Bridging OH Research Articles

A New Type of Acidic OH-Groups in the LTL Zeolite

Acidic properties of ion-exchanged LTL zeolites have been studied using FTIR spectroscopy, complemented by X-ray powder diffraction, SEM-EDX, XRF and N2 physisorption. Infrared spectra of the ion-exchanged zeolites show the presence of two intense bands of the bridging OH-groups: a narrow band at ~3640 cm−1 that is attributed to Si(OH)Al groups freely vibrating in 12 MR and a broad, intense band at ~3250 cm−1 that is assigned to bridging OH groups forming hydrogen bond with neighbouring oxygen atoms, e.g., in six-membered rings. The former can be selectively removed by caesium or rubidium cations with up to 3 Cs+ or Rb+ per unit cell readily ion-exchanged into the LTL zeolite, replacing an equivalent number of acidic OH-groups or K+ cations within the structure. The cation migration of the larger cation, evaluated by the Rietveld refinement method, occurs mostly via the main 12 MR channels. By contrast, less than 1 Li+ or Na+ cation per unit cell can be introduced under similar conditions. Accordingly, the concentration of Si(OH)Al groups in back-exchanged NH4-K-LTL with smaller cations (Li+, Na+) does not differ considerably from the concentration of Brønsted acid sites in the original NH4-K-LTL. Lower concentrations of acid sites have been detected in the samples back-exchanged with Cs+, Rb+ and K+. In addition, the acidic properties of NH4-LTL samples have been compared with a structurally related NH4-MAZ zeolite.

Elucidating the Enzymatic Mechanism of Dihydrocoumarin Degradation: Insight into the Functional Evolution of Methyl-Parathion Hydrolase from QM/MM and MM MD Simulations.

Methyl-parathion hydrolase (MPH), which evolved from dihydrocoumarin hydrolase, offers one of the most efficient enzymes for the hydrolysis of methyl-parathion. Interestingly, the substrate preference of MPH shifts from the methyl-parathion to the lactone dihydrocoumarin (DHC) after its mutation of five specific residues (R72L, L273F, L258H, T271I, and S193Δ, m5-MPH). Here, extensive QM/MM calculations and MM MD simulations have been used to delve into the structure-function relationship of MPH enzymes and plausible mechanisms for the chemical and nonchemical steps, including the transportation and binding of the substrate DHC to the active site, the hydrolysis reaction, and the product release. The results reveal that the five mutations remodel the active pocket and reposition DHC within the active site, leading to stronger enzyme-substrate interactions. The MM/GBSA-estimated binding free energies are about -20.7 kcal/mol for m5-MPH and -17.1 kcal/mol for wild-type MPH. Furthermore, this conformational adjustment of the protein may facilitate the chemical step of DHC hydrolysis and the product release, although there is a certain influence on the substrate transport. The hydrolytic reaction begins with the nucleophilic attack of the bridging OH- with the energy barriers of 22.0 and 18.0 kcal/mol for the wild-type and m5-MPH enzymes, respectively, which is rate-determining for the entire process. Unraveling these mechanistic intricacies may help in the understanding of the natural evolution of enzymes for diverse substrates and establish the enzyme structure-function relationship.

Thermodynamics of Proton-Coupled Electron Transfer at Tricopper μ-Oxo/Hydroxo/Aqua Complexes.

Multicopper oxidases (MCOs) utilize a tricopper active site to reduce dioxygen to water through 4H+ 4e- proton-coupled electron transfer (PCET). Understanding the thermodynamics of PCET at a tricopper cluster is essential for elucidating how MCOs harness the oxidative power of O2 while mitigating oxidative damage. In this study, we determined the O-H bond dissociation free energies (BDFEs) and pKa values of a series of tricopper hydroxo and tricopper aqua complexes as synthetic models of the tricopper site in MCOs. Tricopper intermediates on the path of alternating electron and proton transfer (ET-PT-ET-PT-ET) have modest BDFE(O-H) values in the range of 53.0-57.1 kcal/mol. In contrast, those not on the path of ET-PT-ET-PT-ET display much higher (78.1 kcal/mol) or lower (44.7 kcal/mol) BDFE(O-H) values. Additionally, the pKa of bridging OH and OH2 motifs increase by 8-16 pKa units per oxidation state. The same oxidation state changes have a lesser impact on the pKa of N-H motif in the secondary coordination sphere, with an increase of ca. 5 pKa units per oxidation state. The steeper pKa increase of the tricopper center promotes proton transfer from the secondary coordination sphere. Overall, our study shed light on the PCET pathway least prone to decomposition, elucidating why tricopper centers are an optimal choice for promoting efficient oxygen reduction reaction.

Selective removal of phenolic contaminants for carbon recycling by activated persulfate based on oxidative polymerization mechanism

A novel approach for selective removal of phenolic contaminants and polyphenols recycling based on oxidative polymerization is explored, which is significantly different from conventional degradation processes. Plenty of bridging OH− and lattice oxygen are bound on CuO@CuCeyO1+2y+x/2-IE due to strong coordination between Ce and O, which induced formation of Cu(III) with high redox potential. Cu(III) could not only form outer-sphere complexation with peroxymonosulfate (PMS) for enhancement of O2•– production involving series of chain reactions, but also promote O2•– conversion to singlet oxygen (1O2). Owing to electrophilicity, 1O2 preferentially attacked the phenolic hydroxyl group with the production of phenoxeniums ions, and phenoxide ions could immediately couple with negatively charged hydroxyl groups of other bisphenol A (BPA) molecular so as to make polymer chains get a sustained growth over CuO@CuCeyO1+2y+x/2-IE. Thus, CuO@CuCeyO1+2y+x/2-IE can selectively remove phenolic contaminants from water with low oxidant consumption, and simultaneously recycle more than 80 % of polyphenols. In summary, the present work demonstrated the predominant role and mechanism of 1O2 in triggering the oxidative polymerization of BPA, which contributed to construction of cost-efficient catalytic system for phenolic contaminants conversion into polyphenols.

Unravelling the effect of Cl- on alkaline saline water electrooxidation on NiFe (oxy)hydroxides

One of the major problems for seawater electrolysis is chloride corrosion arising from the chlorine oxidation reaction (ClOR). Although researchers have endeavored to improve the OER activity (overpotentials below 490 mV) to avoid the ClOR, an OER deactivation effect of chloride anions still looms large even before the ClOR becomes a serious issue, and its mechanism remains unclear. Herein using a simple Fourier transform ac voltammetry (FTacV) method, we unveil a hidden fact about the detrimental effect of Cl- over an exemplar catalyst NiFe (oxy)hydroxide: it increases the formation potential of Ni(IV) thus lowering the OER performance. This is borne out by theoretical calculations, which reveal changes in the electronic environment of Ni sites induced by replacing the bridge OH- species with Cl- and the resulting difficulty to form high-valence Ni(IV). The consequence is a large increase in energy barrier of the OH* deprotonation step that lowers the OER activity. The poison effect of Cl- can be restrained by adding carbonate ions, which restores the facile formation of Ni(IV) and stabilizes the electrode for over 140-h saline water oxidation reaction at the current density of 100 mA cm−2. This work helps to guide the design of active and durable seawater-splitting electrocatalysts.

Fundamental Insights into Reaction Centers and Catalytic Mechanisms of Ni- and Co-Based Layered Oxyhydroxides for the Oxygen Evolution Reaction

Water splitting to generate green H2 fuel and O2 is essential for global CO2 reductions toward net-zero emissions. In this process, however, O2 generation at the anode through the oxygen evolution reaction (OER) is inherently slower by orders of magnitude than H2 generation at the cathode. Thus, improving OER efficiency has been a major effort in electrolysis. Ni-based and Co-based layered hydroxides are among the most active and studied non-previous catalysts in alkaline electrolytes. Although tremendous advances have been made toward improving the activity and the stability of the catalysts over the past decade, there is still a lack of fundamental insights into active sites and reaction mechanisms, which has hindered the establishment of structure-property relationships.This talk will first provide fundamental insights into reaction centers and catalytic mechanisms of classic Ni oxyhydroxides and Co oxyhydroxides with and without ligand intercalation. We will further discuss the multiple-site synergy in Ni- and Co-based layered double hydroxides (LDH) and ternary hydroxides. We will show that the OER proceeds via a Mars van Krevelen mechanism, starting with the oxidation of bridge OH at the reaction centers with dual metal sites, i.e., M1-OH-M2. We will demonstrate that, to approach the minimum overpotential dictated by a specific OH-OOH scaling relationship, the key is to break the OH-O scaling relationship. A possible route is to form binary metal oxyhydroxides with dual metal sites at the reaction centers or introduce a third element into NiFe LDH or CoFe LDH. If time permits, We will further discuss the role of the non-covalent interaction and polaron-like electronic states in promoting OER at M1-OH-M2 centers.

QM/MM and MM MD Simulations on Enzymatic Degradation of the Nerve Agent VR by Phosphotriesterase.

V-type nerve agents are hardly degraded by phosphotriesterase (PTE). Interestingly, the PTE variant of BHR-73MNW can effectively improve the hydrolytic efficiency of VR, especially for its Sp-enantiomer. Here, the whole enzymatic degradation of both Sp and Rp enantiomers of VR by the wild-type PTE and its variant BHR-73MNW was investigated by quantum mechanics/molecular mechanics (QM/MM) calculations and MM molecular dynamics simulations. Present results indicate that the degradation of VR can be initiated by the nucleophilic attack of the bridging OH- and the zinc-bound water molecule. The QM/MM-predicted energy barriers for the hydrolytic process of Sp-VR are 19.8 kcal mol-1 by the variant with water as a nucleophile and 22.0 kcal mol-1 by the wild-type PTE with OH- as a nucleophile, and corresponding degraded products are bound to the dinuclear metal site in monodentate and bidentate coordination modes, respectively. The variant effectively increases the volume of the large pocket, allowing more water molecules to enter the active pocket and resulting in the improvement of the degradation efficiency of Sp-VR. The hydrolysis of Rp-VR is triggered only by the hydroxide with an energy span of 20.6 kcal mol-1 for the wild-type PTE and 20.7 kcal mol-1 for the variant BHR-73-MNW PTE. Such mechanistic insights into the stereoselective degradation of VR by PTE and the role of water may inspire further studies to improve the catalytic efficiency of PTE toward the detoxification of nerve agents.

Silane-Functionalized Metal-Organic Frameworks for Stimuli-Responsive Drug Delivery Systems: A New Universal Strategy.

A new universal strategy for silane functionalization of metal-organic frameworks (MOFs) was developed. It was demonstrated that silanes were coupled both with terminal hydroxyl (OH) groups and with bridging OH groups of metal-oxo clusters of MOFs through condensation reactions between the silanols of hydrolyzed silanes and the terminal/bridging OH groups to form metal-O-Si bonds. A wide variety of functionalization of MOFs with conventional silanes can be realized by combining synthesis reactions in the solution phase and chemical modifications on the surface. Multivalent supramolecular nanovalves based on the host-guest chemistry of cyclodextrin polymer (CDP) and benzimidazole stalks silanized on the nanoscale MOF (NMOF) surface were successfully constructed. The CDP-valved NMOFs showed the excellent performance of low pH- and α-amylase-responsive controlled drug release. In vitro and in vivo results demonstrated that the CDP-valved NMOFs had a significant inhibitory effect on tumor growth and almost no damage/toxicity to normal tissues. The silanization strategy is universal and opens up a new way for the functionalization of MOFs, which are endowed with a wide variety of applications spanning gas storage, chemical sensing, adsorption and separation, heterogeneous catalysis, and drug delivery.

Catalytic Reaction Mechanism of Glyoxalase II: A Quantum Mechanics/Molecular Mechanics Study.

Methylglyoxal (MG) is a reactive and toxic compound produced in carbohydrate, lipid, and amino acid metabolism. The glyoxalase system is the main detoxifying route for MG and consists of two enzymes, glyoxalase I (GlxI) and glyoxalase II (GlxII). GlxI catalyzes the formation of S-d-lactoylglutathione from hemithioacetal, and GlxII converts this intermediate to d-lactate. A relationship between the glyoxalase system and some diseases like diabetes has been shown, and inhibiting enzymes of this system may be an effective means of controlling certain diseases. A detailed understanding of the reaction mechanism of an enzyme is essential to the rational design of competitive inhibitors. In this work, we use quantum mechanics/molecular mechanics (QM/MM) calculations and energy refinement utilizing the big-QM and QM/MM thermodynamic cycle perturbation methods to propose a mechanism for the GlxII reaction that starts with a nucleophilic attack of the bridging OH- group on the substrate. The coordination of the substrate to the Zn ions places its electrophilic center close to the hydroxide group, enabling the reaction to proceed. Our estimated reaction energies are in excellent agreement with experimental data, thus demonstrating the reliability of our approach and the proposed mechanism. Additionally, we examined alternative protonation states of Asp-29, Asp-58, Asp-134, and the bridging hydroxide ion in the catalytic process. However, these give less favorable reactions, a poorer reproduction of the crystal structure geometry of the active site, and higher root-mean-squared deviations of the active site residues in molecular dynamics simulations.

Spectroscopic Signatures of Internal Hydrogen Bonds of Brønsted‐Acid Sites in the Zeolite H‐MFI

AbstractThe location of Brønsted‐acid sites (bridging OH groups, b‐OH) at different crystallographic positions of zeolite catalysts influences their reactivity due to varying confinement. Selecting the most stable b‐OH conformers at each of the 12 T‐sites (T=Si/Al) of H‐MFI, a representative set of 26 conformers is obtained which includes free b‐OH groups pointing into the empty pore space and b‐OH groups forming H‐bonds across five‐ or six‐membered rings of TO4 tetrahedra. Chemically accurate coupled‐cluster‐quality calculations for periodic models show that the strength of internal H‐bonds and, hence, the OH bond length vary substantially with the framework position. For 11 of the 19 H‐bonded b‐OH groups examined, our predictions fall into the full width at half maximum range of the experimental signals at 3250±175 cm−1 and 7.0±1.4 ppm which supports previously debated assignments of these signals to H‐bonded b‐OH sites.

Spectroscopic Signatures of Internal Hydrogen Bonds of Brønsted-Acid Sites in the Zeolite H-MFI.

The location of Brønsted-acid sites (bridging OH groups, b-OH) at different crystallographic positions of zeolite catalysts influences their reactivity due to varying confinement. Selecting the most stable b-OH conformers at each of the 12 T-sites (T=Si/Al) of H-MFI, a representative set of 26 conformers is obtained which includes free b-OH groups pointing into the empty pore space and b-OH groups forming H-bonds across five- or six-membered rings of TO4 tetrahedra. Chemically accurate coupled-cluster-quality calculations for periodic models show that the strength of internal H-bonds and, hence, the OH bond length vary substantially with the framework position. For 11 of the 19 H-bonded b-OH groups examined, our predictions fall into the full width at half maximum range of the experimental signals at 3250±175 cm-1 and 7.0±1.4 ppm which supports previously debated assignments of these signals to H-bonded b-OH sites.

Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering.

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO2 (rutile and P25) with increasing oxygen deficiency and Ti3+ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti3+ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti3+ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.

Влияние фторирования катализатора MoO3/Al2O3 на протекание метатезиса пропилена

In the course of this work, fluorinated catalysts MoO3/Al2O3-F for the olefins metathesis have been synthesized. The materials have been characterized by various physicochemical methods and tested in the propylene metathesis reaction. It has been shown that the support fluorination leads to partial replacement of surface hydroxyl groups by F, which is accompanied by an increase in the strength of both Lewis acid sites and residual bridging OH groups. Increasing the fluorine content on γ-Al2O3 up to 3 wt. % leads to an increase in the conversion of propylene in the metathesis reaction by 1.5 times (WHSV = 1.1 h-1, Т = 100 °С, р = 9 atm.) with a selectivity of more than 95%. However, when the reaction is carried out at atmospheric pressure, fluorinated samples show lower activity than unpromoted ones. The results of this work show that the support acidity plays an important role in propylene metathesis. The proposed method of catalyst modification opens up new possibilities for improving classical metathesis catalysts.

Water Photo-Oxidation over TiO2—History and Reaction Mechanism

Photocatalytic water oxidation over titanium dioxide (TiO2) was overviewed by surveying briefly the history of water photo-oxidation, followed by profiling the research for the molecular mechanism of oxygen evolution reaction (OER) at the TiO2 surface. As the experimental approach to investigate the reaction mechanism, ESR, NMR, and STM were described as well as FTIR spectroscopy. Detection of reactive oxygen species, which are the intermediate species in the OER, was also involved in discussing the mechanism. As the theoretical approach to the reaction mechanism, some research with density functional theory (DFT) for anatase (101) surface was illustrated. Since the OER activity of rutile TiO2 is higher than that of anatase, and the rutile (011) surface has been assigned to the oxidation facet, we performed a DFT calculation for a (011) surface model molecule. The results were successfully discussed with the reported mechanism. The first oxidation step occurs at the bridging OH site, which faces a Ti5C site. The water molecule which coordinates both sites is oxidized, and the resultant radical coordinates the Ti5C site to form a trapped hole Ti-O•. In the second step, a coordinated water molecule is oxidized at the Ti-O• site to form a Ti-OOH structure.

Resource utilization of steel converter slag: Efficient degradation of typical organic flotation reagent α-nitroso-β-naphthol via the synergy of radical and non-radical pathways

The organic pollution generated during production and processing in the mining area seriously endangers the ecological security of the surrounding environment. In this study, degradation of α-nitroso-β-naphthol (αNβN), a typical organic flotation reagent in mining area, by using steel converter slag (SCS) as a low-cost catalyst was reported for the first time. The results showed that SCS + H2O2 could effectively remove αNβN from water solutions. In the system used in this study, more than 98.8 % of αNβN could be removed within 60 min. Based on the analysis of the experimental results, the synergistic mechanism of radical and non-radical pathways was proposed. The radical pathway mainly consisted of OH radical oxidation, while the non-free radical pathway consisted of 1O2 and electron transfer. Fe, bridging OH and terminal OH on the surface of SCS were the active sites for H2O2 activation. The removal performance of the system was not affected by common coexisting ions, and showed strong anti-interference ability. After 4 times repeated use, the removal efficiency still reached more than 83 %. HPLC-MS was used to analyze the intermediate products, while the changes in their toxicity effects were analyzed by microcalorimetry for the first time. The results showed that the system could effectively reduce the ecotoxicity of a water solution containing αNβN. This study provides not only a new strategy for treating organic pollution in mining areas, but also a new idea for the green cycle development of industry and mining from the perspective of “treat the wastes with wastes”.

Na Promotion of Pt/m-ZrO2 Catalysts for the Steam Reforming of Formaldehyde

The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H2O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO2 temperature programmed desorption results, as well as a greater splitting observed between the formate νasym(OCO) and νsym(OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer.

Promoting effect of MoO3/Al2O3 catalysts fluorination on their reactivity in propylene metathesis

Supported MoO3/Al2O3-F catalysts were synthesized and characterized by Raman, IR, and NMR spectroscopy. It was shown that support fluorination leads to partial substitution of surface OH groups with F which is accompanied by increases the strength of both LAS (Lewis Acid Sites) and residual bridging OH groups. But the change in the acidity doesn’t affect the structure of surface molybdenum forms. An increase of the fluorine content on γ-Al2O3 up to 6 wt% leads to 4.7-fold increase of the propylene conversion in metathesis reaction (WHSV = 11 h−1, T = 100 °C, p = 9 atm.) with selectivity above 95 %. The results prove that the support acidity plays an important role in the propylene metathesis. The catalyst modification method proposed here opens new opportunities for the improvement of classical metathesis catalysts.

Dehydrogenation of Ammonia Borane by Platinum-Nickel Dimers: Regulation of Heteroatom Interspace Boosts Bifunctional Synergetic Catalysis.

Regulation of the atom-atom interspaces of dual-atom catalysts is essential to optimize the dual-atom synergy to achieve high activity but remains challenging. Herein, we report an effective strategy to regulate the Pt1 -Ni1 interspace to achieve Pt1 Ni1 dimers and Pt1 +Ni1 heteronuclear dual-single-atom catalysts (HDSACs) by tailoring steric hindrance between metal precursors during synthesis. Spectroscopic characterization reveals obvious electron transfers in Pt1 Ni1 oxo dimers but not in Pt1 +Ni1 HDSAC. In the hydrolysis of ammonia borane (AB), the H2 formation rates show an inverse proportion to the Pt1 -Ni1 interspace. The rate of Pt1 Ni1 dimers is ≈13 and 2 times higher than those of Pt1 and Pt1 +Ni1 HDSAC, manifesting the interspace-dependent synergy. Theoretical calculations reveal that the bridging OH group in Pt1 Ni1 dimers promotes water dissociation, while Pt1 facilitates the cleavage of B-H bonds in AB, which boosts a bifunctional synergy to accelerate H2 production cooperatively.

Dehydrogenation of Ammonia Borane by Platinum‐Nickel Dimers: Regulation of Heteroatom Interspace Boosts Bifunctional Synergetic Catalysis

AbstractRegulation of the atom‐atom interspaces of dual‐atom catalysts is essential to optimize the dual‐atom synergy to achieve high activity but remains challenging. Herein, we report an effective strategy to regulate the Pt1‐Ni1 interspace to achieve Pt1Ni1 dimers and Pt1+Ni1 heteronuclear dual‐single‐atom catalysts (HDSACs) by tailoring steric hindrance between metal precursors during synthesis. Spectroscopic characterization reveals obvious electron transfers in Pt1Ni1 oxo dimers but not in Pt1+Ni1 HDSAC. In the hydrolysis of ammonia borane (AB), the H2 formation rates show an inverse proportion to the Pt1‐Ni1 interspace. The rate of Pt1Ni1 dimers is ≈13 and 2 times higher than those of Pt1 and Pt1+Ni1 HDSAC, manifesting the interspace‐dependent synergy. Theoretical calculations reveal that the bridging OH group in Pt1Ni1 dimers promotes water dissociation, while Pt1 facilitates the cleavage of B−H bonds in AB, which boosts a bifunctional synergy to accelerate H2 production cooperatively.

Catalytically-Active Phases and Reaction Mechanism of Ni-Based and Co-Based Layered Double Hydroxides for the Oxygen Evolution Reaction

Electrochemical water splitting using renewable energy is a key route to generate green H2 fuel. In this process, however, O2 generation at the anode through the oxygen evolution reaction (OER) is inherently slower by over four orders of magnitude than H2 generation at the cathode. Thus, improving OER efficiency has been a majority effort in electrolysis. Ni-based and Co-based layered double hydroxides (LDHs) are among the most active and studied catalysts for the oxygen evolution reaction (OER) in alkaline electrolytes. Because it happens under extremely oxidative aqueous conditions, however, in-situ crystal structures of the OER active phase are still largely unknown, significantly hindering the establishment of structure-property relationships.In this talk, we provide the first direct atomic-scale evidence that, under applied anodic potentials, NiFe and CoFe LDHs oxidize from as-prepared α-phases to activated γ-phases. The OER-active γ-phases are characterized by about 8% contraction of the lattice spacing and switching of the intercalated ions from carbonate to potassium. The calculated surface phase diagrams indicate that surface O sites are saturated with H by forming bridge OH, and coordinatively unsaturated metal sites are poisoned by OH adsorption under OER conditions. These structures, and the associated reaction free energies, suggest that the OER proceeds via a Mars van Krevelen mechanism, starting with the oxidation of bridge OH at the reaction centers with dual metal sites, i.e., M1-OH-M2.Our study suggests that the compound-dependent activity originates from the dual-metal site feature of the reaction centers. While this feature does not influence the OH-OOH scaling relationship, it leads to diverse OH-O scaling relationships, including those with near-zero slopes and negative slopes. Breaking OH-OOH scaling relationships were frequently discussed in the literature, as it determines the minimum overpotential. However, our study showed that, to approach the minimum overpotential dictated by a specific OH-OOH scaling relationship, the key is to break the OH-O scaling relationship. A possible route is to form binary metal oxyhydroxides with dual metal sites at the reaction centers or introduce a third element into NiFe LDH or CoFe LDH.