas model can predict the separation region size closer to the experiment than the two reported numerical results. The wall static pressure and heat flux are also shown to well match the experimental results. The present work should shed lights on better understanding thermochemical non-equilibrium effects of complex flow phenomenon like the shock wave/boundary layer interaction in hypersonic propulsion with high enthalpy surroundings.

Spin-cross interface-inducing ultra-high catalytic activity in Co(OH)xPy-MXene toward alkali-free liquid hydrogen generation

Proclaiming the interfacial active sites of non-noble metals on supported catalysts is a paramount topic. Herein, a spin-cross interface (Co(OH)xPy (x/y=3.2)) in the intimate region between Co(OH)2 and CoP is designed by in situ hydroxylation and P-inducing strategy. An ultra-high catalytic hydrogen generation activity with a turnover frequency of 1640 min−1 is achieved for hydrolysis of ammonia borane (NH3BH3). Both experimental observations and computational simulations reveal that the spin-cross interface dramatically reduces the energy barriers for the dissociation of reactant molecules (NH3BH3 and H2O) to expedite the catalytic activity. The coexistence of active interface and MXene create the ensembles of Co atoms coordinated by OH and P. The construction of active sites of Co(OH)xPy simultaneously boosts the adsorption and dissociation of H2O and NH3BH3 molecules. This research provides new paradigm for the rational design of spin-induced catalysts in the future energy system depending on the activation of multi-molecules.

Unraveling Hydrogen Adsorption on Transition Metal-Doped [Mo3S13]2- Clusters: Insights from Density Functional Theory Calculations.

Molecular and dissociative hydrogen adsorption of transition metal (TM)-doped [Mo3S13]2- atomic clusters were investigated using density functional theory calculations. The introduced TM dopants form stable bonds with S atoms, preserving the geometric structure. The S-TM-S bridging bond emerges as the most stable configuration. The preferred adsorption sites were found to be influenced by various factors, such as the relative electronegativity, coordination number, and charge of the TM atom. Notably, the presence of these TM atoms remarkably improved the hydrogen adsorption activity. The dissociation of a single hydrogen molecule on TM[Mo3S13]2- clusters (TM = Sc, Cr, Mn, Fe, Co, and Ni) is thermodynamically and kinetically favorable compared to their bare counterparts. The extent of favorability monotonically depends on the TM impurity, with a maximum activation barrier energy ranging from 0.62 to 1.58 eV, lower than that of the bare cluster (1.69 eV). Findings provide insights for experimental research on hydrogen adsorption using TM-doped molybdenum sulfide nanoclusters, with potential applications in the field of hydrogen energy.

Post‐microwave plasma catalysis: Current developments and future implications

AbstractPost‐microwave plasma catalysis combines plasma preactivation of the gas phase followed by a fixed bed catalyst. This process has the potential to be energy efficient, modular, versatile and to generate high numbers of active species compared with other plasma generation technologies. Specific applications of these post‐microwave plasma systems include the dissociation and activation of stable molecules and the modification of catalyst materials. This concept article will address the current findings in microwave plasma catalysis research and propose future questions that need to be addressed to further develop the technology.

Promoting intermediates transformation by boosting H2O dissociation over core-shell Pd@CoO Janus for acetone efficacious oxidation

Reactivity loss by intermediates aggregation and water vapor inhibition are two major and longstanding challenges for the noble-metal-based catalysts in oxygenated volatile organic compounds (OVOCs) oxidation. Herein, the core-shell Pd@CoO Janus sites are creatively designed and stabilized over the HSAPO-34 support. Quasi in situ XPS spectra reveal that the strong interactions in Pd@CoO Janus sites promote the charge redistribution and electron back-donation through Pd-O-Co coordination. Therefore, abundant positively charged Pd2+ sites are formed and oxygen species transformation is facilitated, which significantly promote the low-temperature efficiency of acetone oxidation. Furthermore, the Pd@CoO/HSAPO-34 catalyst facilitates H2O molecules dissociation and produce reactive OHTer and OHTri species, which considerably promotes the rapid decomposition of aldehyde intermediate via attacked CH2O* group, ensuring low-temperature oxidation of acetone. This work provides valuable guidance to develop specific catalysts with functional active sites for rationally utilizing H2O molecules to improve low-temperature performance and modulate reaction pathways during OVOCs oxidation.

Atomically Dispersed Ga Synergy Lewis Acid‐Base Pairs in F‐doped Mesoporous Cu2O for Efficient Eletroreduction of CO2 to C2+ Products

AbstractElectroreduction of CO2 into high‐value chemicals and fuels driven is an effective way to alleviate the environmental crisis, but it suffers from poor activity and low selectivity of the catalyst. Single‐atom catalysts have excellent selectivity and the highest atomic efficiency, and are widely used in the 2‐electron transfer to produce CO. However, electroreduction of CO2 to C2+ products involves complex processes such as multi‐electron reaction and competitive adsorption, so single‐atom catalysis is often powerless. Herein, a single‐atom Ga‐anchored F‐doped Cu2O catalyst with dual active sites is reported. The Lewis acid‐base pairs and Ga single atom sites promote the adsorption/activation of CO2 and the dissociation of water molecules, respectively, enhance the coverage of *CO and *H, and their synergy optimizes the reaction path. At a high current density of 600 mA cm−2, the FEC2+ reached 72.8 ± 3.2% with remarkable stability. Experiments and theory calculations demonstrate that the dual sites increase the coverage of *CO and *H, and the key intermediate *CO is transformed into *CHO through protonation reaction, which changes the reaction path from the C─C coupling (*OCCO) to the protonation followed by C─C coupling (*OCCHO) with low energy barrier, greatly improving the selectivity for C2+ products.

Unlocking the Potential of Cu/Ti3C2Tx MXene Catalyst in Plasma Catalytic CO2 Hydrogenation

Plasma catalytic CO2 hydrogenation has emerged as a promising approach for converting CO2 into valuable chemicals such as CO, offering a potential solution to mitigate greenhouse gas emissions. In this study, we investigate the synergistic effect between plasma and a Cu/Ti3C2Tx MXene catalyst for CO2 hydrogenation via the reverse water gas shift (RWGS) reaction in a dielectric barrier discharge (DBD) reactor. Our findings reveal a significant enhancement in CO2 conversion (33.1%) and CO yield (31.9%) when using the Cu/Ti3C2Tx catalyst compared to plasma alone or with a Ti3C2Tx foam. Plasma treatment creates unsaturated Ti sites on the Ti3C2Tx surface, dramatically improving CO2 adsorption and activation, while Cu nanoparticles significantly enhances the activation and dissociation of H2 molecules on the catalyst surface. These surface adsorbed hydrogen species readily hydrogenate adsorbed CO2 molecules through the Langmuir-Hinshelwood mechanism. Furthermore, these surface hydrogen species can also participate in the conversion of gas-phase CO2 molecules through the Eley-Rideal pathway. This work sheds light on the synergistic plasma catalytic mechanism and provide insights for optimizing CO2 hydrogenation processes using MXene catalysts.

Preparation of PVA/CNTs film with high stability and humidity sensitivity based on multiple process

Polyvinyl alcohol (PVA) is a polyhydroxylated water-soluble polymer with rapid response to water molecules in environment. In this paper, a humidity sensitive PVA film with both high stability and satisfactory humidity sensitivity were prepared based on multiple process, i.e., crosslinking, foaming, spin coating and composition with hydroxylated carbon nanotubes (CNTs). The crosslinking of PVA with formaldehyde enhances the stability of the film under cyclic test condition, which exhibits deviation ratio of 1.1 and 1.2 in response and recovery process respectively. The pore structure generated by foaming agent promotes the water vapor exchange efficiency and improve the humidity response and recovery performance. The spin coating speed significantly influences the pore structure and thickness of the prepared films. CNTs facilitate the dissociation of water molecule through hole carriers and hydroxyl groups to reduce the resistance of PVA/CNTs films and enlarge the humidity response range. The spin coating speed and CNTs content jointly determine the final foaming structure and film thickness. Based on the multiple methods, the obtained crosslinked open pore film exhibits satisfactory humidity sensitive properties with the response time of 48 s and equilibrium time of 296 s, which should have good application prospect.

Formation of HfCxNy by carbothermal reduction nitridation and their laser ablation behavior

Hafnium carbonitride (HfCxNy) powders have been successfully prepared by heating a mixture of fine-grained HfO2 and nano-carbon powders during 1873 K-2273 K in nitrogen. The carbothermal reduction nitrdation (CTRN) process is composed of two steps: (1) the formation of microporous HfC and (2) catalytic nitridation of microporous HfC. The results demonstrate that the as-prepared HfCxNy powder consists of a single phase and various nitrogen content through different sintering parameters. The mechanism consists of three stages: (1) Formation of cubic mixed crystal HfCxOy, (2) Transformation into microporous hafnium carbide, and (3) Crucially, microporous hafnium carbide catalyzes the activation and dissociation of nitrogen molecules, leading to the formation of HfCxNy. Additionally, we introduce a laser etching method to confirm the ultra-high-temperature melting behavior of HfCxNy. This study enhances our understanding of HfCxNy powders synthesis and their laser ablation performance, offering valuable insights for future material applications.