Tailoring Surface Engineering with Expanded Precursor Libraries via Rapid Mussel-Inspired Chemistry.

Mussel-inspired coating is a substrate-independent surface modification technology. However, its application is limited by time-consuming, tailoring specific functions require tedious secondary reaction. To overcome those drawbacks, a strategy for the rapid fabrication of diverse coatings by expanding the library of precursors using oxidation coupled with polyamine was proposed. Based on DFT simulations of the reaction pathways, a method was developed to achieve rapid deposition of coatings by coupling oxidation and polyamines, which simultaneously accelerated the oxidation of precursors and polymer chain growth. The feasibility and generalizability of the strategy was validated by the rapid coating of 10 catechol derivatives and polyamines on various substrates. The surface properties of the substrates such as functional group densities, Zeta potential and contact angles can be easily tuned. The tailored surface engineering application of the strategy was demonstrated by the heavy metal adsorbents and superwetting materials prepared through the delicate combination of different building blocks. Our strategy was flexible in terms of diverse surface engineering design which greatly enriched the connotation of mussel-inspired technique.

Molecularly Tunable Heterostructured Co-Polymers Containing Electron-Deficient and -Rich Moieties for Visible-Light and Sacrificial-Agent-Free H2O2 Photosynthesis.

As an alternative to hydrogen peroxide (H2O2) production by complex anthraquinone oxidation process, photosynthesis of H2O2 from water and oxygen without sacrificial agents is highly demanded. Herein, a covalently connected molecular heterostructure is synthesized via sequential C-H arylation and Knoevenagel polymerization reactions for visible-light and sacrificial-agent-free H2O2 synthesis. The subsequent copolymerization of the electron-deficient benzodithiophene-4,8-dione (BTD) and the electron-rich biphenyl (B) and p-phenylenediacetonitrile (CN) not only expands the π-conjugated domain but also increases the molecular dipole moment, which largely promotes the separation and transfer of the photoinduced charge carriers. The optimal heterostructured BTDB-CN0.2 manifested an impressive photocatalytic H2O2 production rate of 1920 µmol g-1 h-1, which is 2.2 and 11.6 times that of BTDB and BTDCN. As revealed by the femtosecond transient absorption (fs-TA) and theoretical calculations, the linkage serves as a channel for the rapid transfer of photogenerated charge carriers, enhancing the photocatalytic efficiency. Further, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) uncovers that the oxygen reduction reaction occurs through the step one-electron pathway and the mutual conversion between C=O and C-OH with the anchoring of H+ during the catalysis favored the formation of H2O2. This work provides a novel perspective for the design of efficient organic photocatalysts.

From Criegee to Breslow: How π-Donors Steer the Route of Olefin Ozonolysis.

While π-bonds typically undergo cycloaddition with ozone, resulting in the release of much-noticed carbonyl O-oxide Criegee intermediates, lone-pairs of electrons tend to selectively accept a single oxygen atom from O3, producing singlet dioxygen. We questioned whether the introduction of potent electron-donating groups, akin to N-heterocyclic olefins, could influence the reactivity of double bonds - shifting from cycloaddition to oxygen atom transfer or generating lesser-known, yet stabilized, donor-substituted Criegee intermediates. Consequently, we conducted a comparative computational study using density functional theory on a series of model olefins with increasing polarity due to (asymmetric) π-donor substitution. Reaction path computations indicate that highly polarized double bonds, instead of forming primary ozonides in their reaction with O3, exhibit a preference for accepting a single oxygen atom, resulting in a zwitterionic species formally identified as a carbene-carbonyl adduct. This previously unexplored reactivity potentially introduces aldehyde umpolung chemistry (Breslow intermediate) through olefin ozonolysis. Considering solvent effects implicitly reveals that increased solvent polarity further directs the trajectories toward a single oxygen atom transfer reactivity by stabilizing the zwitterionic character of the transition state. The competing modes of chemical reactivity can be explained by a bifurcation of the reaction valley in the post-transition state region.

Understanding cellulose pyrolysis via ab initio deep learning potential field.

Comprehensive and dynamic studies of cellulose pyrolysis reaction mechanisms are crucial in designing experiments and processes with enhanced safety, efficiency, and sustainability. The details of the pyrolysis mechanism are not readily available from experiments but can be better described via molecular dynamics (MD) simulations. However, the large size of cellulose molecules challenges accurate ab initio MD simulations, while existing reactive force field parameters lack precision. In this work, precise ab initio deep learning potentials field (DPLF) are developed and applied in MD simulations to facilitate the study of cellulose pyrolysis mechanisms. The formation mechanism and production rate of both valuable and greenhouse products from cellulose at temperatures larger than 1073 K are comprehensively described. This study underscores the critical role of advanced simulation techniques, particularly DLPF, in achieving efficient and accurate understanding of cellulose pyrolysis mechanisms, thus promoting wider industrial applications.

Exploring the formation pathway and antioxidant properties of the sugar-smoking pigment 5-GGMF.

The present study aimed to elucidate the pathway of pigment formation and identify the source of antioxidant activity during sugar smoking. Building upon previous research, this investigation replicated the sucrose cleavage process involved in sugar-smoking through model reactions to obtain distinct model reaction products. The products were analyzed using various techniques such as ultraviolet-visible spectrometry, Fourier-transform infrared spectroscopy, high-performance liquid chromatography, and high-performance liquid chromatography-tandem mass spectrometry. The findings revealed that the pyrolysis of sucrose at 330 °C yielded glucose and fructose, with fructose pyrolysis producing significantly more 5-HMF than glucose. Moreover, the antioxidant capacity of 5-HMF was found to make a substantial contribution. The primary source of 5-HMF was identified as fructose resulting from the cleavage of sucrose at 330 °C, while the primary pathway for the formation of the sugar-smoking pigment 5-GGMF was attributed to the intermolecular dehydration of 5-HMF and glucose at 150 °C.

Solvent and Substituent Size Influence on the Cyclochiral Rigidity of Aminomethylene Derivatives of Resorcin[4]arene.

Resorcin[4]arenes (R[4]A) are a group of macrocyclic compounds whose peculiar feature is the presence of eight hydroxyl groups in their structure. The directional formation of intramolecular hydrogen bonds with their participation leads to the formation of a cyclochiral racemic mixture of these compounds. Their stability strongly depends on the substituent and especially the environment in which they are located. The paper discusses the cyclochiral nature of aminomethylene derivatives of R[4]A (AMD-R[4]A). Their cyclochiral rigidity in non-polar solvents has been shown. The influence of the size of the alkyl groups in the amino substituents of AMD-R[4]A on their cyclochiral nature was noted. To calculate the reaction paths for their racemization, the nudged elastic band (NEB) method was employed using the semi-empirical DFT (GFN1-xTB) approach. The calculated activation barrier energies for their racemization in chloroform, obtained through various semi-empirical quantum chemical methods (SE), Hartree-Fock (HF), and density functionals theory (DFT), show good correlation with experimental observations. Among the tested methods, the B38LYP-D4 method is highly recommended due to its fast computational speed and accuracy, which is comparable to the time-consuming double-hybrid DH-revDSD-PBEP86 approach.

Reaction heat effect and change characteristics of key groups in coal-oxygen intrinsic reaction path.

The intrinsic reaction of coal with oxygen in the process of low-temperature oxidation is the main reaction path leading to self-heating and spontaneous combustion of coal. Most of the existing studies regard the coal oxidation as an overall reaction, ignoring the multi-path characteristics of coal low-temperature oxidation, and it is difficult to accurately explore the intrinsic reaction characteristics between coal with oxygen. Therefore, the low-temperature oxidation process of coal was studied by using a C80 microcalorimeter and in situ FTIR technology from the macro and micro levels. The "profile subtraction method" was used to study the coal-oxygen intrinsic reaction process, and the reaction heat effect and the change characteristics of key functional groups in the process were analyzed. Furthermore, the gray correlation analysis method was used to study the relevant characteristic parameters in the reaction process and grasp the essential structure-activity relationship. The experimental results show that, compared with the overall reaction process in air atmosphere, the change in the heat release of the coal-oxygen intrinsic reaction path has changed to different degrees, and the change in the slow oxidation stage is the most significant (the heat absorption decreases by 70.1-90.9%). In addition, the characteristic temperature points show different degrees of advance, of which the initial exothermic temperature point is the largest (about 21-46 °C), which directly leads to a significant shortening of the slow oxidation stage (30.1-47.4%). The changes of functional groups in the intrinsic reaction path are more regular. With the increase of temperature, the oxygen-containing functional groups -C=O and the aliphatic hydrocarbon functional groups -CH2- and -CH3 showed a fluctuating trend of increasing and decreasing, respectively. The oxidation heat-contributing functional groups of coal are mainly related to the degree of metamorphism and the functional group reaction characteristics during the reaction. With the deepening of coalification degree, the main heat-contributing functional groups as a whole showed the change rule of oxygen-containing functional groups → aliphatic hydrocarbon functional groups → aromatic hydrocarbon functional groups. In addition, the change of -OH content in the three coal samples has a high correlation with the change of the total heat release of coal.

Promoting Solar-driven Hydrogen Peroxide Production over Thiazole-based Conjugated Polymers via Generating and Converting Singlet Oxygen.

Solar-driven synthesis of hydrogen peroxide (H2 O2 ) from water and air provides a low-cost and eco-friendly alternative route to the traditional anthraquinone method. Herein, four thiazole-based conjugated polymers (Tz-CPs: TTz, BTz, TBTz and BBTz) are synthesized via aldimine condensation. BBTz exhibits the highest H2 O2 production rate of 7274 µmol g-1 h-1 in pure water. Further, the reaction path is analyzed by electron paramagnetic resonance (EPR), in situ diffuse reflectance infrared Fourier transform (DRIFT) and theoretical calculation, highlighting the prominent role of singlet oxygen (1 O2 ). The generation of 1 O2 occurs through the oxidation of superoxide radical (⋅O2 - ) and subsequent conversion into endoperoxides via [4+2] cycloaddition over BBTz, which promotes charge separation and reduces the barrier for H2 O2 production. This work provides new insight into the mechanism of photocatalytic O2 reduction and the molecular design of superior single-polymer photocatalysts.

Understanding the Synthesis Kinetics of Single-Crystal Co-Free Ni-Rich Cathodes.

Non-equilibrium kinetic intermediates are usually preferentially generated instead of thermodynamic stable phases in the solid-state synthesis of layered oxides. Understanding the inherent complexity between thermodynamics and kinetics is important for designing high cationic ordering cathodes. Single-crystal strategy is an effective way to solve the intrinsic chemo-mechanical problems of Ni-rich cathodes. However, the synthesis of high-performance single-crystal is very challenging. Herein, the kinetic reaction path and the formation mechanism of non-equilibrium intermediates in the synthesis of single-crystal Co-free Ni-rich were explored. We demonstrate that the formation of non-equilibrium intermediate and the electrochemical-thermo-mechanical failure can be effectively inhibited by driving low-temperature topotactic lithiation. This work provides a basis for designing high-performance single-crystal Ni-rich layered oxides by regulating the defective structures.

Toward Ab Initio Reaction Discovery Using the Artificial Force Induced Reaction Method.

Predicting the whole process of a chemical reaction while solving kinetic equations presents an opportunity to realize an on-the-fly kinetic simulation that directly discovers chemical reactions with their product yields. Such a simulation avoids the combinatorial explosion of reaction patterns to be examined by narrowing the search space based on the kinetic analysis of the reaction path network, and would open a new paradigm beyond the conventional two-step approach, which requires a reaction path network prior to performing a kinetic simulation. The authors addressed this issue and developed a practical method by combining the artificial force induced reaction method with the rate constant matrix contraction method. Two algorithms are available for this purpose: a forward mode with reactants as the input and a backward mode with products as the input. This article first numerically verifies these modes for known reactions and then demonstrates their application to the actual reaction discovery. Finally, the challenges of this method and the prospects for ab initio reaction discovery are discussed.

Engineering the interfacial orientation of MoS2/Co9S8 bidirectional catalysts with highly exposed active sites for reversible Li-CO2 batteries.

Sluggish CO2 reduction reaction (CO2RR) and evolution reaction (CO2ER) kinetics at cathodes seriously hamper the applications of Li-CO2 batteries, which have attracted vast attention as one kind of promising carbon-neutral technology. Two-dimensional transition metal dichalcogenides (TMDs) have shown great potential as the bidirectional catalysts for CO2 redox, but how to achieve a high exposure of dual active sites of TMDs with CO2RR/CO2ER activities remains a challenge. Herein, a bidirectional catalyst that vertically growing MoS2 on Co9S8 supported by carbon paper (V-MoS2/Co9S8@CP) has been designed with abundant edge as active sites for both CO2RR and CO2ER, improves the interfacial conductivity, and modulates the electron transportation pathway along the basal planes. As evidenced by the outstanding energy efficiency of 81.2% and ultra-small voltage gap of 0.68 V at 20 µA cm-2, Li-CO2 batteries with V-MoS2/Co9S8@CP show superior performance compared with horizontally growing MoS2 on Co9S8 (H-MoS2/Co9S8@CP), MoS2@CP, and Co9S8@CP. Density functional theory calculations help reveal the relationship between performance and structure and demonstrate the synergistic effect between MoS2 edge sites and Co9S8. This work provides an avenue to understand and realize rationally designed electronic contact of TMDs with specified crystal facets, but more importantly, provides a feasible guide for the design of high-performance cathodic catalyst materials in Li-CO2 batteries.

Insight into the application of supercritical water oxidation for dichlorvos degradation: experimental and simulation aspects.

Dichlorvos or 2,2-dichlorovinyl dimethyl phosphate (DDVP) (C4H7Cl2O4P) is a chlorinated organophosphorus pesticide, which is frequently detected in agricultural wastewater. Herein, a batch reactor was used to carry out the supercritical water oxidation (SCWO) of a synthetic wastewater containing dichlorvos as a very hazardous agricultural pollutant. To do so, the impact of four operating parameters including dichlorvos concentration (100-500 ppm), oxidant coefficient (0.7-2), temperature (300-500°C) and time (0-100 s) on dichlorvos removal was optimized by the response surface method (RSM). According to the obtained results, at optimal conditions (i.e. initial concentration of dichlorvos 107.5 ppm, oxidation ratio 1.9234, temperature 419.9°C and time 79.94 s), as an index for dichlorvos removal, the chemical oxygen demand (COD) was found to be about 96.34%. Also, the results of high-performance liquid chromatography test showed that dichloroacetaldehyde (C2CL2H2O) and dichloroacetic acid (C2CL2H2O2) were created as intermediate substances during the dichlorvos degradation. Further, the molecular dynamics simulation was performed using ReaxFF force field to show the reaction path and products obtained in each step of the dichlorvos removal. Finally, as an indication, the simulation results indicated a good coordination with the experimental results.

Curvature-weighted nudged elastic band method using the Riemann curvature.

The nudged elastic band (NEB) method is utilized to find reaction paths (RPs) using discretized intermediate structures called "images" between a reactant and a product. In fact, NEB calculations do not always converge because of the bent of RPs. Mathematically, more images are needed for complex curves, and here, we focused on the curvature. In this study, we propose a new method for calculating the curvature of the RPs as well as a method for weighting the spring constant of the NEB with the curvature, which we named the curvature weighted NEB (CW-NEB) method. In addition, we will propose the CW-NEB method with the climbing image (CI) method (CW-CI-NEB). To show the efficiency of our method, calculations for the ene-reaction of the CW-CI-NEB method were performed and compared with those of the CI-NEB methods. The CW-CI-NEB methods converged in shorter iteration times than the CI-NEB calculation, which was found by gathering the bent of RPs.

Automated input structure generation for single-ended reaction path optimizations.

The exploration of a reaction network requires highly automated workflows to avoid error-prone and time-consuming manual steps. In this respect, a major bottleneck is the search for transition-state (TS) structures, which frequently fails and, therefore, makes (manual) revision necessary. In this work, we present a technique for obtaining suitable input structures for automated TS searches based on single-ended reaction path optimization algorithms, which makes subsequent TS searches via this method significantly more robust. First, possible input structures are generated based on the spatial alignment of the reactants. The appropriate orientation of reacting groups is achieved via stepwise rotations along selected torsional degrees of freedom. Second, a ranking of the obtained structures is performed according to selected geometric criteria. The main goals are to properly align the reactive atoms, to avoid hindrance within the reaction channel and to resolve steric clashes between the reactants. The developed procedure has been carefully tested on a variety of examples and provides suitable input structures for TS searches within seconds. The method is in daily use in an industrial setting.

Molecular dynamics simulation of initial thermal decomposition mechanism of DNTF.

In order to understand the thermal decomposition characteristics of 3,4-Bis(3-nitrofurazan-4-yl)furoxan (DNTF), the thermal decomposition reaction of DNTF at 300-4000 K temperature programmed and constant temperatures of 2000 K, 2500 K, 3000 K, 3500 K, and 4000 K was simulated by ab initio computational molecular dynamics method. The thermal decomposition mechanism of DNTF at different temperatures was analyzed from the aspects of product evolution, cluster, potential energy curve, and reaction path. The analysis of products shows that the initial small molecular products are NO, NO2, CO, CO2, and N2, and the final small molecular products are CO2 and N2. In the early stage, the ring-opening reaction of furoxan in DNTF structure is the main trigger reaction, and the C-C bond is broken at the initial stage of reaction. The carbon chain structure produced by decomposition forms various cluster structures in the form of C-N bond. In addition, it was found that temperature significantly affects the decomposition rate of DNTF, but does not change its initial decomposition path.

Reaction Space Projector (ReSPer) for Visualizing Dynamic Reaction Routes Based on Reduced-Dimension Space.

To analyze chemical reaction dynamics based on a reaction path network, we have developed the "Reaction Space Projector" (ReSPer) method with the aid of the dimensionality reduction method. This program has two functions: the construction of a reduced-dimensionality reaction space from a molecular structure dataset, and the projection of dynamic trajectories into the low-dimensional reaction space. In this paper, we apply ReSPer to isomerization and bifurcation reactions of the Au5 cluster and succeed in analyzing dynamic reaction routes involved in multiple elementary reaction processes, constructing complicated networks (called "closed islands") of nuclear permutation-inversion (NPI) isomerization reactions, and elucidating dynamic behaviors in bifurcation reactions with reference to bundles of trajectories. Interestingly, in the second application, we find a correspondence between the contribution ratios in the ability to visualize and the symmetry of the morphology of closed islands. In addition, the third application suggests the existence of boundaries that determine the selectivity in bifurcation reactions, which was discussed in the phase space. The ReSPer program is a versatile and robust tool to clarify dynamic reaction mechanisms based on the reduced-dimensionality reaction space without prior knowledge of target reactions.

Reaction Mechanism for the Removal of NOx by Wet Scrubbing Using Urea Solution: Determination of Main and Side Reaction Paths.

Secondary problems, such as the occurrence of side reactions and the accumulation of by-products, are a major challenge in the application of wet denitrification technology through urea solution. We revealed the formation mechanism of urea nitrate and clarified the main and side reaction paths and key intermediates of denitrification. Urea nitrate would be separated from urea absorption solution only when the concentration product of [urea], [H+] and [NO3-] was greater than 0.87~1.22 mol3/L3. The effects of the urea concentration (5-20%) and reaction temperature (30-70 °C) on the denitrification efficiency could be ignored. Improving the oxidation degree of the flue gas promoted the removal of nitrogen oxides. The alkaline condition was beneficial to the dissolution process, while the acidic condition was beneficial to the reaction process. As a whole, the alkaline condition was the preferred process parameter. The research results could guide the optimization of process conditions in theory, improve the operation efficiency of the denitrification reactor and avoid the occurrence of side reactions.

Arsenic polluted waters: Application of geochemical modelling as a tool to understand the release and fate of the pollutant in crystalline aquifers.

Arsenic (As) is one of the most investigated elements worldwide due to its negative impact on the natural system. Its geochemical behavior depends on several geogenic processes, which can cause hazardous enrichment into natural waters, even in remote areas, far from anthropogenic sources. In this work the arsenic pollution issue has been addressed by studying water-rock interaction processes and applying reaction path modelling as a tool to understand the rock-to-water release of As and the fate of this natural pollutant in crystalline aquifers. In-depth geochemical characterization of several water samples discharging from crystalline aquifers was performed. The obtained data were used to fix the boundary conditions and validate the modelling outcomes. The performed modelling allowed to reconstruct the water-rock interaction processes which occur (i) in shallow and relatively shallow crystalline aquifers in which no As anomalies were observed and (ii) in As-rich areas, coupling reaction path modelling of granite dissolution with adsorption of dissolved As onto precipitating crystalline and amorphous Fe(III)-oxyhydroxides given the widespread presence of these phases in the studied environment. The results of the geochemical modelling are in agreement with the analytical data and reproduce them satisfactorily. The performed geochemical modelling is of high environmental significance because it is a flexible and powerful tool that correctly defines the water-rock interaction processes occurring in crystalline aquifers, providing valuable data to improve the knowledge on As behavior, not only in the study area, but also in similar geological settings worldwide. Therefore, the present research has broad future perspectives in the environmental field.

Influence of hydrogeochemical reactions along flow paths on contrasting groundwater arsenic and manganese distribution and dynamics across the Ganges River.

The groundwater within the aquifers of the Ganges River delta exhibits significant spatial variability in concentrations of redox-sensitive solutes [e.g., arsenic (As), iron (Fe), manganese (Mn)]. The groundwater As and Mn concentrations show conspicuous contrasting distribution on the opposite banks of the Bhagirathi-Hooghly (B-H) River, the Indian distributary of the Ganges River. Here, we investigate the differences in hydrostratigraphic framework and groundwater evolutionary pathways across the B-H River that might have resulted in such variations. We developed a hydrostratigraphic model for the region and also used inverse reaction-path modeling along three hypothesized end-member flow paths to understand the dominant processes that might control As and Mn cycling within the aquifers. Our results indicate that the variability of As and Mn across the B-H River is a function of a complex interplay between the aquifer architecture, groundwater chemistry, and redox conditions.

Catalytic Descriptors to Investigate Catalytic Power in the Reaction of Haloalkane Dehalogenase Enzyme with 1,2-Dichloroethane.

Enzymes play a fundamental role in many biological processes. We present a theoretical approach to investigate the catalytic power of the haloalkane dehalogenase reaction with 1,2-dichloroethane. By removing the three main active-site residues one by one from haloalkane dehalogenase, we found two reactive descriptors: one descriptor is the distance difference between the breaking bond and the forming bond, and the other is the charge difference between the transition state and the reactant complex. Both descriptors scale linearly with the reactive barriers, with the three-residue case having the smallest barrier and the zero-residue case having the largest. The results demonstrate that, as the number of residues increases, the catalytic power increases. The predicted free energy barriers using the two descriptors of this reaction in water are 23.1 and 24.2 kcal/mol, both larger than the ones with any residues, indicating that the water solvent hinders the reactivity. Both predicted barrier heights agree well with the calculated one at 25.2 kcal/mol using a quantum mechanics and molecular dynamics approach, and also agree well with the experimental result at 26.0 kcal/mol. This study shows that reactive descriptors can also be used to describe and predict the catalytic performance for enzyme catalysis.