Chemical Reactions In Solution Research Articles

In‐Situ Ultrafast Construction of Zinc Tungstate Interface Layer for Highly Reversible Zinc Anodes

AbstractConstructing artificial solid electrolyte interface on the Zn anode surface is recognized as an appealing method to inhibit zinc dendrites and side reactions, whereas the current techniques are complex and time‐consuming. Here, a robust and zincophilic zinc tungstate (ZnWO4) layer has been in situ constructed on the Zn anode surface (denoted as ZWO@Zn) by an ultrafast chemical solution reaction. Comprehensive characterizations and theoretical calculations demonstrate that the ZWO layer can effectively modulate the interfacial electric field distribution and promote the Zn2+ uniform diffusion, thus facilitating the uniform Zn2+ nucleation and suppressing zinc dendrites. Besides, ZWO layer can prevent direct contact between the Zn/water and increase the hydrogen evolution reaction overpotential to eliminate side reactions. Consequently, the in situ constructed ZWO layer facilitates remarkable reversibility in the ZWO@Zn||Ti battery, achieving an impressive Coulombic efficiency of 99.36 % under 1.0 mA cm−2, unprecedented cycling lifespan exceeding 1800 h under 1.0 mA cm−2 in ZWO@Zn||ZWO@Zn battery, and a steady and reliable operation of the overall ZWO@Zn||VS2 battery. The work provides a simple, low cost, and ultrafast pathway to crafting protective layers for driving advancements in aqueous zinc‐metal batteries.

Immobilization properties and reaction mechanism of municipal solid waste incineration fly ash with alkali activation technology

Municipal solid waste incineration fly ash (MSWIFA) needs proper treatment prior to security landfilling because of considerable amounts of heavy metals and soluble chloride. Nowadays, alkali activation technology has become an effective solidification/stabilization (S/S) technology for MSWIFA. But few studies have been systematically carried out on the preparation techniques and reaction mechanism of MSWIFA S/S body. The effects of the technical parameters (alkali activator, sodium silicate modulus, alkali equivalent, water-solid ratio, curing regime) on the immobilization properties (compressive strength and heavy metal leaching toxicity) of MSWIFA S/S bodies were studied in this work. The hydration characteristics and reaction mechanism were also explored in depth based on the structure properties and microstructure characterization. Ca2+, Na+, SiO42−, [Al(OH)4]-, OH− dissociated from MSWIFA and alkali activator solution chemical reaction to form the silicates, aluminates and aluminosilicates with lower polymerization, and promoted the gel hydration products formation via depolycondensation. Lower Ca/Si molar ratio was conductive to the formation of amorphous substance, compactness of matrix pore structure and immobilization properties. Compared to the hydration products including halite, sylvine, glauberite, gypsum, calcite crystal, C–S–H gel contributed much more to the pore structure and strength improvement of MSWIFA S/S bodies. These findings will provide valuable theoretical basis for MSWIFA management and resource utilization promotion.

Revisiting Textbook Azide-Clock Reactions: A "Propeller-Crawling" Mechanism Explains Differences in Rates.

An ongoing challenge to chemists is the analysis of pathways and kinetics for chemical reactions in solution, including transient structures between the reactants and products that are difficult to resolve using laboratory experiments. Here, we enabled direct molecular dynamics simulations of a textbook series of chemical reactions on the hundreds of ns to μs time scale using the weighted ensemble (WE) path sampling strategy with hybrid quantum mechanical/molecular mechanical (QM/MM) models. We focused on azide-clock reactions involving addition of an azide anion to each of three long-lived trityl cations in an acetonitrile-water solvent mixture. Results reveal a two-step mechanism: (1) diffusional collision of reactants to form an ion-pair intermediate; (2) "activation" or rearrangement of the intermediate to the product. Our simulations yield not only reaction rates that are within error of experiment but also rates for individual steps, indicating the activation step as rate-limiting for all three cations. Further, the trend in reaction rates is due to dynamical effects, i.e., differing extents of the azide anion "crawling" along the cation's phenyl-ring "propellers" during the activation step. Our study demonstrates the power of analyzing pathways and kinetics to gain insights on reaction mechanisms, underscoring the value of including WE and other related path sampling strategies in the modern toolbox for chemists.

Femtosecond Collisional Dissipation of Vibrating D_{2}^{+} in Helium Nanodroplets.

We explored the collision-induced vibrational decoherence of singly ionized D_{2} molecules inside a helium nanodroplet. By using the pump-probe reaction microscopy with few-cycle laser pulses, we captured in real time the collision-induced ultrafast dissipation of vibrational nuclear wave packet dynamics of D_{2}^{+} ion embedded in the droplet. Because of the strong coupling of excited molecular cations with the surrounding solvent, the vibrational coherence of D_{2}^{+} in the droplet interior only lasts for a few vibrational periods and completely collapses within 140fs. The observed ultrafast coherence loss is distinct from that of isolated D_{2}^{+} in the gas phase, where the vibrational coherence persists for a long time with periodic quantum revivals. Our findings underscore the crucial role of ultrafast collisional dissipation in shaping the molecular decoherence and solvation dynamics during solution chemical reactions, particularly when the solute molecules are predominantly in ionic states.

Temperature dependent resistivity switching in CuxO thin films chemically synthesized from high pressure plasma-deposited copper iodide

A facile chemical synthetic method was used to synthesize CuxO thin films on glass substrate via in-situ chemical reaction of CuI thin films in NaOH solution at ambient temperature. CuI thin films were produced by a low-cost plasma-assisted dissociation of the chemical vapor of CuI in acetonitrile (CH3CN) at a pressure of 60 Torr. The prepared CuxO thin films were annealed at various temperatures. The XRD studies unveiled the amorphous character of the CuxO thin films. The SEM images indicated that the surfaces of the films were smooth and smoothness depended on annealing temperature. The EDS studies revealed the presence of huge amounts of C and O with a little amount of Cu in the films which resulted due to the deposition of C produced through dissociation of CH3CN in plasma and O produced from chemical reaction in solution. The optical studies showed that transmittance of the CuxO thin films decreased from that of the CuI thin films and depended on the annealing temperatures. The bandgap of the CuxO thin films decreased with annealing temperature and was in the range of 2.30–2.98 eV. The CuxO thin films exhibited resistivity switching behavior in the first heating-cooling cycle and then the resistivity increased with temperature indicating the metallic behavior. These results are propitious for the application CuxO thin films in solar cells and memristor devices.

Speeding-up Hybrid Functional-Based Ab Initio Molecular Dynamics Using Multiple Time-stepping and Resonance-Free Thermostat.

Ab initio molecular dynamics (AIMD) based on density functional theory (DFT) has become a workhorse for studying the structure, dynamics, and reactions in condensed matter systems. Currently, AIMD simulations are primarily carried out at the level of generalized gradient approximation (GGA), which is at the second rung of DFT functionals in terms of accuracy. Hybrid DFT functionals, which form the fourth rung in the accuracy ladder, are not commonly used in AIMD simulations as the computational cost involved is 100 times or higher. To facilitate AIMD simulations with hybrid functionals, we propose here an approach using multiple time stepping with adaptively compressed exchange operator and resonance-free thermostat, that could speed up the calculations by ∼30 times or more for systems with a few hundred of atoms. We demonstrate that by achieving this significant speed up and making the compute time of hybrid functional-based AIMD simulations at par with that of GGA functionals, we are able to study several complex condensed matter systems and model chemical reactions in solution with hybrid functionals that were earlier unthinkable to be performed.

Combining X-ray Absorption and NMR spectroscopies to investigate a chemical reaction in solution

Transition metal chemistry in solution is central to key processes in biology and catalysis. Achieving accurate knowledge on the structural and electronic properties of the relevant reaction intermediates requires the use of innovative and complementary spectroscopic probes. Herein, we combine X-ray Absorption Spectroscopy (XAS) and 1H-NMR to investigate the exchange reaction between two prototypical Cu coordination complexes in solution. By means of multivariate and theoretical analyses, we identify the number, nature and concentration time evolution of the relevant reaction intermediates and quantitatively determine their structures. The XAS and NMR techniques are proven to be complementary experimental tools to track the fate of both the metal and organic portions of reactive systems involving transition metals. The employed combined experimental and theoretical method may be useful in the study of reactive systems involving intermediates that may be labile or silent to conventional detection.

Hydration Rearrangement in the 4-Aminobenzonitrile-(H2 O)2 Cluster Induced by Photoionization: The Effect of Solvent-Solvent Interactions.

The interplay between solute-solvent and solvent-solvent interactions plays an essential role in solvation dynamics that has important effects on the mechanism and dynamics of chemical reactions in solution. In this study, the rearrangement of the hydration shell induced by photoionization of a solute molecule is probed in a state- and isomer-specific manner by resonant multiphoton ionization detected IR spectroscopy of the prototypical 4-aminobenzonitrile-(H2 O)2 cluster produced in a molecular beam. IR spectra reveal that the water molecules form a cyclic solvent network around the CN group in the initial neutral state (S0 ). Different from the singly-hydrated cluster, in which either the CN or the NH2 group is hydrated, hydration of the NH2 group is not observed in the dihydrated cluster. IR spectra obtained after ionizing the solute molecule into the cation ground state (D0 ) exhibit features ascribed to both NH-bound and CN-bound isomers, indicating that water molecules migrate from the CN to the NH site upon ionization with a yield depending on the ionization excess energy. Analysis of the IR spectra as a function of the excess energy shows that migration produces two different NH2 solvated structures, namely (i) the most stable structure in which both N-H bonds are singly hydrated and (ii) the second most stable isomer in which one of the N-H bonds is hydrated by a H-bonded (H2 O)2 dimer. The product branching ratio of the two isomers depends on the excess energy. The role of the water-water interaction in the hydration rearrangement is discussed based on the potential energy landscape. Solvation dynamics plays an important role in reaction mechanisms in the condensed phase, where not only solute-solvent solvation but also solvent-solvent interactions have a significant influence on the dynamics. Thus, the investigation of solvation dynamics at the molecular level substantially contributes to our understanding of the reaction mechanism. In this study, the dihydrated cluster of 4ABN was utilized as a model for the first solvation layer to elucidate solvent motions induced by ionization of the solute and the role of W-W interactions for the solvent relaxation.

Assessing an aqueous flow cell designed for in situ crystal growth under X-ray nanotomography and effects of radiolysis products.

Nucleation and growth of minerals has broad implications in the geological, environmental and materials sciences. Recent developments in fast X-ray nanotomography have enabled imaging of crystal growth in solutions in situ with a resolution of tens of nanometres, far surpassing optical microscopy. Here, a low-cost, custom-designed aqueous flow cell dedicated to the study of heterogeneous nucleation and growth of minerals in aqueous environments is shown. To gauge the effects of radiation damage from the imaging process on growth reactions, radiation-induced morphological changes of barite crystals (hundreds of nanometres to ∼1 µm) that were pre-deposited on the wall of the flow cell were investigated. Under flowing solution, minor to major crystal dissolution was observed when the tomography scan frequency was increased from every 30 min to every 5 min (with a 1 min scan duration). The production of reactive radicals from X-ray induced water radiolysis and decrease of pH close to the surface of barite are likely responsible for the observed dissolution. The flow cell shown here can possibly be adopted to study a wide range of other chemical reactions in solutions beyond crystal nucleation and growth where the combination of fast flow and fast scan can be used to mitigate the radiation effects.

A theory of chemical reactions in biomolecules in solution: Generalized Langevin mode analysis (GLMA).

The generalized Langevin mode analysis (GLMA) is applied to chemical reactions in biomolecules in solution. The theory sees a chemical reaction in solution as a barrier-crossing process, similar to the Marcus theory. The barrier is defined as the crossing point of two free-energy surfaces that are attributed to the reactant and product of the reaction. It is assumed that both free-energy surfaces are quadratic or harmonic. The assumption is based on the Kim-Hirata theory of structural fluctuation of protein, which proves that the fluctuation around an equilibrium structure is quadratic with respect to the structure or atomic coordinates. The quadratic surface is a composite of many harmonic functions with different modes or frequencies. The height of the activation barrier will be dependent on the mode or frequency-the less the frequency, the lower the barrier. Hence, it is essential to decouple the fluctuational modes into a hierarchical order. GLMA is impeccable for this purpose. It is essential for a theoretical study of chemical reactions to choose a reaction coordinate along which the reaction proceeds. We suppose that the mode whose center of coordinate and/or the frequency changes most before and after the reaction is the one relevant to the chemical reaction and choose the coordinate as the reaction coordinate. The rate of reaction along the reaction coordinate is krate=ν⁡exp-ΔF(†)/kBT, which is similar to the Marcus expression for the electron transfer reaction. In the equation, ΔF(†) is the activation barrier defined by ΔF(†)≡F(r)Q†-F(r)(Qeq (r)), where F(r)(Qeq (r)) and F(r)Q† denote the free energies at equilibrium Qeq (r) and the crossing point Q†, respectively, both on the free energy surface of the reactant.

Residue Levels and Dietary Intake Risk Assessments of 139 Pesticides in Agricultural Produce Using the m-PFC Method Based on SBA-15-C18 with GC-MS/MS.

A survey was designed to investigate the pesticide residues in agricultural produce and to estimate their potential intake risks to inhabitants. A total of 314 samples of nine types of fruits and vegetables were collected from the supermarkets and vegetable markets of Shandong Province (China) from October 2020 to February 2022. An accurate and reliable multi-residue method, based on GC-MS/MS detection, as well as the multiplug filtration cleanup method, based on SBA-15-C18, was prepared by a solution chemical reaction. Additionally, an in situ co-condensation method was established for the quantification of 139 pesticide residues. Residues that contained no pesticides were detected in 66.5% of the 314 samples. Moreover, of the samples, 30.6% were at or below the MRLs, and 2.9% were above the MRLs. Residues of procymidone were found to be the one that most often exceeded the MRLs (1.3% of the samples). Tebuconazole was found most frequently in 22.0% of the samples analyzed. Consumer exposure to the 139 pesticides did not exceed 100% ADI and ARfD. This led to a consideration that these pesticide residues in the nine commodities may not raise the health risk of the consumers in the long and short term. The highest value of chronic dietary intake was obtained from spirodiclofen, which resulted in a 24.1% of ADI. Furthermore, the highest exposure levels in the short term were obtained from the consumption of leeks with procymidone (58.3% ARfD).

Development and application of a miniature mass spectrometer with continuous sub-atmospheric pressure interface and integrated ionization source

For the miniature mass spectrometer (MS) with a continuous atmospheric pressure interface (CAPI), the gas in the multi-stage chambers directly affects the performance of the instrument. In this study, a sealed ionization chamber is designed to couple with a conventional mini CAPI-MS. In this configuration, the gas environment in the first ionization chamber can be flexibly changed to regulate the gas conditions throughout the entire instrument. By studying the effect of gas pressure on the performance of the instrument, we found that the instrument shows some unique advantages when the first ionization chamber is under sub-atmospheric pressure (SAP) conditions, such as reducing the load of the vacuum pump by 40%, achieving pump-free injection for gas and liquid samples, and improving the resolution by a factor of 2 without loss of detection sensitivity. Therefore, we propose a new integrated interface called continuous sub-atmospheric pressure interface (CSAPI) for building a miniature ion trap mass spectrometer. The CSAPI specially integrates sample introduction, gas/ions interface, and ionizations, including electrospray ionization (ESI) and secondary electrospray ionization (SESI), making this system more convenient for non-professional handlers to rapidly identify or monitor target analytes in gaseous- and solution-phase samples. We also use this system to study gas composition to further improve performance, being able to achieve a 5-fold sensitivity and 2-fold resolution improvement. At last, some custom applications of the current CSAPI-MS platform are explored and demonstrated, including real-time monitoring of chemical reactions in solution and long-distance sampling and analysis of dried Chinese herbs. In conclusion, this study provides a new approach to constructing a complete, versatile and practical miniature MS instrument.

3D Spectroscopic Tracking of Individual Brownian Nanoparticles during Galvanic Exchange.

Monitoring chemical reactions in solutions at the scale of individual entities is challenging: single-particle detection requires small confocal volumes, which are hardly compatible with Brownian motion, particularly when long integration times are necessary. Here, we propose a real-time (10 Hz) holography-based nm-precision 3D tracking of single moving nanoparticles. Using this localization, the confocal collection volume is dynamically adjusted to follow the moving nanoparticle and allow continuous spectroscopic monitoring. This concept is applied to study galvanic exchange in freely moving colloidal silver nanoparticles with gold ions generated in situ. While the Brownian trajectory reveals particle size, spectral shifts dynamically reveal composition changes and transformation kinetics at the single-object level, pointing at different transformation kinetics for free and tethered particles.

Combining Machine Learning Approaches and Accurate Ab Initio Enhanced Sampling Methods for Prebiotic Chemical Reactions in Solution.

The study of the thermodynamics, kinetics, and microscopic mechanisms of chemical reactions in solution requires the use of advanced free-energy methods for predictions to be quantitative. This task is however a formidable one for atomistic simulation methods, as the cost of quantum-based ab initio approaches, to obtain statistically meaningful samplings of the relevant chemical spaces and networks, becomes exceedingly heavy. In this work, we critically assess the optimal structure and minimal size of an ab initio training set able to lead to accurate free-energy profiles sampled with neural network potentials. The results allow one to propose an ab initio protocol where the ad hoc inclusion of a machine-learning (ML)-based task can significantly increase the computational efficiency, while keeping the ab initio accuracy and, at the same time, avoiding some of the notorious extrapolation risks in typical atomistic ML approaches. We focus on two representative, and computationally challenging, reaction steps of the classic Strecker-cyanohydrin mechanism for glycine synthesis in water solution, where the main precursors are formaldehyde and hydrogen cyanide. We demonstrate that indistinguishable ab initio quality results are obtained, thanks to the ML subprotocol, at about 1 order of magnitude less of computational load.

A hierarchically porous and hygroscopic carbon-based catalyst from natural wood for efficient catalytic reduction of industrial high-concentration 4-nitrophenol

4-Nitrophenol (4-NP) with high toxicity and non-biodegradability has been causing a great threat to the environment and human health. Catalytic reduction of high-concentrated 4-NP in wastewater to 4-aminophenol (4-AP) and the subsequent recovery and reuse of catalysts are highly demanded for the practical treatment of industrial pollutants, yet are still limited in low mass transfer efficiency and poor stability of catalysts. Herein, we developed a composite catalyst of Pd nanoparticles (NPs) decorated 3D-activated carbon (Pd/3D-AC) to synergistically catalytic reduce high-concentrated industrial 4-NP (14.38 mM) by using natural wood as a 3D scaffold. The hierarchically porous 3D-AC demonstrates abundant surface-active sites (929 m2·g−1) for adequate and unaggregated anchoring Pd NPs (0.61 %), and the interconnected mass transfer channels and hygroscopic behavior of Pd/3D-AC yield an efficient chemical reaction in solution. As a result, the turnover frequency of the Pd/3D-AC is up to 1.68 min−1, and the synergistic interaction occurs to the 3D-AC and Pd NPs. Even after 10 cycles of catalysis, no deactivation was observed to Pd/3D-AC, demonstrating excellent stability and reusability. Moreover, the Pd/3D-AC catalyst contributes to a high conversion rate to 4-NP, with the yield of obtained 4-AP more than 99.9 % within 10 min. This facile strategy of loading metal nano-catalysts on hierarchically porous wood puts forward a flexible and effective approach for promoting the catalytic performance and the practical treatment of industrial wastewater.

Li/Na Ion Storage Performance of a FeOF Nano Rod with Controllable Morphology

Although the conversion material iron oxyfluoride (FeOF) possesses a high theoretical specific capacity as a cathode material for Li/Na ion batteries, its poor rate and cycling performances, caused mainly by sluggish (Li+/Na+) reaction kinetics, restrict its practical application. Herein, FeOF with high purity, a fusiform nanorod shape and high crystallinity is prepared through a facile chemical solution reaction. The electrochemical measurements show that the present FeOF exhibits high capacity and good cycling stability as a cathode material for Li-ion batteries. Capacities of 301, 274, 249, 222, and 194 mAh/g at stepwise current densities of 20, 50, 100, 200, and 400 mA/g are achieved, respectively. Additionally, the capacity at 100 mA/g retains 123 mAh/g after 140 cycles. Meanwhile, as a cathode material for Na ion battery, it delivers discharge capacities of 185, 167, 151, 134 and 115 mAh/g at stepwise current densities of 20, 50, 100, 200, and 400 mA/g, respectively. A discharge capacity of 83 mAh/g at 100 mA/g is achieved after 140 cycles. The excellent lithium/sodium-storage performance of the present FeOF material is ascribed to its unique nanostructure.

Likelihood-based non-Markovian models from molecular dynamics

SignificanceThe analysis of complex systems with many degrees of freedom generally involves the definition of low-dimensional collective variables more amenable to physical understanding. Their dynamics can be modeled by generalized Langevin equations, whose coefficients have to be estimated from simulations of the initial high-dimensional system. These equations feature a memory kernel describing the mutual influence of the low-dimensional variables and their environment. We introduce and implement an approach where the generalized Langevin equation is designed to maximize the statistical likelihood of the observed data. This provides an efficient way to generate reduced models to study dynamical properties of complex processes such as chemical reactions in solution, conformational changes in biomolecules, or phase transitions in condensed matter systems.

Bifunctional biohybrid magnetically propelled microswimmer

Inspired by the intrinsic helical structures of vessels in banana leaves, a novel bifunctional biohybrid magnetic microswimmer with both environment remediation and biomedical application was synthesized by a simple chemical method. Here, spiral vessels isolated from banana leaves were used as biological templates, where nickel layers with magnetic properties and Fe3+-TA (tannic acid, TA) films with pH-dependent degradation capabilities were modified on their surfaces by simple chemical reactions in solution at room temperature. The obtained magnetic helical (Helix/Ni/Fe3+-TA) microswimmers can be efficiently propelled in either pollutant solution (rhodamine B, RhB) or biofluid solution (DMEM culture medium and fetal bovine serum) in the presence of a magnetic field. The developed Helix/Ni/Fe3+-TA microswimmers can be used to efficiently degrade organic pollutant RhB due to the Fe3+-TA films which can produce reactive oxygen species under the action of hydrogen peroxide (H2O2). Moreover, due to the specific chemical interaction between the microswimmers and the surface of cancer cells, the microswimmers can precisely capture cancer cells and then produce heat under light irradiation to kill those cells. These novel helical microswimmers with simple and economic fabrication, efficient magnetic propulsion and diverse functionality show great potential in future environmental and biological applications.

Liquid metal enabled continuous flow reactor: A proof-of-concept

Liquid metal enabled continuous flow reactor: A proof-of-concept

Development of Range-Corrected Deep Learning Potentials for Fast, Accurate Quantum Mechanical/Molecular Mechanical Simulations of Chemical Reactions in Solution.

We develop a new deep potential─range correction (DPRc) machine learning potential for combined quantum mechanical/molecular mechanical (QM/MM) simulations of chemical reactions in the condensed phase. The new range correction enables short-ranged QM/MM interactions to be tuned for higher accuracy, and the correction smoothly vanishes within a specified cutoff. We further develop an active learning procedure for robust neural network training. We test the DPRc model and training procedure against a series of six nonenzymatic phosphoryl transfer reactions in solution that are important in mechanistic studies of RNA-cleaving enzymes. Specifically, we apply DPRc corrections to a base QM model and test its ability to reproduce free-energy profiles generated from a target QM model. We perform these comparisons using the MNDO/d and DFTB2 semiempirical models because they differ in the way they treat orbital orthogonalization and electrostatics and produce free-energy profiles which differ significantly from each other, thereby providing us a rigorous stress test for the DPRc model and training procedure. The comparisons show that accurate reproduction of the free-energy profiles requires correction of the QM/MM interactions out to 6 Å. We further find that the model's initial training benefits from generating data from temperature replica exchange simulations and including high-temperature configurations into the fitting procedure, so the resulting models are trained to properly avoid high-energy regions. A single DPRc model was trained to reproduce four different reactions and yielded good agreement with the free-energy profiles made from the target QM/MM simulations. The DPRc model was further demonstrated to be transferable to 2D free-energy surfaces and 1D free-energy profiles that were not explicitly considered in the training. Examination of the computational performance of the DPRc model showed that it was fairly slow when run on CPUs but was sped up almost 100-fold when using NVIDIA V100 GPUs, resulting in almost negligible overhead. The new DPRc model and training procedure provide a potentially powerful new tool for the creation of next-generation QM/MM potentials for a wide spectrum of free-energy applications ranging from drug discovery to enzyme design.