Per- and polyfluoroalkyl substances (PFASs) are synthetic contaminants found in drinking groundwater sources a wide variety of consumer products. Because their adverse environmental human health effects, remediation these persistent compounds has attracted significant recent attention. To gain mechanistic insight into remediation, we present the first ab initio study PFAS degradation via hydrated electrons─a configuration that not been correctly considered previous computational studies up...

Porous organic polymers (POPs) continue to garner immense attention for CO2 capture and sequestration (CCS) as well fixation generate useful chemicals alleviating global warming. Functionally engineered, visible light responsive photopolymers with extended π-conjugation abundant heteroatoms enable photogenerated charge carriers, enhancement in absorption, higher separation, reduction recombination during photocatalysis. In this work, we have explored the construction of a chemically stable,...

Perfluorooctanoic acid (PFOA) is a part of large group anthropogenic, persistent, and bioaccumulative contaminants known as per- polyfluoroalkyl substances (PFAS) that can be harmful to human health. In this work, we present the first ab initio molecular dynamics (AIMD) study temperature-dependent degradation PFOA on (100) (110) surfaces γ-Al2O3. Our results show does not occur pristine surface, even when carried out at high temperatures. However, introducing an oxygen vacancy surface...

Abstract Systematic optimization of the photocatalyst and investigation role each component is important to maximizing catalytic activity comprehending photocatalytic conversion CO 2 reduction solar fuels. A surface‐modified Ag@Ru‐P25 with H O treatment was designed in this study convert vapor into highly selective CH 4 . Ru doping followed by Ag nanoparticles (NPs) cocatalyst deposition on P25 (TiO ) enhances visible light absorption charge separation, whereas modifies surface hydroxyl...

Computational chemistry methods, such as density functional theory (DFT), have now become more common in environmental research, particularly for simulating the degradation of per- and polyfluoroalkyl substances (PFAS). However, vast majority PFAS computational studies focused on conventional DFT approaches that only probe static, time-independent properties near stationary points potential energy surface. To demonstrate rich mechanistic information can be obtained from time-dependent...

Metalated nanoporous organic polymers (M-POPs) combine covalent bonds and open metal sites to enable structural stability single-site catalysis. In this work, we constructed two Pd-metalated knitting aromatic (Pd@KAP-1 Pd@KAP-2) explored their catalytic activity in lignocellulosic biomass-derived furfural (FFR) upgrading tetrahydrofurfuryl alcohol (THFAL), a green industrial solvent. Pd@KAP-1 exhibits superior performance compared Pd@KAP-2 toward FFR conversion, resulting 80% conversion with...

We have performed an extensive investigation of the parameters affecting degree nitrogen fixation and its energy cost in a low-pressure, radio frequency-driven plasma reactor. find that hydrogen-to-nitrogen ratio has strong effect on both yield cost. A significant (∼8%) can be achieved under hydrogen-rich mixtures, but unfortunately these conditions require higher input compared to one-to-one ratio. The high largely exceeds dissociation plasma, suggesting that, while likely contributes...

The rational synthesis of durable, earth-abundant efficient electrocatalysts for the oxygen evolution reaction (OER) from water is one most important routes storing renewable energy and minimizing fossil fuel combustion. prime hurdles effectively utilizing commercial RuO2 as are its very low stability, catalyst deactivation, high cost. In this work, we explored a Ru-integrated porous organic polymer (Ru@Bpy-POP) by facile one-pot Friedel-Crafts alkylation strategy between redox-active...

Near-surface nitrogen vacancy (NV) centers are promising candidate materials for quantum sensors, but their properties have not been examined as thoroughly compared to bulk counterparts. To shed mechanistic insight into electronic and stabilities, we present the first ab initio molecular dynamics study mechanical analysis of these near-surface NV center configurations. Our calculations predict that near 111 surface more energetically stable than defects located deeper in diamond structure....

The enhanced degradation of organophosphorous-based chemical warfare agents (CWAs) on metal oxide surfaces holds immense promise for neutralization efforts; however, the underlying mechanisms in this process remain poorly understood. For first time, we utilize large-scale quantum calculations to probe high-temperature diisopropyl methylphosphonate (DIMP), a nerve agent simulant. Our Born–Oppenheimer molecular dynamics (BOMD) show that γ-Al2O3 surface shows quickly adsorbing and destroying...

The elimination of per- and polyfluoroalkyl substances (PFAS) in water continues to garner significant attention due their enduring presence the environment associated health concerns. emergence advanced reduction processes (ARPs) holds promise reducing persistent PFAS water, primarily its ability produce short-lived yet highly reductive hydrated electrons. This concise review offers insights into latest developments ARP-based degradation, encompassing both experimental theoretical...

Nonthermal plasmas provide a unique approach to electrically driven heterogeneous catalytic processes. Despite much interest from the community, fundamental activation pathways in these processes remain poorly understood. Here, we investigate how exposure nonthermal plasma sustained an argon nonreactive atmosphere affects desorption of carbon monoxide (CO) platinum nanoparticles. Temperature-programmed measurements indicate that reduces effective binding energy (BE) CO Pt surfaces by as ∼0.3...

Many anomalous properties of water can be explained on the basis coexistence more than one density states: high-density (HDW) and low-density (LDW). We investigated these two phases molecules through first-principles molecular dynamics simulations using functional theory (DFT) in conjunction with various van der Waals-corrected exchange correlation functionals. Different regions were found to exist due difference short-range long-range forces present DFT potentials. These identified analyzed...

Free energy landscape obtained from <italic>ab initio</italic> metadynamics calculations for dimethylamine protonation at the air–water interface.

The hydrogen-bonded structure and dynamics of aqueous N,N-dimethylformamide (DMF) solutions varying compositions are investigated by means molecular simulations at three different temperatures ambient pressure. dynamical aspects the solution in terms single-particle mutual diffusion coefficients, calculated from mean square displacement, also lifetimes water–water water–DMF hydrogen bonds. densities coefficients compared with available experimental data; it is observed that they agree...

Abstract We performed Car‐Parrinello molecular dynamics (CPMD) simulations of deuterated aqueous solution methylamine (MA) to investigate the structure, and time dependent vibrational spectra water molecules in first solvation shell. Our results show that hydrogen bond DOD…ND 2 is dominant interaction between ND D O as compared O…D N. The involving has longer lifetime (2.6 ps) than both N (1.1 water‐water bonds. residence molecule inside shell 5.72 ps. spectral diffusion hydration amine...

The fluctuation dynamics of amine stretching frequencies, hydrogen bonds, dangling N–D and the orientation profile group methylamine (MA) were investigated under ambient conditions by means dispersion-corrected density functional theory-based first principles molecular (FPMD) simulations.

The elimination of per- and polyfluoroalkyl substances (PFAS) in water continues to garner significant attention due their enduring presence the environment associated health concerns. emergence advanced reduction processes (ARPs) holds promise reducing persistent PFAS water, primarily its ability produce short-lived yet highly reductive hydrated electrons. This concise review offers insights into latest developments ARP-based degradation, encompassing both experimental theoretical...

We present the characteristic proton transfer process from water to pyrazole anion, infrared signatures of hydroxyl groups and free energy profile in aqueous solution combining first principles simulations, wavelet analysis metadynamics. Our results show that presence minimum three molecules gas phase cluster with a particular arrangement is sufficient facilitate anion. The overall reaction very rapid solution, barrier for this found be 4.2 kcal mol-1. One earlier reported fundamental...