Reaction Pathways Research Articles

Cobalt single-site molecular Catalyst-mediated electrochemical Hydrodechlorination for detoxification of halogenated Antibiotics: Performance, reaction pathway and mechanism

Electrocatalytic hydrodehalogenation (ECHD) offers a promising approach for detoxification of the halogenated antibiotics via hydrogenolysis of the C-X bonds (X = F, Cl or Br). Herein we demonstrated that the commercially-available cobalt phthalocyanine (CoPc) molecules with a high-loading of −[Co-N4]- moieties (Co wt%: 10.8 %) were exceptionally active for hydrogenolysis of the C-Cl bonds in florfenicol (FLO). It afforded an impressive mass activity of 6.2 gFLO h−1 g-1Co, a low Co leaching of 0.34 μg/L and a strong tolerance to interference from impurities in water, significantly surpassing reported Co/Fe/Ni-based particle and single-site counterparts. Mechanistic studies revealed that the ECHD on CoPc underwent a direct electron transfer manner rather than the atomic hydrogen (H*)-mediated indirect way, and the ECHD efficacy was affected by both the electron and proton transfer kinetics. The single-atom Co, with its d orbitals constituting the lowest unoccupied molecular orbitals of CoPc, served as the primary active site. It facilitated both electron and proton transfer, as well as the cleavage of the C-Cl bond but not the C-F bond. In a continuous-flow cell, the CoPc/C-driven ECHD reduced the antibacterial activity of a FLO-contaminated natural lake water sample by 90.8 % with an energy consumption of 0.19 kwh g-1FLO. This study highlighted great promise of the single-atom metal-bearing molecular catalyst toward the sustainable detoxification of halogenated antibiotics-contaminated water.

Influence mechanism of divalent metals in the laminates of M2+Al-layered double hydroxides on peroxymonosulfate activation reaction pathway: Radical vs nonradical

Radical and nonradical reaction pathways have been commonly validated in peroxymonosulfate (PMS) based advanced oxidation progresses (AOPs) using layered double hydroxides (LDHs) as catalysts, but achieving efficient and selective degradation of organic pollutants remains challenging due to the unclear regulatory mechanism of laminate M2+ in PMS activation. Here, the d-orbital electrons configuration of M2+ was found to influence the degree of overlap between M−OH and O of PMS, which results in the selective dissociation of PMS to form reactive oxygen species (ROS) or achieve electron transfer pathway. Further analysis revealed that Co(II, 3d7) and Ni(II, 3d8) with filled 3d orbital electrons can serve as electron donors for PMS, leading to the cleavage of O–O bond and the efficient generation of radical-based ROS. In contrast, Mg(II, 3d0) with unfilled 3d orbital electrons and Zn(II, 3d10) with full filled 3d orbital electrons tend to act as electron shuttles, and the outermost orbitals substantially overlap with the O of PMS to form metastable complexes. Consequently, MgAl-LDH interacts with PMS to selectively degrade quinolones as electron donor through electron transfer pathway, and its performance was not inhibited by common anions and organic matter in actual water. The above results provide a basis for optimizing the design of LDH-based catalysts according to the type of laminate M2+ to achieve high selectivity and efficiency of PMS-AOPs in water purification applications.

Cholesterol-Based B-Ring 2H-Pyran: Synthesis and Reaction Mechanism by Using Density Functional Theoretical Study

Abstract: The steroidal B-ring 2H-pyran 2 is synthesized by reacting steroidal B-ring α,β- unsaturated ketone 1 and 2-cyano-N-methylacetamide by refluxing for 18 h in methanol in the presence of a catalyst, i.e., chitosan. The product is obtained with a yield of 67%. The structure of the final product 2 is confirmed by utilizing IR, Mass, 13C and 1H NMR spectra. The reaction mechanism of the steroidal pyran ring formation is explored in this paper. The reaction pathway is described by using FMO analysis and relative energies of starting material, intermediate, and transition states, calculated by using the theoretical method, i.e., DFT with B3LYP/6-31G(d). It is found that two intermediates are formed throughout the reaction, which undergo a respective transition state (TS1 and TS2). The energy barrier of each step of the reaction is also calculated. It is also concluded that the reaction is endothermic. The green synthetic method reported in this study would be very useful for the synthetic and medicinal chemists involved in the synthesis of biologically important pyran ring-containing heterocyclic compounds.

Enhanced CO2-to-CH4 conversion via grain boundary oxidation effect in CuAg systems

The authentic active sites of oxide-derived copper (OD-Cu), namely grain boundaries (GBs) and oxidized Cuδ+ species, is still debatable, and their role in governing CH4 conversion remains unclear. Herein, this study answers these questions using bimetallic catalysts by novel electro-shock strategy with controllable GBs for the oxidization of Cuδ+ species by modulating Ag loading. The Ag enrichment at the GBs facilitates the bonding of oxygen with the uncoordinated Cu atoms, resulting in GB oxidation effect. The obtained CH4 selectivity is twice that of GBs or nanoalloy effect. The enhanced performance is attributed to the stable Cuδ+ species and unique electron transfer mechanism from GB oxidation structure. Operando attenuated-total-reflection Fourier-transform-infrared-spectroscopy unveils the reaction pathway of CO2-to-CH4 and the sluggish reversible quenching processes of intermediates. Theoretical calculations indicate that the weak *CO adsorption on GB oxidation structure facilitates *CO hydrogenation, promoting CO2-to-CH4 conversion.

Unraveling the atomic structure evolution of titanium nitride upon oxidation

In this study, state-of-the-art aberration-corrected environmental transmission electron microscopy is utilized to investigate the atomic-scale structural evolution of titanium nitride during dynamic oxidation. Titanium nitride oxidation originates from the migration of Ti atoms along {200} that results in two distinct reaction pathways, characterized by the formation of chains of titanium vacancies and staggered titanium vacancies. We demonstrate that titanium atoms exhibit varied oxidation activity on different crystal facets, with the selection of oxidation pathways significantly influenced by the curvature of the crystal surface, which is also supported by the First Principles Calculations.

Catalyzing PET-RAFT Polymerizations Using Inherently Photoactive Zinc Myoglobin.

Protein photocatalysts provide a modular platform to access new reaction pathways and affect product outcomes, but their use in polymer synthesis is limited because co-catalysts and/or co-reductants are required to complete catalytic cycles. Herein, we report using zinc myoglobin (ZnMb), an inherently photoactive protein, to mediate photoinduced electron/energy transfer (PET) reversible addition-fragmentation chain transfer (RAFT) polymerizations. Using ZnMb as the sole reagent for catalysis, photomediated polymerizations of N,N-dimethylacrylamide in PBS were achieved with predictable molecular weights, dispersity values approaching 1.1, and high chain-end fidelity. We found that initial apparent rate constants of polymerization increased from 4.6×10-5 s-1 for zinc mesoporpyhrin IX (ZnMIX) to 6.5×10-5 s-1 when ZnMIX was incorporated into myoglobin to yield ZnMb, indicating that the protein binding site enhanced catalytic activity. Chain extension reactions comparing ZnMb-mediated RAFT polymerizations to thermally-initiated RAFT polymerizations showed minimal differences in block copolymer molecular weights and dispersities. This work enables studies to elucidate how protein modifications (e.g., secondary structure folding, site-directed mutagenesis, directed evolution) can be used to modulate polymerization outcomes (e.g., selective monomer additions towards sequence control, tacticity control, molar mass distributions).

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High-Performance Oxygen Reduction Reaction Activity for Quasi-Solid-State Rechargeable Zn-Air Batteries.

Dimeric metal sites (DiMSs) in carbon-based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, which inspires the investigations on the rational design of DiMSs-based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe-N/CBs) are prepared using the precursor of metal-organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe-N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a high half-wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager-type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi-solid-state Zn-air batteries assembled using DiFe-N/CBs-based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High‐Performance Oxygen Reduction Reaction Activity for Quasi‐Solid‐State Rechargeable Zn‐Air Batteries

AbstractDimeric metal sites (DiMSs) in carbon‐based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, which inspires the investigations on the rational design of DiMSs‐based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe‐N/CBs) are prepared using the precursor of metal‐organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe‐N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a high half‐wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager‐type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi‐solid‐state Zn‐air batteries assembled using DiFe‐N/CBs‐based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Zn-doped hollow cubic MnO2 as a high-performance cathode material for Zn ion batteries.

Manganese-based compounds have the characteristics of high theoretical capacity, low cost and stable performance, thus become a research hotspot for cathode materials of zinc-ion batteries (ZIBs). However, in the process of charging and discharging, it is accompanied by problems such as structural collapse and low conductivity, which resulted in severe capacity degration during cycles. In this paper, a kind of Zn2+ doped MnO2 hollow cube cathode material (Zn-MnO2) was prepared by self-sacrificing template method. The Zn2+ doped in MnO2 crystals can induce oxygen vacancies in the structure, thereby improving the structural stability ion diffusion coefficient and electrical conductivity of the material. After 100 cycles at 0.3 A g-1, the high specific capacity of 281.2 mA h g-1 is still maintained. Through ex-situ XPS and ex-situ XRD tests, the mechanism of charge-discharge process was discussed. The results show that the storage mechanism of Zn-MnO2 is H+ and Zn2+ insertion/removal and Mn3+/Mn2+ two-electron reaction pathway. The total state density (TDOS) and partial state density (PDOS) of Zn-MnO2 and MnO2 further demonstrated that the doping of Zn2+ enhanced the electron conductivity and is beneficial to the electron transfer during the electrochemical reaction.

Catalyzing PET‐RAFT Polymerizations Using Inherently Photoactive Zinc Myoglobin

AbstractProtein photocatalysts provide a modular platform to access new reaction pathways and affect product outcomes, but their use in polymer synthesis is limited because co‐catalysts and/or co‐reductants are required to complete catalytic cycles. Herein, we report using zinc myoglobin (ZnMb), an inherently photoactive protein, to mediate photoinduced electron/energy transfer (PET) reversible addition‐fragmentation chain transfer (RAFT) polymerizations. Using ZnMb as the sole reagent for catalysis, photomediated polymerizations of N,N‐dimethylacrylamide in PBS were achieved with predictable molecular weights, dispersity values approaching 1.1, and high chain‐end fidelity. We found that initial apparent rate constants of polymerization increased from 4.6×10–5 s−1 for zinc mesoporpyhrin IX (ZnMIX) to 6.5×10–5 s−1 when ZnMIX was incorporated into myoglobin to yield ZnMb, indicating that the protein binding site enhanced catalytic activity. Chain extension reactions comparing ZnMb‐mediated RAFT polymerizations to thermally‐initiated RAFT polymerizations showed minimal differences in block copolymer molecular weights and dispersities. This work enables studies to elucidate how protein modifications (e.g., secondary structure folding, site‐directed mutagenesis, directed evolution) can be used to modulate polymerization outcomes (e.g., selective monomer additions towards sequence control, tacticity control, molar mass distributions).

Layered Perovskite La2Ti2O7 Nanostructures for Photocatalytic Degradation of Congo Red Dye Pollutant

AbstractIn photocatalytic innovation, there has been a lot of interest in creating broad spectral responsive photocatalysts to get superior catalytic performance. In this study, we synthesized highly visible‐light responsive La2Ti2O7 perovskite photocatalysts by the probe ultrasonication procedure followed by high‐temperature calcination. Such materials are characterized using UV‐vis diffuse reflectance spectra, powder X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy to illustrate the optical absorption activities, crystalline properties, chemical composition, and microscopic features. La2Ti2O7 extends optical absorption towards the visible light spectrum and narrows the band gap. The photocatalytic efficacy of the resulting La2Ti2O7 nanostructures was investigated by performing photocatalytic degradation of persistent Congo red (CR) dye while subjected to visible photon illumination using three Osram 150 W tungsten halogen lamp ((λ≥400 nm), 5000 lm nominal luminous flux, 80,600 lx radiation intensity. With effective efficiency, the optimum degradation of the 10 ppm CR dye with a percentage of 95.9 was achieved after 90 min during exposure to the La2Ti2O7 perovskite with a catalyst dosage of 30 mg/100 mL at pH 6. Consequently, La2Ti2O7 nanostructures alone depicted 19.8 % adsorption efficiency for CR dye. In addition, OH⋅ and holes were important in degrading CR dye, which included many different reaction pathways. The treated solution can also demonstrate the environment's safety for accepting water. In summary, under natural visible light irradiation, the synthesized La2Ti2O7 showed enormous promise for eliminating different organic contaminants using photocatalytic methodology.

Mn-doped ZnO nanopowders prepared by sol–gel and microwave-assisted sol–gel methods and their photocatalytic properties

Although the microwave-assisted sol–gel method is quite frequently used for the preparation of oxide nanostructures, the synergism of the reaction pathways is not fully explained. However, state-of-the-art theoretical and practical results of high novelty can be achieved by continuously evaluating the as-synthesized materials. The present paper presents a comparative study of Mn-doped ZnO nanopowders prepared by both sol–gel and microwave-assisted sol–gel methods. The structural, morphological, and optical properties of the as-obtained powders were established and correlated with their newly proved functionality, namely, the ability to photogenerate distinct reactive oxygen species (·OH or O2−) and to act as photoactive materials in aqueous media. The solar light-induced mineralization of oxalic acid by Mn-doped ZnO materials was clearly observed while similar amounts of generated CO2 were measured for both catalysts. These inexpensive semiconductor materials, which proved to be light-responsive, can be further used for developing water depollution technologies based on solar light energy.

Ambient pressure x-ray photoelectron spectroscopy study on the initial atomic layer deposition process of platinum

The initial adsorption of MeCpPtMe3 is investigated using synchrotron-based ambient pressure x-ray photoelectron spectroscopy (XPS). The experiments are done on a native oxide-covered Si substrate. In addition, a reaction with O2 and the created Pt surface was investigated. Inspiration for the reaction studies was found from atomic layer deposition of metallic Pt, process that uses the same compounds as precursors. With time-resolved XPS, we have been able to observe details of the deposition process and especially see chemical changes on the Pt atoms during the initial deposition of the Pt precursor. The change of the binding energy of the Pt 4f core level appears to occur on a different timescale than the growth of the active surface sites. The very long pulse of the Pt precursor resulted in a metallic surface already from the beginning, which suggest chemical vapor deposition-like reactions occurring between the surface and the precursor molecules in this experiment. Additionally, based on the XPS data measured after the Pt precursor pulse, we can make suggestions for the reaction pathway, which point toward a scenario that leaves carbon from the MeCpPtMe3 precursor on the surface. These carbon species are then efficiently removed by the subsequent coreactant pulse, leaving behind a mostly metallic Pt film.

A Carborane-Derived Proton-Coupled Electron Transfer Reagent.

Reagents capable of concerted proton-electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C'-diaryl-o-carboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured o-carborane (PhCbPhN) can be reduced and protonated to generate an N-H bond with a weak effective bond dissociation free energy (BDFEeff) of 31 kcal/mol, estimated with measured thermodynamic data. This N-H bond is among the lowest measured element-H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-o-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-o-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.

Unearthing Atomic Dynamics in Nanocatalysts.

Being able to access the rich atomic-scale phenomenology, which occurs during the reactions pathways, is a pressing need toward the pursued knowledge-based design of more efficient nanocatalysts, precisely tailored atom by atom for each reaction. However, to reach this goal of achieving maximum optimization, it is mandatory, first, to address how exposure to the experimental conditions, which will be needed to activate the processes, affects the internal configuration of the nanoparticles at the atomic level. In particular, the most critical experimental parameter is probably the temperature, which among other unwanted effects can induce nanocatalyst aggregation. This work highlights the high potential of experimental techniques such as the scanning probe microscopies, which are able to investigate matter in real space with atomic resolution, to reach the key challenge in heterogeneous catalysis of achieving access to the atomic-scale processes taking place in the nanocatalysts. Specifically, the phenomenology occurring in a nanoparticle system during annealing is studied with atomic precision by scanning tunneling microscopy. As a result, the existence of an internal atomic restructuring, occurring already at relatively low temperatures, within Ir nanoparticles grown over h-BN/Ru(0001) surfaces is demonstrated. Such restructuration, which reduces the undercoordination of the outer Ir atoms, is expected to have a significant effect on the reactivity of the nanoparticles. Going a step further, an internal restructuring of the nanoparticles during their involvement as catalysts has also been also identified.

Research on reaction mechanisms on chemical looping gasification of naphthalene over NiFe2O4 for syngas production: An experimental and theoretical study

The effective removal of tar during biomass gasification is a significant challenge that can be addressed by chemical looping gasification (CLG), which offers a promising alternative for converting biomass into syngas with reduced tar generation. In this study, we investigated the mechanism of CLG of naphthalene as a model biomass tar compound over NiFe2O4 to produce syngas. Both experimental and simulation results indicate the optimal operating conditions for syngas production are 1000℃ and an O/C ratio of 1:1. Under the optimal reaction conditions, the experimental and simulated CO yields were 67 vol% and 73 vol%, respectively, while H2 yields were 22 vol% and 24 vol%. Additionally, carbon conversion rates reached 78% and 76%. Thermodynamic calculations and molecular dynamics simulations revealed that the reactions proceed spontaneously, with increasing temperature favoring naphthalene conversion and syngas production. Density functional theory results indicate that the reaction pathway centered on the carbon at the α-position is the key to naphthalene and NiFe2O4 conversion. The optimal reaction pathways for H2 and CO formation were explored. This study on the CLG of naphthalene over NiFe2O4 provides a theoretical basis for the development of more efficient CLG processes with reduced tar formation.

Examining 1,4,2‐Dioxazol‐5‐One as an Alternative Reagent to Acyl Azides in the Staudinger Reaction

AbstractIn this study, we explore 1,4,2‐dioxazol‐5‐one as an alternative reagent to acyl azides in the Staudinger reaction, providing a safe and efficient method for synthesizing N‐acyliminophosphoranes under metal‐free conditions. This approach involves a heat‐promoted nucleophilic attack of phosphines on 1,4,2‐dioxazol‐5‐ones, followed by the extrusion of CO2 gas, resulting in the formation of the P−N coupling product. The synthetic utility of this metal‐free imidization of phosphine was demonstrated through a gram‐scale reaction and its suitability for subsequent transformations. Density functional theory (DFT) calculations were employed to elucidate the overall reaction pathway leading to the formation of N‐acyliminophosphoranes.

Explosion limits of binary mixtures of ammonia and additives (hydrogen, natural gas, and diethyl ether)

This study investigates the explosion limits of ammonia (NH3) and the effect of three different active fuels, hydrogen (H2), natural gas (NG), and diethyl ether (C2H5OC2H5, DEE), on the explosive characteristics of NH3 through comprehensive chemical kinetics analysis. The results reveal that the explosion limits of NH3 exhibit the narrowest explosive range and display comparatively weakest explosive reactivity among the four fuels, presenting a monotonic changing trend. Reaction pathway analysis unveils that with increasing temperature, NH2 tends to oxidize more predominantly through the NH-N2H2-NNH-N2 pathway, while the conversion of NH2 to H2NO pathway decreases. Therefore, the introduction of active fuels significantly enhances the explosive reactivity of NH3. However, their impact under various temperature-pressure conditions presents nuanced and diversified characteristics. When a 0.5 % mole fraction of active fuel is added to NH3, DEE exhibits the most significant enhancement in medium to high-pressure conditions, while H2 predominates at low pressure, with NG consistently demonstrating the least pronounced enhancement. Upon the active fuel proportion being increased to 20 %, the promoting effect of DEE remains the most significant in the medium to high-pressure region, while NG has surpassed H2 as the secondary dominant fuel. In the low-pressure region, NH3-H2 still demonstrates the highest reactivity, followed by NH3-DEE, while NH3-NG exhibits the least reactivity. These findings provide valuable insights into the widespread utilization and scientific exploration of ammonia as a fuel source.

Mechanistic Study of Highly Active Bifunctional Double-Atom Electrocatalysts for Oxygen Reduction and Oxygen Evolution Reactions.

Dual-atom catalysts (DACs) can be very effective for catalyzing both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, we present theoretical evidence of a new class of highly active DACs, namely, the double-atom embedded in nitrogen-doped graphene sheet 2M-N-C (M = Mn, Fe) on the basis of density functional theory calculations. Importantly, we find that the double active sites of 2M-N-C DACs entail an unconventional catalytic reaction pathway for ORR and OER. We also show that the local coordination environment of the active sites can significantly affect the stability and oxygen catalytic activity of 2M-N-C DACs. In particular, MnFe-N-C DAC not only exhibits good stability but also possesses outstanding bifunctional ORR/OER catalytic activity with the potential difference (ΔE) between the OER and ORR as low as 0.34 V, notably lower than most bifunctional electrocatalysts reported in the literature. This finding suggests a new strategy toward the design of stable and highly active bifunctional electrocatalysts for both ORR/OER.

Revealing the Reaction Pathway of Anodic Hydrogen Evolution at Magnesium Surfaces in Aqueous Electrolytes.

Aqueous metal corrosion is a major economic concern in modern society. A phenomenon that has puzzled generations of scientists in this field is the so-called anomalous hydrogen evolution: the violent dissolution of magnesium under electron-deficient (anodic) conditions, accompanied by strong hydrogen evolution and a key mechanism hampering Mg technology. Experimental studies have indicated the presence of univalent Mg+ in solution, but these findings have been largely ignored because they defy our common chemical understanding and evaded direct experimental observation. Using recent advances in the ab initio description of solid-liquid electrochemical interfaces under controlled potential conditions, we describe the full reaction path of Mg atom dissolution from a kinked Mg surface under anodic conditions. Our study reveals the formation of a solvated [Mg2+(OH)-]+ ion complex, challenging the conventional assumption of Mg2+ ion formation. This insight provides an intuitive explanation for the postulated presence of (Coulombically) univalent Mg+ ions, and the absence of protective oxide/hydroxide layers normally formed under anodic/oxidizing conditions. The discovery of this unexpected and unconventional reaction mechanism is crucial for identifying new strategies for corrosion prevention and can be transferred to other metals.