Hydrogen Evolution Reactivity of Pentagonal Carbon Rings and p-d Orbital Hybridization Effect with Ru.

Topological defects are inevitable existence in carbon-based frameworks, but their intrinsic electrocatalytic activity and mechanism remain under-explored. Herein, the hydrogen evolution reaction (HER) of pentagonal carbon-rings is probed by constructing pentagonal ring-rich carbon (PRC), with optimized electronic structures and higher HER activity relative to common hexagonal carbon (HC). Furthermore, to improve the reactivity, we couple Ru clusters with PRC (Ru@PRC) through p-d orbital hybridization between C and Ru atoms, which drives a shortcut transfer of electrons from Ru clusters to pentagonal rings. The electron-deficient Ru species leads to a notable negative shift in d-band centers of Ru and weakens their binding strength with hydrogen intermediates, thus enhancing the HER activity in different pH media. Especially, at a current density of 10 mA cm-2, PRC greatly reduces alkaline HER overpotentials from 540 to 380 mV. And Ru@PRC even exhibits low overpotentials of 28 and 275 mV to reach current densities of 10 and 1000 mA cm-2, respectively. Impressively, the mass activity and price activity of Ru@PRC are 7.83 and 15.7 times higher than that of Pt/C at the overpotential of 50 mV. Our data unveil the positive HER reactivity of pentagonal defects and good application prospects.

Theoretical Design and Study of a Single-Atom Catalyst in Lithium-Sulfur Batteries: Edge-Type FeN4 Active Site Electron Density Redistribution Driven by Heteroatoms.

Lithium-sulfur (Li-S) batteries are considered to be the most promising next-generation high energy density storage systems. However, they still face challenges, such as the shuttle effect of lithium polysulfides (LiPSs) and slow sulfur oxidation-reduction kinetics. In this work, heteroatom (P and S)-doped edge-type Fe single-atom catalytic materials (FeN4S2/P2-DG) for sulfur reduction reactions (SRRs) and sulfur oxidation reactions in Li-S batteries are investigated using density functional theory calculations. Theoretical analysis suggests that compared to planar Fe-N4 fragments, the charge density accumulation around edge-type Fe-N4 fragments in S- or P-doped structures is higher. Furthermore, the doping of P or S reduces the electron filling state of Fe_3d orbitals, leading to a decrease in electron occupancy in the antibonding orbitals, which is beneficial for the formation of d-p orbital hybridization, strengthening the anchoring strength of FeN4P2/S2-DG for S8/LiPSs. Specifically, FeN4P1,2-DG showed the lowest free energy barriers (0.57 eV) for SRRs and reduced the dissociation energy barrier of Li2S from 1.85 eV (for planar FeN4-G) to 0.96 eV during the charging process, demonstrating excellent catalytic ability. Additionally, this theoretical study provides further insights into the application of graphene-supported single-atom catalyst materials as anchoring materials for Li-S batteries.

Uncovering an Interfacial Band Resulting from Orbital Hybridization in Nickelate Heterostructures.

The interaction of atomic orbitals at the interface of perovskite oxide heterostructures has been investigated for its profound impact on the band structures and electronic properties, giving rise to unique electronic states and a variety of tunable functionalities. In this study, we conducted an extensive investigation of the optical and electronic properties of epitaxial NdNiO3 synthesized on a series of single-crystal substrates. Unlike nanofilms synthesized on other substrates, NdNiO3 on SrTiO3 (NNO/STO) gives rise to a unique band structure featuring an additional unoccupied band situated above the Fermi level. Our comprehensive investigation, which incorporated a wide array of experimental techniques and density functional theory calculations, revealed that the emergence of the interfacial band structure is primarily driven by orbital hybridization between the Ti 3d orbitals of the STO substrate and the O 2p orbitals of the NNO thin film. Furthermore, exciton peaks have been detected in the optical spectra of the NNO/STO film, attributable to the pronounced electron-electron (e-e) and electron-hole (e-h) interactions propagating from the STO substrate into the NNO film. These findings underscore the substantial influence of interfacial orbital hybridization on the electronic structure of oxide thin films, thereby offering key insights into tuning their interfacial properties.

f-π* Back Bonding Orbital Induced by Lutetium-Based Conducting MOF Promotes Highly Selective CO 2 to CH 4 at Low Potential.

The research on electrocatalytic carbon dioxide reduction (ECR) catalysts using renewable energy is particularly crucial in energy conversion studies, especially for viable hydrocarbon production. This study employs density functional theory calculations to screen a series of non-radioactive lanthanide two-dimensional metal-organic frameworks (MOFs) for product selectivity in ECR. Based on theoretical screening, our focus is on a lutetium (Lu)-based conducting MOF (Lu-HHTP), which exhibits a Faradaic efficiency of approximately 77% for methane (CH4) production and maintains a stable current density of -280 mA/cm2 at -1.1 V vs. RHE. In situ electrochemical experiments and material characterization demonstrate that the Lu sites possess high coordination stability and structural recoverability during catalytic CO2 reduction, attributed to the overlap between Lu's f-orbitals and the π*-orbitals of the ligand O, and the formation of back bonding orbitals between the f-orbitals of Lu and the π* orbitals of CO contribute increasing CH4 selectivity and lowering the potential. This study leverages rare-earth MOF-type materials, offering a novel approach to addressing low conductivity and stabilizing rare-earth materials, thereby establishing a theoretical framework for the conversion of linearly adsorbed *CO into hydrocarbons.

Main group metal elements enhance electrochemical nitrogen reduction reaction of vanadium-based single atom catalysts through d-p orbital hybridization.

Developing active sites with flexibility and diversity is crucial for single atom catalysts (SACs) towards sustainable nitrogen fixation at ambient conditions. Herein, the effects of doping main group metal elements (MGM) on the stability, catalytic activity, and selectivity of vanadium-based SACs is systematically investigated based on density functional theory calculations. It is found that the catalytic activity of V site can be significantly enhanced by the synergistic effect between MGM and vanadium atoms. More importantly, a volcano curve between the catalytic activity and the adsorption free energy of NNH* can be established, in which V-Pb dimer embedded on N-coordinated graphene (VPb-NG) exhibits optimal NRR activity due to its location at the top of volcano. Further analysis of electronic structures reveals that the unoccupancy ratio (eg/t2g) of V site is dramatically increased by the strong d-p orbital hybridization between V and Pb atoms, subsequently, N2 is activated to a larger extent. These interesting findings may provide a new path for designing active sites in SACs with excellent performance.

Light-element and purely charge-based topological materials.

We examine a class of Hamiltonians characterized by interatomic, interorbital even-odd parity hybridization as a model for a family of topological insulators without the need for spin-orbit coupling. Non-trivial properties of these materials are exemplified by studying the topologically-protected edge states ofs-phybridized alkali and alkaline earth atoms in one and two-dimensional lattices. In 1D the topological features are analogous to the canonical Su-Schrieffer-Heeger model but, remarkably, occur in the absence of dimerization. Alkaline earth chains, with Be standing out due to its gap size and near particle-hole symmetry, are of particular experimental interest since their Fermi energy without doping lies directly at the level of topological edge states. Similar physics is demonstrated to occur in a 2D honeycomb lattice system ofs-pbonded atoms, where dispersive edge states emerge. Lighter elements are predicted using this model to host topological states in contrast to spin-orbit coupling-induced band inversion favoring heavier atoms.

Energy-Saving Ambient Electrosynthesis of Nylon-6 Precursor Coupled with Electrocatalytic Upcycling of Polyethylene Terephthalate.

Cyclohexanone oxime is an important intermediate in the chemical industry, especially for the manufacture of nylon-6. The traditional cyclohexanone oxime production strongly relies on cyclohexanone-hydroxylamine and cyclohexanone ammoxidation processes, which require harsh reaction conditions and consume considerable amounts of energy. Herein, direct electrosynthesis of cyclohexanone oxime is reported from environmental pollutants nitrite and cyclohexanone with almost 100% yield by using low-cost Cu2Se nanosheets as electrocatalysts. Combination of in situ Fourier transform infrared spectroscopy and theoretical calculations verifies that the p-d orbital hybridization between Cu and Se elements could synergistically optimize the surface electronic structure and enable improved adsorption and formation of the key active N intermediate NH2OH*, thereby enhancing cyclohexanone/nitrite-to-cyclohexanone oxime conversion over the Cu2Se nanosheets. Based on these, an efficient asymmetric co-electrolysis system is further demonstrated by coupling cyclohexanone/nitrite-to-cyclohexanone oxime conversion with the upcycling of polyethylene terephthalate plastics, achieveing energy-saving simultaneously production of value-added products (cyclohexanone oxime and glycolic acid).

Enhancing d/p-2π* Orbitals Hybridization via Strain Engineering for Efficient Photoreduction CO2.

The photoconversion of CO2 into valuable chemical products using solar energy is a promising strategy to address both energy and environmental challenges. However, the strongly adsorbed CO2 frequently impedes the seamless advancement of the subsequent reaction by significantly increasing the reaction activation energy. Here, we present a BiFeO3 material with lattice strain that collaboratively regulates the d/p-2π* orbitals hybridization between metal sites and *CO2 as well as *COOH intermediates to achieve rapid conversion of solidly adsorbed CO2 to critical *COOH intermediates, accelerating the overall CO2 reduction kinetics. Quasi in-situ X-ray photoelectron spectroscopy and in-situ Fourier Transform infrared spectroscopy combined with theoretical calculation reveals that the optimized Fe sites enhance the adsorption and activation effect of CO2, and continuous internal electrons are rapidly transferred to the reaction sites and injected into the surface *CO2 and *COOH under the condition of illumination, which promotes the rapid formation and stability of *COOH. Certainly, the performance of CO2 photoreduction to CO is improved by 12.81-fold compared with the base material. This work offers a new perspective for the rapid photoreduction process of strongly adsorbed CO2.

The "d-p orbital hybridization"-guided design of novel two-dimensional MOFs with high anchoring and catalytic capacities in Lithium - Sulfur batteries.

The energy system of lithium-sulfur batteries is quite promising, however, lithium-sulfur batteries still suffer from considerable problems, such as the abominable shuttle effect of polysulfides (LiPSs), the low conductivity of the solid-phase products, the slow redox kinetics during charging and discharging, and the volume expansion. Herein, the hybridization pattern between the d-orbitals of various transition metal atoms and the p-orbitals of sulfides is revealed grounded in the theory of density function, which explains the high adsorption strength of two-dimensional metal-organic frameworks (MOFs) with LiPSs and accelerates the screening of high-performance anchoring and catalytic materials. The results elucidate that the coordinated transition metal-organic frameworks (Mo-NH MOF) monolayers increase the capacity of LiPSs to anchor by forming more π-bonds from the hybridization of the S p orbitals and Mo d orbitals. Notably, Mo-NH MOF exhibits bifunctional catalytic activity for sulfur reduction as well as Li2S decomposition reactions during charging and discharging, which improves the conversion efficiency of redox reactions. As a result, new MOF materials featuring unique active centers and the potential mechanism by which the active centers modulate the performance of the substrate materials are revealed, and this finding may accelerate the development of high-performance Li-S batteries.

p-d Orbital Hybridization in Ag-based Electrocatalysts for Enhanced Nitrate-to-Ammonia Conversion.

Considering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate-to-ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p-d orbital hybridization via doping p-block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn-doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5±1.85 % for NH3 at -0.4 V vs. RHE and reaches the highest NH3 yield rate to 482.3±14.1 mg h-1 mgcat. -1. In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere-level current density of 1.1 A cm-2 with an NH3 yield of 78.6 mg h-1 cm-2, during which NH3 can be further extracted to prepare struvite as high-quality fertilizer. A mechanistic study reveals that a strong p-d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate-determining step for NH3 synthesis, which as a general principle, can be further extended to Bi- and In-doped Ag catalysts. Moreover, when integrated into a Zn-nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L-1, high power density of 18.1 mW cm-2, and continuous NH3 production.

Modulating the Bader Charge Transfer in Single p-Block Atoms Doped Pd Metallene for Enhanced Oxygen Reduction Electrocatalysis.

Metallene is considered as an emerging family of electrocatalysts due to its atomically layered structure and unique surface stress. Here we propose a strategy to modulate the Bader charge transfer (BCT) between Pd surface and oxygenated intermediates via p-d electronic interaction by introducing single-atom p-block metal (M=In, Sn, Pb, Bi) into Pd metallene nanosheets towards efficient oxygen reduction reaction (ORR). X-ray absorption and photoelectron spectroscopy suggests that doping p-block metals could facilitate electron transfer to Pd sites and thus downshift the d-band center of Pd and weaken the adsorption energy of O intermediates. Among them, the developed Bi-Pd metallene shows extraordinarily high ORR mass activity of 11.34 A mgPd -1 and 0.86 A mgPd -1 at 0.9 V and 0.95 V in alkaline solution, respectively, representing the best Pd-based ORR electrocatalysts ever reported. In the cathode of a Zinc-air battery, Bi-Pd metallene could achieve an open-circuit voltage of 1.546 V and keep stable for 760 h at 10 mA cm-2. Theoretical calculations suggest that the BCT between Pd surface and *OO intermediates greatly affects the bond length between them (dPd-*OO) and Bi doping could appropriately reduce the amount of BCT and stretch the dPd-*OO, thus enhancing the ORR activity.

Modulating Hydrogen Adsorption by Unconventional p-d Orbital Hybridization over Porous High-Entropy Alloy Metallene for Efficient Electrosynthesis of Nylon-6 Precursor.

Renewable electricity driven electrosynthesis of cyclohexanone oxime (C6H11NO) from cyclohexanone (C6H10O) and nitrogen oxide (NOx) is a promising alternative to traditional environment-unfriendly industrial technologies for green synthesis of C6H11NO. Precisely controlling the reaction pathway of the C6H10O/NOx-involved electrochemical reductive coupling reaction is crucial for selectively producing C6H11NO, which is yet still challenging. Herein, we report a porous high-entropy alloy PdCuAgBiIn metallene (HEA-PdCuAgBiInene) to boost the electrosynthesis of C6H11NO from C6H10O and nitrite, achieving a high Faradaic efficiency (47.6 %) and almost 100 % yield under ambient conditions. In situ Fourier transform infrared spectroscopy and theoretical calculations demonstrate that unconventional orbital hybridization between d-block metals and p-block metals could regulate the local electronic structure of active sites and induce electron localization of electron-rich Pd sites, which tunes the active hydrogen supply, facilitates the generation and enrichment of key intermediates NH2OH* and C6H10O*, and efficiently promotes their C-N coupling to selectively produce C6H11NO.

Lattice-Strain Engineering in Ni-Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride.

Ru-based catalysts have emerged as promising alternatives to HgCl2 in vinyl chloride monomer (VCM) production by acetylene hydrochlorination. However, poor C2H2 activation and the generation of key intermediates (*CH2═CH) have posed grand challenges for enhanced catalytic performances. Herein, we synthesized a Ni-intercalated Ru heterostructure using a lattice-strain engineering strategy, resulting in the desired electronic and chemical environments. The collaboration of Ni splits the adsorption centers of C2H2 and HCl by weakening the strong steric hindrance, and it also promotes the activation of the linear C≡C configurations. The well-controlled lattice strain enables strong d-d hybridization interactions between Ni and Ru, resulting in an upshift of the d-band center from -3.72 eV (for Ru/C) to -3.49 eV and electronic delocalization. This optimized local Ni-Ru/C structure thus enhances *H adsorption while weakening the energy barrier for generating *CH2═CH intermediates. Furthermore, the energy barrier for VCM formation was simultaneously reduced. Accordingly, the Ni-Ru/C heterostructures achieve improved performance in pilot-scale trials, with a conversion of >99.2% and stability for over 500 h. These performances significantly surpass most reported Ru-based moieties and the traditional Hg catalysts, offering a promising avenue for C2H2 activation in industrial applications.

Inhibition effect of p-d orbital hybridized PtSn nanozymes for colorimetric sensor array of antioxidants.

Rational design of peroxidase (POD)-like nanozymes with high activity and specificity still faces a great challenge. Besides, the investigations of nanozymes inhibitors commonly focus on inhibition efficiency, the interaction between nanozymes-involved catalytic reactions and inhibitors is rarely reported. In this work, we design a p-block metal Sn-doped Pt (p-d/PtSn) nanozymes with the selective enhancement of POD-like activity. The p-d orbital hybridization interaction between Pt and Sn can effectively optimize the electronic structure of PtSn nanozymes and thus selectively enhance POD-like activity. In addition, the antioxidants as nanozymes inhibitors can effectively inhibit the POD-like activity of p-d/PtSn nanozymes, which results in the fact that antioxidants absorbed on the p-d/PtSn surface can hinder the adsorption of hydrogen peroxide. The inhibition type (glutathione as a model molecule) is reversible mixed-inhibition with inhibition constants (Ki' and Ki) of 0.21 mM and 0.03 mM. Finally, based on the varying inhibition levels of antioxidant molecules, a colorimetric sensor array is constructed to distinguish and simultaneously detect five antioxidants. This work is expected to design highly active and specific nanozymes through p-d orbital hybrid engineering, and also provides insights into the interaction between nanozymes and inhibitors.

Nanoengineering of Cathode Catalysts for Li-O2 Batteries.

Lithium-oxygen (Li-O2) batteries have obtained widespread attention as next-generation energy storage systems due to their extremely high energy density. However, the high charge overpotential, attributed to the insulating property of Li2O2, significantly limits the energy efficiency and triggers solvent degradation. The high electrochemical activities of oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) on the cathode are crucial for alleviating the high charging polarizations and enhancing the lifetime of Li-O2 batteries, which are also top challenges of state-of-art research. In this review, the scientific challenges and the proposed solutions in the development of cathode catalysts have been summarized. The recent research advancements on the nanoengineering of cathode catalysts for Li-O2 batteries have been comprehensively discussed, and the perspectives on the structure optimization are presented. Meanwhile, we have elucidated the structure-performance relationship between the electronic state and performance of the cathode catalysts at the nanoscale level. This review intends to provide guidelines for the design and construction of cathode catalysts in advanced Li-O2 batteries.

Augmented Electrochemical Oxygen Evolution by d-p Orbital Electron Coupling.

While high-entropy alloys, high-entropy oxides, and high-entropy hydroxides, are advanced as a novel frontier in electrocatalytic oxygen evolution, their inherent activity deficiency poses a major challenge. To achieve the unlimited goal to tailor the structure-activity relationship in multicomponent systems, entropy-driven composition engineering presents substantial potential, by fabricating high-entropy anion-regulated transition metal compounds as sophisticated oxygen evolution reaction electrocatalysts. Herein, a versatile 2D high-entropy metal phosphorus trisulfide is developed as a promising and adjustable platform. Leveraging the multiple electron couplings and d-p orbital hybridizations induced by the cocktail effect, the exceptional oxygen evolution catalytic activity is disclosed upon van der Waals material (MnFeCoNiZn)PS3, exhibiting an impressively low overpotential of 240 mV at a current density of 10 mA cm-2, a minimal Tafel slope of 32 mV dec-1, and negligible degradation under varying current densities for over 96 h. Density functional theory calculations further offer insights into the correlation between orbital hybridization and catalytic performance within high-entropy systems, underscoring the contribution of active phosphorus centers on the substrate to performance enhancements. Moreover, by achieving electron redistribution to optimize the electron coordination environment, this work presents an effective strategy for advanced catalysts in energy-related applications.

Tailoring d-p Orbital Hybridization to Decipher the Essential Effects of Heteroatom Substitution on Redox Kinetics.

The heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although the dissimilar metal identification and essential mechanism that dominate the kinetics remain unclear. It is presented that d-p orbital hybridization between the metal and electrolyte ions can be utilized as a descriptor for understanding the redox kinetics. Herein, a series of Co, Fe and Cu heteroatoms are respectively introduced into Ni3Se4 cathodes, among them, only the moderate Co-substituted Ni3Se4 can hold the optimal d-p orbital hybridization resulted from the formed more unoccupied antibonding states π*. It inevitably enhances the interfacial charge transfer and ensures the balanced OH- adsorption-desorption to accelerate the redox kinetics validated by the lowest reaction barrier (0.59 eV, matching well with the theoretical calculations). Coupling with the lower OH- diffusion energy barrier, the prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even the current density increases by 200 times), and an assembled HSC also presents high energy/power density. This work establishes the principles for determining heteroatoms and deciphers the underlying effects of the heteroatom substitution on improving redox kinetics and the rate performance of battery-type electrodes from a novel perspective of orbital-scale manipulation.

Realizing Room-Temperature Ferromagnetism in Molecular-Intercalated Antiferromagnet VOCl.

2D van der Waals (vdW) magnets are gaining attention in fundamental physics and advanced spintronics, due to their unique dimension-dependent magnetism and potential for ultra-compact integration. However, achieving intrinsic ferromagnetism with high Curie temperature (TC) remains a technical challenge, including preparation and stability issues. Herein, an applicable electrochemical intercalation strategy to decouple interlayer interaction and guide charge doping in antiferromagnet VOCl, thereby inducing robust room-temperature ferromagnetism, is developed. The expanded vdW gap isolates the neighboring layers and shrinks the distance between the V-V bond, favoring the generation of ferromagnetic (FM) coupling with perpendicular magnetic anisotropy. Element-specific X-ray magnetic circular dichroism (XMCD) directly proves the source of the ferromagnetism. Detailed experimental results and density functional theory (DFT) calculations indicate that the charge doping enhances the FM interaction by promoting the orbital hybridization between t2 g and eg. This work sheds new light on a promising way to achieve room-temperature ferromagnetism in antiferromagnets, thus addressing the critical materials demand for designing spintronic devices.

Promotion of Acid-Water Oxidation by Lattice Distortion and Orbital Hybridization Induced by Ionic Dopant in Pyrochlore Y2Ru2O7.

For acid-water oxidation, pyrochloric ruthenates are thought to be extremely effective electrocatalysts. In this work, through partial B-site replacement with larger M2+ cations, the electronic states of Y2Ru2O7 with strong electron correlations are reasonably managed, by which the inherent performance is tremendously promoted. Based on this, the improved Y2Ru1.9Sr0.1O7 electrocatalyst exhibits an outstanding durability and presents a highly inherent mass activity of 1915.1 A gRu-1 (at 1.53 V vs RHE). The enhanced oxygen-evolving reaction (OER) activity by ionic dopant in YRO pyrochlore can be attributed to two aspects, i.e., the lattice distortion induced inhibition of the grain coarsening, which results in a large surface area for YRO-M and increases the OER active sites, and the weakening of electron correlation via broadening of the Ru 4d bandwidths due to the increase of the average radius of B-site ions, which gives rise to an enhancement of conductivity and a strengthened hybridization between Ru 4d and O 2p orbitals and improves the reaction kinetics. The synergistic effects of lattice distortion and orbital hybridization promote the enhanced OER activity. The results would provide fresh concepts for the design of improved electrocatalysts and underscore the significance of managing the intrinsic performance through the dual modification of microstructure morphology and electronic structure.

Cascaded p-d Orbital Hybridization Interaction in Ultrathin High-Entropy Alloy Nanowires Boosts Complete Non-CO Pathway of Methanol Oxidation Reaction.

Designing high efficiency platinum (Pt)-based catalysts for methanol oxidation reaction (MOR) with high "non-CO" pathway selectivity is strongly desired and remains a grand challenge. Herein, PtRuNiCoFeGaPbW HEA ultrathin nanowires (HEA-8 UNWs) are synthesized, featuring unique cascaded p-d orbital hybridization interaction by inducing dual p-block metals (Ga and Pb). In comparison with Pt/C, HEA-8 UNWs exhibit 15.0- and 4.2-times promotion of specific and mass activity for MOR. More importantly, electrochemical in situ FITR spectroscopy reveals that the production/adsorption of CO (CO*) intermediate is effectively avoided on HEA-8 UNWs, leading to the complete "non-CO" pathway for MOR. Theoretical calculations demonstrate the optimized electronic structure of HEA-8 UNWs can facilitates a lower energy barrier for the "non-CO" pathway in the MOR.