Fundamental Reaction Research Articles

Neural network potential-based molecular investigation of thermal decomposition mechanisms of ethylene and ammonia

This study developed neural network potentials (NNPs) specifically tailored for pure ethylene and ethylene-ammonia blended systems for the first time. The NNPs were trained on a dataset generated from density functional theory (DFT) calculations, combining the computational accuracy of DFT with a calculation speed comparable to reactive force field methods. The NNPs are employed in reactive molecular dynamics simulations to explore the thermal decomposition reaction mechanisms of ethylene and ammonia. The simulation results revealed that adding ammonia reduces the activation energy for ethylene decomposition, thereby accelerating ethylene consumption. Furthermore, the addition of ammonia uncovers a new reaction pathway for hydrogen radical consumption, which reduces the occurrence of H-abstraction reactions from ethylene by hydrogen radicals. The inhibition effect of ammonia addition on soot formation mainly acts in two aspects: on the one hand, ammonia decomposition products react with carbon-containing species, ultimately producing C1N products, thereby decreasing the carbon numbers involved in soot formation. This significantly reduces the concentrations of C5C9 molecules and key polycyclic aromatic hydrocarbons (PAHs) precursors like C2H2 and C3H3. On the other hand, ammonia promotes the ring-opening reactions of six-membered carbon rings at high-temperature conditions, thereby reducing the formation of PAHs precursors. The results show that with the addition of ammonia, six-membered carbon rings tend to convert into seven-membered carbon rings at lower temperatures, while at higher temperatures, they are more likely to transform into three- and five-membered carbon rings. These variations in the transformation of six-membered carbon rings may also affect soot formation. The insights gained from understanding these fundamental chemical reaction mechanisms can guide the development of ethylene-ammonia co-firing systems.

Influence of the C + H2O -> H2CO solid-state reaction onastrochemical networks and the formation of complex organic molecules

The solid-state reaction C + H$_2$O rightarrow H$_2$CO has recently been studied experimentally and claimed as a new `non-energetic' pathway to complex organic and prebiotic molecules in cold astrophysical environments. We compared results of astrochemical network modelling with and without the C + H$_2$O surface reaction. A typical, generic collapse model in which a dense core forms from initially diffuse conditions was used along with the astrochemical kinetics model MAGICKAL. The inclusion of the reaction does not notably enhance the abundance of formaldehyde itself; however, it significantly enhances the abundance of methanol (formed by the hydrogenation of formaldehyde) on the dust grains at early times, when the high gas-phase abundance of atomic C leads to relatively rapid adsorption onto the grain surfaces. As a result, the gas-phase abundance of methanol is also increased due to chemical desorption, quickly reaching abundances close to sim 10$^ $ n$_H$, which decline strongly under late-time, high-density conditions. The reaction also influences the abundances of simple ice species, with the CO$_2$ abundance increased in the earliest, deepest ice layers, while the water-ice abundance is somewhat depressed. The abundances of various complex organic molecules are also affected, with some species becoming more abundant and others less. When gas-phase atomic carbon becomes depleted, the grain-surface chemistry returns to behaviour that would be expected if there had been no new reaction. Our results show that fundamental reactions involving the simplest atomic and molecular species can be of great importance for the evolution of astrochemical reaction networks, thus providing motivation for future experimental and theoretical studies.

Unmasking the reverse catalytic activity of 'ene'-reductases for asymmetric carbonyl desaturation.

Carbonyl desaturation is a fundamental reaction widely practised in organic synthesis. While numerous methods have been developed to expand the scope of this important transformation, most of them necessitate multi-step protocols or suffer from the use of high loadings of metal or strong oxidizing conditions. Moreover, approaches that can achieve precise stereochemical control of the desaturation process are extremely rare. Here we report a biocatalytic platform for desymmetrizing desaturation of cyclohexanones to generate diverse cyclohexenones bearing a remote quaternary stereogenic centre, by reengineering 'ene'-reductases to efficiently mediate dehydrogenation, the reverse process of their native activity. This 'ene'-reductase-based desaturation system operates under mild conditions with air as the terminal oxidant, tolerates oxidation-sensitive or metal-incompatible functional groups and, more importantly, exhibits unparalleled stereoselectivity compared with those achieved with small-molecule catalysts. Mechanistic investigations suggest that the reaction proceeded through α-deprotonation followed by a rate-determining β-hydride transfer.

Unveiling the Mechanism of Deprotonation and Proton Transfer of DNA Polymerase Catalysis via Single-Molecule Conductance.

DNA polymerases (Pols) play important roles in the transmission of genetic information. Although the function and (de)regulation of Pols are linked to many human diseases, the key mechanism of 3'-OH deprotonation and the PPi formation are not totally clear. In this work, a method is presented to detect the full catalytic cycle of human Pol (hPol β) in graphene-molecule-graphene single-molecule junctions. Real-time in situ monitoring successfully revealed the spatial and temporal properties of the open and closed conformation states of hPol β, distinguishing the reaction states in the Pols catalytic cycle and unveiling 3'-OH deprotonation and pyrophosphate (PPi) formation mechanism of hPol β. Proton inventory experiment demonstrated that the rate-limiting step of PPi formation is deprotonation, which occurs before a reverse conformational change. Additionally, by detecting the acidity (pKa), it is found that MgA-bound OH- acted as a general base and activated the nucleophile of 3'-OH, and that acidic residue D190 or D192 coordinated with MgB as a proton donor to PPi. This work provides useful insights into a fundamental chemical reaction that impacts genome synthesis efficiency and Pol fidelity, which the discovery of Pol-targeting drugs and design of artificial Pols for DNA synthetic applications are expected to accelerated.

Recent Progress on Organic Electron Donors (OEDs) Enabled Radical Reactions

AbstractOver the past few decades, organic transformations facilitated by small organic molecules have witnessed considerable advancements. Small organic molecules have been widely applied to the construction of various skeletons. However, reduction as one of the fundamental reactions is generally initiated by metal‐containing reducing agents, although the initial progress of organic electron donors (OEDs) enabled reductive cleavage of some chemical bonds had been achieved in 1990s. Due to their structural diversity and tunability, OEDs can overcome the limitations of metal‐based reducing agents, such as low selectivity and poor functional group tolerance as well as the environmental problems caused by substantial inorganic waste after reactions. Building on a brief historical overview of OED research, this review focuses on the rencent advancements of the OEDs promoted radical reactions. It covers the reduction of C−X (X=C, O, N etc.) single bonds, radical cyclization, intermolecular radical addition to unsaturated bonds, radical coupling, functionalization of aromatics, and C−H bond activation. Additionally, the mechanistic insights of the typical reactions are highlighted for well understanding of the reaction mode involving OEDs.

Quasi-Solid-State Conversion with Fast Redox Kinetics Enabled by a Sulfonamide-Based Electrolyte in Li-Organic Batteries.

The serious dissolution of organic electrode materials (e.g., perylene-3,4,9,10-tetracarboxylic dianhydride, PTCDA) in electrolytes is a major challenge, deteriorating their electrochemical performances and hindering the interpretation of the fundamental redox reaction mechanisms including the intrinsic kinetics and the solvent cointercalation. To address these issues, we propose a rationally designed sulfonamide-based electrolyte to enable a quasi-solid-state conversion (QSSC) of the PTCDA cathode by effectively suppressing its dissolution in the electrolyte. Benefiting from the QSSC, the Li||PTCDA cells can retain ∼95.8% of the original capacity after 300 cycles with both high and stable energy efficiencies >95%, even comparable to the layered transition-metal oxide cathodes, greatly outperforming an ether-based electrolyte with a high PTCDA solubility. The high energy efficiencies indicate that the QSSC of PTCDA has intrinsic fast redox kinetics. Furthermore, the solvent cointercalation mechanism was investigated by density functional theory/molecular dynamic calculations. This work develops a strategy for designing electrolytes for highly stable and efficient Li-organic batteries.

Experimental Insights into the Formation, Reactivity, and Crosstalk of Thionitrite (SNO−) and Perthionitrite (SSNO−)

AbstractHydrogen sulfide (H2S) and nitric oxide (NO) are important gaseous biological signaling molecules that are involved in complex cellular pathways. A number of physiological processes require both H2S and NO, which has led to the proposal that different H2S/NO⋅ crosstalk species, including thionitrite (SNO−) and perthionitrite (SSNO−), are responsible for this observed codependence. Despite the importance of these S/N hybrid species, the reported properties and characterization, as well as the fundamental pathways of formation and subsequent reactivity, remain poorly understood. Herein we report new experimental insights into the fundamental reaction chemistry of pathways to form SNO− and SSNO−, including mechanisms for proton‐mediated interconversion. In addition, we demonstrate new modes of reactivity with other sulfur‐containing potential crosstalk species, including carbonyl sulfide (COS).

Experimental Insights into the Formation, Reactivity, and Crosstalk of Thionitrite (SNO-) and Perthionitrite (SSNO-).

Hydrogen sulfide (H2S) and nitric oxide (NO) are important gaseous biological signaling molecules that are involved in complex cellular pathways. A number of physiological processes require both H2S and NO, which has led to the proposal that different H2S/NO⋅ crosstalk species, including thionitrite (SNO-) and perthionitrite (SSNO-), are responsible for this observed codependence. Despite the importance of these S/N hybrid species, the reported properties and characterization, as well as the fundamental pathways of formation and subsequent reactivity, remain poorly understood. Herein we report new experimental insights into the fundamental reaction chemistry of pathways to form SNO- and SSNO-, including mechanisms for proton-mediated interconversion. In addition, we demonstrate new modes of reactivity with other sulfur-containing potential crosstalk species, including carbonyl sulfide (COS).

Pyrolysis features of Dracaena draco lignocellulosic fibers: Kinetic and thermodynamic analysis at various heating rates through coats-redfern method

This study evaluated the thermokinetic and thermodynamic properties of Dracaena draco fibers (DDFs) through thermogravimetric analysis (TGA). The DDFs underwent non-isothermal heating in a nitrogen atmosphere, with 5, 10, and 20 °C/min heating rates starting at 20 °C and reaching 800 °C. TGA analysis demonstrated that the pyrolysis of DDFs took place in three clearly defined phases: dehydration, devolatilization, and solid biochar. The thermokinetic and thermodynamic properties were computed for the devolatilization phase of mass reduction. The Coats-Redfern technique employed twenty-one separate kinetic equations derived from four fundamental solid-state reaction processes. Out of all the diffusivity models (DMs), the Ginstlinge-Brounshtein (DM5), Jander (3D diffusion) (DM7), and Ginstling models (DM8) had the best fit, as indicated by their highest coefficient of regression values (R2 > 0.990) across all the three heating rates. The activation energy values found by the DM5, DM7, and DM8 models are 76.5, 82.32, and 76.47 kJ/mol, respectively, for the 5 °C/min heating rate. The thermodynamic variables, including the entropy, free energy, and enthalpy change, were calculated based on the kinetic data. The study’s findings are significant for evaluating the DDFs' potential as an energy source, constructing reactors, producing chemicals, and understanding the DDFs’s features for composite synthesis.

Fueling the future of clean energy with self‐supported layered double hydroxides‐based electrocatalysts: A step toward sustainability

AbstractAmid the ongoing transition toward renewable fuels, the self‐supported layered double hydroxides (LDHs) are envisioned as propitious electrocatalysts for reinvigorating the electrocatalysis realm, thereby facilitating environmental remediation and bolstering sustainable global energy security. Exploiting appealing attributes such as unique lamellar structure, abundant active sites, tunable intercalation spacing and compositional flexibility, LDHs boast remarkable activity, selectivity and stability across diverse energy‐related applications. By virtue of addressing the technological and time prominence of excavating their renaissance, this review first encompasses the facile state‐of‐the‐art synthetic approaches alongside intriguing modification strategies, toward deciphering the authentic structure–performance correlations for advancing more robust and precise catalyst design. Aside from this, heterostructure engineering employing diversified ranges of coupling materials is highlighted, to construct ground‐breaking binder‐free LDHs‐based heterostructures endowing with unprecedented activity and stability. Subsequently, the milestone gained from experimental research and theoretical modeling of this frontier in multifarious electrocatalytic applications, including HER, OER, UOR, AOR, seawater splitting and other fundamental conversion reactions is rigorously unveiled. As a final note, a brief conclusion is presented with an outline of future prospects. Essentially, this review aspires to offer enlightenment and incite wise inspiration for the future evolution of innovative and resilient next‐generation catalysts.image

Catalytic Biomaterials-Activated In Situ Chemical Reactions: Strategic Modulation and Enhanced Disease Treatment.

Chemical reactions underpin biological processes, and imbalances in critical biochemical pathways within organisms can lead to the onset of severe diseases. Within this context, the emerging field of "Nanocatalytic Medicine" leverages nanomaterials as catalysts to modulate fundamental chemical reactions specific to the microenvironments of diseases. This approach is designed to facilitate the targeted synthesis and localized accumulation of therapeutic agents, thus enhancing treatment efficacy and precision while simultaneously reducing systemic side effects. The effectiveness of these nanocatalytic strategies critically hinges on a profound understanding of chemical kinetics and the intricate interplay of reactions within particular pathological microenvironments to ensure targeted and effective catalytic actions. This review methodically explores in situ catalytic reactions and their associated biomaterials, emphasizing regulatory strategies that control therapeutic responses. Furthermore, the discussion encapsulates the crucial elements-reactants, catalysts, and reaction conditions/environments-necessary for optimizing the thermodynamics and kinetics of these reactions, while rigorously addressing both the biochemical and biophysical dimensions of the disease microenvironments to enhance therapeutic outcomes. It seeks to clarify the mechanisms underpinning catalytic biomaterials and evaluate their potential to revolutionize treatment strategies across various pathological conditions.

Insight into the Pyrolysis Behaviors of Petroleum-Driven Mesophase Pitch via ReaxFF Molecular Dynamics and In Situ TG-FTIR/MS.

Mesophase pitch is regarded as a profoundly promising candidate for the production of advanced carbon-based multifunctional materials such as carbon fibers, carbon microspheres, and carbon foams owing to its excellent intrinsic properties. Consequently, a deeper understanding of pyrolytic chemistry is indispensable for the efficient and environmentally friendly utilization of mesophase pitch. In this study, details about the structure compositions and microscopic morphologies of petroleum-driven mesophase pitch (pMP) were investigated through ultimate, FTIR, XPS, and 13C-NMR analyses. Furthermore, a large-scale molecular model of typical pMP with 11,835 atoms was constructed to unveil the comprehensive pyrolysis behaviors and the underlying reactions. Significantly, the evolution of specific chemical bonds and the decomposition of crucial molecular fragments were elucidated within an amalgamation of experimental TG-FTIR/MS and ReaxFF MD simulation. Accordingly, three fundamental reaction stages were artificially divided, including the low-temperature reaction, rapid thermal decomposition, and the molecular condensation reaction. During the rapid thermal decomposition stage, the cleavages of C-C and C-O bonds cooperatively contributed to the formation of C2H4 and H2O gaseous products. As the temperature escalated to the molecular condensation stage, the pyrolysis process was governed by the dehydrogenation condensation, accompanied by an augmentation of C-C and H-H bonds and a diminution of C-O and C-H bonds. Additionally, the rare graphitization phenomenon was observed, suggesting a remarkable degree of structural organization in pMP. Overall, the results of ReaxFF MD simulations complement experimental observations, successfully reproducing the microstructure of pMP and atomic-scale pyrolysis behavior, thereby providing invaluable insights for the rational guidance of efficient utilization of pMP and other related carbonaceous precursors.

Revealing Asymmetric Phase Transformation of the BiVO4 Anodes for Potassium-Ion Batteries by In Situ Transmission Electron Microscopy.

Potassium-ion batteries (PIBs) have emerged as a promising alternative to lithium-ion batteries (LIBs), thanks to the cost-effectiveness of potassium resources and a favorable redox potential of approximately -2.936 V. The monoclinic BiVO4, known for its layered structure, shows noteworthy electrochemical properties when utilized as an anode material for both LIBs and sodium-ion batteries. However, the fundamental electrochemical reaction mechanisms of the BiVO4 anode during the potassium insertion/extraction processes remain unclear. Here, we constructed a BiVO4 anode PIB inside the transmission electron microscope (TEM) to explore the real-time potassiation/depotassiation behaviors of BiVO4 during electrochemical cycling. Utilizing the state-of-art in situ TEM technique, the BiVO4 nanorods are found to undergo an asymmetric phase transformation for the first time, where the pristine BiVO4 material is transformed into an amorphous KxBiVO4 phase after the first cycle. More interestingly, the anode materials near and far from the potassium source exhibit opposite volume-changing trends under the same voltage potential. Also, this phenomenon should be attributed to the mass flow of the unstable K-Bi alloy under the electric field. Our findings provide significant insights into the electrochemical mechanism of BiVO4 nanorods during the potassiation/depotassiation process, with the hope of assistance in designing anodes for high-performance PIBs.

Unraveling the adsorption-limited hydrogen oxidation reaction at palladium surface via in situ electron microscopy

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H2O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remain elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied in situ, to investigate intermediate reaction stages via gas cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by precursors' adsorption. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions.

Mechanism of Fe-rich phase supercooling induced by CDS process to regulating microstructure and strengthen properties of Al-Si-Fe alloy

Excessive iron in aluminum alloys forms compounds that weaken their strength and workability. Therefore, controlling the morphology of the Fe-rich phase is vital for developing strong, high-quality aluminum alloys. This research explores the controlled diffusion solidification (CDS) process, an innovative approach designed to optimize the morphology and distribution of the Fe-rich phase, thereby enhancing the alloy properties beyond what conventional methods can achieve. Specifically, the CDS process uniquely modifies the solidification behavior of the alloy, suppressing the growth of the primary Fe-rich phase and enhancing the overall properties. This demonstrating the ability of process to refine microstructural characteristics effectively. The experimental results confirm the presence of primary Si and Al3Fe in the CDS process samples. Consequently, the nucleation of Al3Fe in the precursor alloy leads to the concentration of Fe solutes reduce, impeding the nucleation and growth of the primary Fe-rich phase during the subsequent solidification process. The key factors are temperature difference between two mixed alloy and mass ratio of precursor alloys. The mass ratio influences the precipitation sequence of the precursor alloys, while the difference of temperature and concentration induces the undercooling necessary for nucleation. The study reveals that an optimal mass ratio of 4:1 in the CDS process achieves the best mechanical properties with a 73.78 % increase in ultimate tensile strength (UTS) and a 107.77 % increase in elongation (UL) compared to conventional casting. The findings provide a theoretical basis for controlling the Fe-rich phase evolution, significantly augmenting the performance of Al-Si-Fe alloys. The findings not only enhancing the optimizing fundamental reactions in the CDS process for other alloy systems but also enriching the broader field of materials science.

Probing Asymmetric Interactions with Time-Separated Mutual Information: A Case Study Using Golden Shiners.

Leader-follower modalities and other asymmetric interactions that drive the collective motion of organisms are often quantified using information theory metrics like transfer or causation entropy. These metrics are difficult to accurately evaluate without a much larger number of data than is typically available from a time series of animal trajectories collected in the field or from experiments. In this paper, we use a generalized leader-follower model to argue that the time-separated mutual information between two organism positions can serve as an alternative metric for capturing asymmetric correlations that is much less data intensive and more accurately estimated by popular k-nearest neighbor algorithms than transfer entropy. Our model predicts a local maximum of this mutual information at a time separation value corresponding to the fundamental reaction timescale of the follower organism. We confirm this prediction by analyzing time series trajectories recorded for a pair of golden shiner fish circling an annular tank.

Enhancing oil production via radical reactions during hydrothermal coliquefaction of biomass model compounds and plastics: A molecular dynamic simulation study

Recently, hydrothermal coliquefaction of biomass and plastic waste has attracted considerable research interest. However, there is a notable gap in understanding the fundamental reaction mechanisms between biomass and plastics during coliquefaction. This study focused on the coliquefaction of biomass model compounds and plastic polymers using ReaxFF molecular dynamics simulations under both subcritical and supercritical water conditions. Molecular-level tracking and probing of the reaction mechanisms between biomass model compounds and plastics were conducted to purposefully enhance oil production. The study observed related radical reactions between by-product molecules, with detailed mechanisms primarily involving (1) ▪OH radicals released by aqueous phase molecules from biomolecules, transferring as H2O molecules and facilitating plastic depolymerization, and (2) C1–C4 radicals in the gaseous phase, emitted from biomolecule and plastic, colliding and subsequently recombining to form oil molecules. Moreover, the yield of multiple products from various mixtures were evaluated by considering the key reaction parameters including reaction temperature and feedstock blended ratio. An exploration into the effect of coliquefaction on oil yield was conducted to precisely identify the optimal coliquefaction conditions. The positive effect of coliquefaction was more pronounced between biomass model compounds and aromatic polymers compared to aliphatic polymers. Analysis of reaction mechanisms and product outcomes has shown that hydrothermal coliquefaction is a viable approach to improving oil production from multi-source organic solid waste.

An experimental and modeling study on pyrolysis reaction kinetics of oxygenated biofuel blended with aviation kerosene RP-3

Blending the renewable oxygenated biofuels with conventional fossil fuels is one of the feasible approaches to achieve carbon-neutral in the aviation industry, while there is very limited research available on the fundamental reaction characteristics of blended fuels. The primary objective of the present study is to conduct experimental investigations on the pyrolysis and oxidative pyrolysis reaction kinetics of oxygenated biofuels blended with China aviation kerosene RP-3 and establish a kinetic model. Pyrolysis experiments were conducted in a flow reactor at atmospheric pressure and temperature of 1130 K for blended fuels (methyl butanoate blended with RP-3, and n-butanol with RP-3) to examine fuel reactivity and formation of critical intermediates. The introduction of alternative oxygenated biofuel to the conventional hydrocarbon fuel RP-3 leads to the generation of CO during the pyrolysis reactions, as well as the reduced formation of olefin products. Notably, the CO yield from pyrolysis reactions of the blended fuel is increasing almost linearly with the concentrations of added oxygenated biofuels. A Two-Step Reaction Scheme (TSRS) modeling approach was extended for describing the reaction kinetics of oxygenated biofuels. TSRS models for methyl butanoate and n-butanol were constructed and merged with the HyChem model of RP-3 to complete the blended fuel model. Results show that the blended model predicts well the evolution of key intermediates with time, demonstrating the applicability of the model based on the two-stage characteristics of high-temperature reaction kinetics for describing the pyrolysis reactions of oxygenated fuels and hydrocarbon fuels.

Magnesium induced structural reorganization in the active site of adenylate kinase.

Phosphoryl transfer is a fundamental reaction in cellular signaling and metabolism that requires Mg2+ as an essential cofactor. While the primary function of Mg2+ is electrostatic activation of substrates, such as ATP, the full spectrum of catalytic mechanisms exerted by Mg2+ is not known. In this study, we integrate structural biology methods, molecular dynamic (MD) simulations, phylogeny, and enzymology assays to provide molecular insights into Mg2+-dependent structural reorganization in the active site of the metabolic enzyme adenylate kinase. Our results demonstrate that Mg2+ induces a conformational rearrangement of the substrates (ATP and ADP), resulting in a 30° adjustment of the angle essential for reversible phosphoryl transfer, thereby optimizing it for catalysis. MD simulations revealed transitions between conformational substates that link the fluctuation of the angle to large-scale enzyme dynamics. The findings contribute detailed insight into Mg2+ activation of enzymes and may be relevant for reversible and irreversible phosphoryl transfer reactions.

(Invited) Unveiling Fundamental Reaction Mechanisms at the Electrochemical Interface by Ab Initio Simulations

Direct experimental exploration of atomistic mechanisms governing electrocatalysis or wet corrosion at the solid-liquid interface is notoriously difficult. While fully parameter-free ab initio calculations have the potential to accurately elucidate such mechanisms, they encounter substantial conceptual challenges. Recent methodological breakthroughs, including the advent of efficient computational electrodes and the development of effective thermopotentiostats, overcame many of these limitations thus providing new research opportunities. This presentation outlines the fundamental concepts underlying these innovative methodologies and demonstrates their application in performing fully explicit calculations of structure and chemical reactions at electrified solid-water interfaces. The power of this approach in discovering new mechanisms will be demonstrated for fundamental electrochemical reactions such as metal dissolution and the hydrogen evolution reaction (HER). The identified mechanisms challenge existing understandings and empfasize the active involvement of water molecules in electrochemical reactions, challenging the perception that they are passive bystanders.