Local Coordination Environment Research Articles

Synergy Between Supported Metal Single Atoms and Nanoparticles and their Relevance in Catalysis

AbstractCatalytic active sites consisting in isolated metal single atoms can be found in enzymatic, homogenous and heterogeneous catalysts. In heterogeneous catalysis, single‐atom catalysts (SACs) may offer high reactivity and selectivity towards some reactions provided their local coordination environment and electronic properties are correctly tuned. These sites generally possess specific properties compared to metal nanoparticles or clusters. Because of the difficulty, inherent in supported catalysis, of preparing catalysts having a high homogeneity of active sites, these two species have had to coexist in many supported catalysts. If the current trend is often limited to comparing the reactivity of these two types of species, we will see in this mini‐review that for few years, work has highlighted a possible synergy between these species to improve catalytic performance. The different types of synergies are discussed, as well as challenges and opportunities for such catalysts in thermal‐, electro‐ and photo‐catalysis.

Modulating the local coordination environment of cobalt single-atomic nanozymes for enhanced catalytic therapy against bacteria.

Single-atomic nanozymes (SANZs) characterized by atomically dispersed single metal atoms have recently contributed to breakthroughs in biomedicine due to their satisfactory catalytic activity and superior selectivity compared to their nanoscale counterparts. The catalytic performance of SANZs can be improved by modulating their coordination structure. Therefore, adjusting the coordination number of the metal atoms in the active center is a potential method for enhancing the catalytic therapy effect. In this study, we synthesized various atomically dispersed Co nanozymes with different nitrogen coordination numbers for peroxidase (POD)-mimicking single-atomic catalytic antibacterial therapy. Among the polyvinylpyrrolidone modified single-atomic Co nanozymes with nitrogen coordination numbers of 3 (PSACNZs-N3-C) and 4 (PSACNZs-N4-C), single-atomic Co nanozymes with a coordination number of 2 (PSACNZs-N2-C) had the highest POD-like catalytic activity. Kinetic assays and Density functional theory (DFT) calculations indicated that reducing the coordination number can lower the reaction energy barrier of single-atomic Co nanozymes (PSACNZs-Nx-C), thereby increasing their catalytic performance. In vitro and in vivo antibacterial assays demonstrated that PSACNZs-N2-C had the best antibacterial effect. This study provides proof of concept for enhancing single-atomic catalytic therapy by regulating the coordination number for various biomedical applications, such as tumor therapy and wound disinfection. STATEMENT OF SIGNIFICANCE: The use of nanozymes that contain single-atomic catalytic sites has been shown to effectively promote the healing of bacteria-infected wounds by exhibiting peroxidase-like activity. The homogeneous coordination environment of the catalytic site has been associated with high antimicrobial activity, which provides insight into designing new active structures and understanding their mechanisms of action. In this study, we designed a series of cobalt single-atomic nanozymes (PSACNZs-Nx-C) with different coordination environments by shearing the Co-N bond and modifying polyvinylpyrrolidone (PVP). The synthesized PSACNZs-Nx-C demonstrated enhanced antibacterial activity against both Gram-positive and Gram-negative bacterial strains, and showed good biocompatibility in both in vivo and in vitro experiments.

Oxidation rates and redox stabilization of ferrous iron in trioctahedral smectites

Iron(II)-bearing trioctahedral smectites (saponites) form during anoxic alteration of basaltic rock. They are predicted to have been widespread on the early Earth and are observed in the oceanic subsurface today. Smectite structures, including the occupancy of sites in the octahedral sheet, affect iron redox behavior but the rates and products of trioctahedral smectite oxidation have been largely unexplored to date. In this study we synthesized two Fe(II)-bearing trioctahedral smectites, one moderate (22 wt% Fe) and one high (27 wt% Fe) in iron content. We then examined the rate, extent, and products of their oxidation by dissolved oxygen, nitrite, and hydrogen peroxide. Dissolved oxygen caused partial oxidation of Fe(II) in the smectites with 14 to 43% of Fe(II) unoxidized after 20 to 30 days of exposure. The rate and extent of oxidation correlated with the dissolved oxygen concentration and the Fe(II) content of the clay. The incomplete oxidation in these experiments is consistent with the mixed-valent trioctahedral smectites observed in oxidized natural samples but contrasts with the complete reoxidation by oxygen shown by chemically- or microbially-reduced dioctahedral smectites. Oxidation of structural Fe(II) by 5 mmol L−1 nitrite was negligible for the moderate-iron smectite and yielded only ∼17% oxidation after 54 days of reaction for the high-iron smectite. Hydrogen peroxide caused rapid and near-complete oxidation of both clays. Powder X-ray diffraction, variable-temperature Mössbauer spectroscopy, and extended X-ray absorption fine structure spectroscopy together detected no crystalline or short-range-ordered secondary phases and show that oxidized iron remained in the trioctahedral smectite structure. The recalcitrant Fe(II) pool in oxidized trioctahedral smectites exists in less distorted sites than Fe(II) in the initial clays. Its unreactive nature at prolonged reaction times indicates an elevated redox potential generated by the local coordination environment. Slower oxidation rates create a larger recalcitrant Fe(II) pool, suggesting kinetic competition between oxidation and a process involved in redox stabilization, such as electron exchange between octahedral iron sites or deprotonation of hydroxyl groups in the structure. The resistance to complete oxidation of trioctahedral ferrous smectites and their full retention of iron demonstrates that transitions from anoxic to oxic conditions generate mixed-valence smectites rather than a mixture of new phases. Identifying the diagenetic products of mixed-valent trioctahedral smectites may provide an indicator in the rock record of past redox cycling. Substantial portions of structural Fe(II) in trioctahedral smectites display slow abiotic oxidation kinetics and represent potential electron donors for both microaerophilic iron oxidizing and nitrate-reducing, iron-oxidizing microorganisms in altered mafic rocks and related settings.

Hierarchically Porous Carbons with Highly Curved Surfaces for Hosting Single Metal FeN4 Sites as Outstanding Oxygen Reduction Catalysts.

Iron-nitrogen-carbon (FeNC) materials have emerged as a promising alternative to platinum-group metals for catalyzing the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells. However, their low intrinsic activity and stability are major impediments. Herein, an FeN-C electrocatalyst with dense FeN4 sites on hierarchically porous carbons with highly curved surfaces (denoted as FeN4 -hcC) is reported. The FeN4 -hcC catalyst displays exceptional ORR activity in acidic media, with a high half-wave potential of 0.85V (versus reversible hydrogen electrode) in 0.5m H2 SO4 . When integrated into a membrane electrode assembly, the corresponding cathode displays a high maximum peak power density of 0.592W cm-2 and demonstrates operating durability over 30000 cycles under harsh H2 /air conditions, outperforming previously reported Fe-NC electrocatalysts. These experimental and theoretical studies suggest that the curved carbon support fine-tunes the local coordination environment, lowers the energies of the Fe d-band centers, and inhibits the adsorption of oxygenated species, which can enhance the ORR activity and stability. This work provides new insight into the carbon nanostructure-activity correlation for ORR catalysis. It also offers a new approach to designing advanced single-metal-site catalysts for energy-conversion applications.

Structure and Dynamics of NaCl/KCl/CaCl2-EuCln (n = 2, 3) Molten Salts.

Modern molten salt reactor design and the techniques of electrorefining spent nuclear fuels require a better understanding of the chemical and physical behavior of lanthanide/actinide ions with different oxidation states dissolved in various solvent salts. The molecular structures and dynamics that are driven by the short-range interactions between solute cations and anions and long-range solute and solvent cations are still unclear. In order to study the structural change of solute cations caused by different solvent salts, we performed first-principles molecular dynamics simulations in molten salts and extended X-ray absorption fine structure (EXAFS) measurements for the cooled molten salt samples to identify the local coordination environment of Eu2+ and Eu3+ ions in CaCl2, NaCl, and KCl. The simulations reveal that with the increasing polarizing the outer sphere cations from K+ to Na+ to Ca2+, the coordination number (CN) of Cl- in the first solvation shell increases from 5.6 (Eu2+) and 5.9 (Eu3+) in KCl to 6.9 (Eu2+) and 7.0 (Eu3+) in CaCl2. This coordination change is validated by the EXAFS measurements, in which the CN of Cl- around Eu increases from 5 in KCl to 7 in CaCl2. Our simulation shows that the fewer Cl- ions coordinated to Eu leads to a more rigid first coordination shell with longer lifetime. Furthermore, the diffusivities of Eu2+/Eu3+ are related to the rigidity of their first coordination shell of Cl-: the more rigid the first coordination shell is, the slower the solute cations diffuse.

Cover Feature: Boosting the Electrochemical Performance of Lithium‐Rich Cathodes by Oxygen Vacancy Engineering (Batteries & Supercaps 7/2023)

The Cover Feature shows the Li-rich layered oxide, as promising cathode materials for powering electric vehicle (EVs) applications due to their high energy density. Post-annealing strategy is developed to pre-introduce oxygen vacancies (OVs) into Li1.2Mn0.457Ni0.229Co0.114O2 cathode to modify the local Mn coordination environments, enhance structural stability, and suppress oxygen release. The presence of oxygen vacancies through thermal expansion diminishes the phase transitions in cathode materials during the heating process. More information can be found in the Research Article by H. Gao, G. Wang and co-workers.

In Situ Charge Modification within Prussian Blue Analogue Nanocubes by Plasma for Oxygen Evolution Catalysis.

A targeted defect-induced strategy of metal sites in a porous framework is an efficient avenue to improve the performance of a catalyst. However, achieving such an activation without destroying the ordered framework is a major challenge. Herein, a dielectric barrier discharge plasma can etch the Fe(CN)6 group of the NiFe Prussian blue analogue framework in situ through reactive oxygen species generated in the air. Density functional theory calculations prove that the changed local electronic structure and coordination environment of Fe sites can significantly improve oxygen evolution reaction catalytic properties. The modified NiFe Prussian blue analogue is featured for only 316 mV at a high current density (100 mA cm-2), which is comparable to that of commercial alkaline catalysts. In a solar cell-driven alkaline electrolyzer, the overall electrolysis efficiency is up to 64% under real operation conditions. Over 80 h long-time continuous test under 100 mA cm-2 highlights superior durability. The density functional theory calculations confirm that the formation of OOH* is the rate-determining step over Fe sites, and Fe(CN)6 vacancy and extra oxygen atoms can introduce charge redistribution to the catalyst surface, which finally enhances the oxygen evolution reaction catalytic properties by reducing the overpotential by 0.10 V. Both experimental and theoretical results suggest that plasma treatment strategy is useful for modifying the skeletal material nondestructively at room temperature, which opens up a broad prospect in the field of catalyst production.

Insight into Eu3+-Doped Phase-Change K3Lu(PO4)2 Phosphate toward Data Encryption.

Adjusting the local coordination environment of lanthanide luminescent ions can modulate their crystal-field splittings and broaden their applications in the relevant optical fields. Here, we introduced Eu3+ ions into the phase-change K3Lu(PO4)2 phosphate and found that the temperature-induced reversible phase transitions of K3Lu(PO4)2 (phase I ⇆ phase II and phase II ⇆ phase III, below room temperature) give rise to an obvious photoluminescence (PL) difference of Eu3+ ions. The Eu3+ emission mainly focused on the 5D0 → 7F1 transition in phase III but manifested comparable 5D0 → 7F1,2 transitions in the two low-temperature phases. On this basis, the change of Eu3+-doped concentration led to the phase evolution in Eu3+:K3Lu(PO4)2, which could stabilize two types of low-temperature polymorphs to the specific temperature by controlling the doping content. Finally, we proposed a feasible information encryption strategy based on the PL modulation of Eu3+:K3Lu(PO4)2 phosphors, which was caused by the temperature hysteresis of the relevant phase transition, exhibiting good stability and reproducibility. Our findings pave an avenue for exploring the optical application of lanthanide-based luminescent materials by introducing phase-change hosts.

Fe/Co dual metal catalysts modulated by S-ligands for efficient acidic oxygen reduction in PEMFC.

Here, we report a conceptual strategy for introducing spatial sulfur (S)-bridge ligands to regulate the coordination environment of Fe-Co-N dual-metal centers (Spa-S-Fe,Co/NC). Benefiting from the electronic modulation, Spa-S-Fe,Co/NC catalyst showed remarkably enhanced oxygen reduction reaction (ORR) performance with a half-wave potential (E1/2) of 0.846 V and satisfactory long-term durability in acidic electrolyte. Combined experimental and theoretical studies revealed that the excellent acidic ORR activity with a remarkable stability observed for Spa-S-Fe,Co/NC is attributable to the optimal adsorption-desorption of ORR oxygenated intermediates achieved through charge-modulation of Fe-Co-N bimetallic centers by the spatial S-bridge ligands. These findings provide a unique perspective to regulate the local coordination environment of catalysts with dual-metal-centers to optimize their electrocatalytic performance.

Active Site Descriptors from 95Mo NMR Signatures of Silica-Supported Mo-Based Olefin Metathesis Catalysts.

The olefin metathesis activity of silica-supported molybdenum oxides depends strongly on metal loading and preparation conditions, indicating that the nature and/or amounts of the active sites vary across compositionally similar catalysts. This is illustrated by comparing Mo-based (pre)catalysts prepared by impregnation (2.5-15.6 wt % Mo) and a model material (2.3 wt % Mo) synthesized via surface organometallic chemistry (SOMC). Analyses of FTIR, UV-vis, and Mo K-edge X-ray absorption spectra show that these (pre)catalysts are composed predominantly of similar isolated Mo dioxo sites. However, they exhibit different reaction properties in both liquid and gas-phase olefin metathesis with the SOMC-derived catalyst outperforming a classical catalyst of a similar Mo loading by ×1.5-2.0. Notably, solid-state 95Mo NMR analyses leveraging state-of-the-art high-field (28.2 T) measurement conditions resolve four distinct surface Mo dioxo sites with distributions that depend on the (pre)catalyst preparation methods. The intensity of a specific deshielded 95Mo NMR signal, which is most prominent in the SOMC-derived catalyst, is linked to reducibility and catalytic activity. First-principles calculations show that 95Mo NMR parameters directly manifest the local strain and coordination environment: acute (SiO-Mo(O)2-OSi) angles and low coordination numbers at Mo lead to highly deshielded 95Mo chemical shifts and small quadrupolar coupling constants, respectively. Natural chemical shift analyses relate the 95Mo NMR signature of strained species to low LUMO energies, which is consistent with their high reducibility and corresponding reactivity. The 95Mo chemical shifts of supported Mo dioxo sites are thus linked to their specific electronic structures, providing a powerful descriptor for their propensity toward reduction and formation of active sites.

Novel AMoO4:Eu3+ (A = Ca and Ba) optical thermometer: Investigation of effect of local ionic coordination environment on optical performance and temperature measurement sensitivity

A range of Eu3+-doped AMoO4 (A = Ca and Ba) phosphors were successfully synthetized, and their crystal structures, optical performance, and temperature measurement sensitivities were investigated in detail. Peak doping concentration of CaMoO4:Eu3+ phosphor was 0.18, while peak doping concentration of BaMoO4:Eu3+ phosphor may be greater than 0.18. Then, temperature-dependent photoluminescence emission spectra of representative CaMoO4:0.09Eu3+ and BaMoO4:0.03Eu3+ phosphors were recorded. CaMoO4:0.09Eu3+ phosphor exhibited abnormal thermal quenching, which was attributed to defects caused by heterovalent substitution of ions and increase in the temperature, and good thermal stability. Finally, the possibility of using both phosphors as optical thermometers was discussed, which exhibited good temperature sensitivity. However, CaMoO4:0.09Eu3+ phosphor exhibited two peak absolute (Sa, 1.28 %K−1 and 1.39 %K−1) and relative sensitivities (Sr, 1.21 %K−1 and 1.20 %K−1). In addition, variation trend of Sr value with temperature was considerably peculiar. Two optimum Sa and Sr values were attributed to abnormal thermal quenching of CaMoO4:0.09Eu3+ phosphor. Peak Sa and Sr values of BaMoO4:0.03Eu3+ phosphor was 12.39 %K−1 and 0.89 %K−1, respectively. In addition, Sa of AMoO4:Eu3+ phosphor was negatively related to Eu3+ central asymmetry, while peak Sr value was more inclined to appropriate ionic central asymmetry.

Regulating local coordination environment of Mg−Co single atom catalyst for improved direct methanol fuel cell cathode

Fuel cells operated with a reformate fuel such as methanol are promising power systems for portable electronic devices due to their high safety, high energy density and low pollutant emissions. However, several critical issues including methanol crossover effect, CO-tolerance electrode and efficient oxygen reduction electrocatalyst with low or non-platinum usage have to be addressed before the direct methanol fuel cells (DMFCs) become commercially available for industrial application. Here, we report a highly active and selective Mg−Co dual-site oxygen reduction reaction (ORR) single atom catalyst (SAC) with porous N-doped carbon as the substrate. The catalyst exhibits a commercial Pt/C-comparable half-wave potential of 0.806 V (versus the reversible hydrogen electrode) in acid media with good stability. Furthermore, practical DMFCs test achieves a peak power density of over 200 mW cm−2 that far exceeds that of commercial Pt/C counterpart (82 mW cm−2). Particularly, the Mg−Co DMFC system runs over 10 h with negligible current loss under 10 M concentration methanol work condition. Experimental results and theoretical calculations reveal that the N atom coordinated by Mg and Co atom exhibits an unconventional d-band-ditto localized p-band and can promote the dissociation of the key intermediate *OOH into *O and *OH, which accounts for the near unity selective 4e− ORR reaction pathway and enhanced ORR activity. In contrast, the N atom in SACCo remains inert in the absorption and desorption of *OOH and *OH. This local coordination environment regulation strategy around active sites may promote rational design of high-performance and durable fuel cell cathode electrocatalysts.

Insights into local coordination environment of main group metal-nitrogen-carbon catalysts for enhanced oxygen reduction reaction

For the 4e– oxygen reduction reaction (ORR) on main group metal-nitrogen-carbon catalysts, the effect of the local coordination environment of main group metals on ORR has rarely been reported. By performing density functional theory (DFT) calculations, we screen 18 MN4–xOx (x = 0–2, M = Mg, Ca, Sr, Al, Ga, In) candidates with different metal coordination environments and construct volcano curve between the adsorption free energy of OH* (ΔGOH*) and ORR overpotential, yielding MgN2O2 at the peak of the volcano with the overpotential as low as 0.55 V. The lower ORR overpotential on Mg coordinated with 2 N and 2 O atoms than other coordination environments is well explained by the decreased ΔGOH* because of more shifts of p-band position of Mg away from the Fermi energy level as well as the lower O highest occupied energy level when the number of the coordinated O atoms increases. Our DFT work provides theoretical guidance for engineering ORR performance of main group metal-nitrogen-carbon catalysts by modulating coordination environments.

Boosting the Hydroformylation Activity of a Rh/CeO2 Single-Atom Catalyst by Tuning Surface Deficiencies

Controlling the interactions between atomically dispersed metal atoms and the support plays significant roles in determining the activity and selectivity of single-atom catalysts. In this report, we tuned the local coordination environment of Rh single atoms on CeO2 via calcination to construct a highly active hydroformylation catalyst. Single-atom Rh/CeO2 calcined at a high temperature exhibits more oxygen vacancies, which lead to the formation of a large amount of low-coordination Rh active species that are more active for hydroformylation. Under the optimum conditions, the best Rh/CeO2 catalyst achieved a TOF at approximately 5000 h–1 with 100% aldehyde selectivity in propylene hydroformylation to butanal. In situ FTIR spectroscopy and in situ XPS characterizations provide strong evidence that Rh on 800 °C-calcined CeO2 is easily activated to form surface HRh(CO)2 active species, favoring propylene adsorption and CO insertion. This work highlights the significance of engineering metal–support interactions in tuning the hydroformylation performance of single-atom catalysts and contributes to mechanistic insights into single-atom Rh-catalyzed hydroformylation reactions.

Enhanced nitrogen electroreduction performance by the reorganization of local coordination environment of supported single atom on N(O)-dual-doped graphene

Enhanced nitrogen electroreduction performance by the reorganization of local coordination environment of supported single atom on N(O)-dual-doped graphene

Surface Self‐Reconstruction of Fe‐Ni3S2 Electrocatalyst for Value‐Generating Nitrile Evolution Reaction to Drive Efficient Hydrogen Production

AbstractThermodynamically favorable electrooxidation of organics coupled with hydrogen production as an alternative to overall water splitting is rapidly developing due to low energy consumption and high value. But understanding the relationship between catalyst reconstruction and performance in depth remains a challenge. Herein, DFT calculations are used as a theoretical guide to adjust the local coordination environment and electronic structure of Ni3S2 by Fe doping, which promotes the self‐reconstruction of catalyst and nitrile evolution reaction performance. The overall reaction of benzylamine electrooxidation coupled with hydrogen production achieves a 14.5‐fold improvement in hydrogen production compared to water electrolysis at the same potential, almost completely converting benzylamine to high‐value benzonitrile (99% product yield). In situ spectroscopy and X‐ray absorption fine structure spectroscopy demonstrate that the excellent electrocatalytic performance due to Fe doping induces surface self‐reconstruction of Ni3S2 to NiOOH at low potential, and significantly reduces the rate‐determining step energy barriers for CN bonds to CN bonds. This work provides theoretical guidance in designing and preparing efficient catalysts for the electrosynthesis of nitrile compounds coupled with hydrogen production.

Rational Design of Cu-Doped Tetrahedron of Spinel Oxide for High-Performance Nitric Oxide Electrochemical Sensor

The real-time detection of nitric oxide (NO) in living cells is essential to reveal its physiological processes. However, the popular electrochemical detection strategy is limited to the utilization of noble metals. The development of new detection candidates without noble metal species still maintaining excellent catalytic performance has become a big challenge. Herein, we propose a spinel oxide doped with heteroatom-Cu-doped Co3O4 (Cu-Co3O4) for the sensitive and selective detection of NO release from the living cells. The material is strategically designed with Cu occupying the tetrahedral (Td) center of Co3O4 through the formation of a Cu-O bond. The introduced Cu regulates the local coordination environment and optimizes the electronic structure of Co3O4, hybridizing with the N 2p orbital to enhance charge transfer. The CuTd site can well inhibit the current response to nitrite (NO2-), resulting in a high improvement in the electrochemical oxidation of NO. The selectivity of Cu-Co3O4 can be markedly improved by the pore size of the molecular sieve and the negative charge on the surface. The rapid transmission of electrons is due to the fact that Cu-Co3O4 can be uniformly and densely in situ grown on Ti foil. The rationally designed Cu-Co3O4 sensor displays excellent catalytic activity toward NO oxidation with a low limit of detection of 2.0 nM (S/N = 3) and high sensitivity of 1.9 μA nM-1 cm-2 in cell culture medium. The Cu-Co3O4 sensor also shows good biocompatibility to monitor the real-time NO release from living cells (human umbilical vein endothelial cells: HUVECs; macrophage: RAW 264.7 cells). It was found that a remarkable response to NO was obtained in different living cells when stimulated by l-arginine (l-Arg). Moreover, the developed biosensor could be used for real-time monitoring of NO released from macrophages polarized to a M1/M2 phenotype. This cheap and convenient doping strategy shows universality and can be used for sensor design of other Cu-doped transition metal materials. The Cu-Co3O4 sensor presents an excellent example through the design of proper materials to implement unique sensing requirements and sheds light on the promising strategy for electrochemical sensor fabrication.

Probing the Evolution of Active Sites in MoO2 for Hydrogen Generation in Acidic Medium

MoO2 is an effective host and catalytic material for electrochemical hydrogen evolution reaction in the form of composites, heterostructures, core–shell structures, and doped systems. Using pristine MoO2 as the electrocatalyst is less known due to a lack of knowledge of the active sites and their development during the hydrogen evolution reaction (HER). In this work, we have correlated the active-site evolution on applying a cathodic potential to pristine MoO2 and the corresponding improvement in catalytic activity. The activity enhancement is observed as a progressive reduction of overpotential from 0.62 to 0.42 V (vs RHE) at 1 mA/cm2 during potential cycles accompanied by a tremendous lowering of the Tafel slope (b) from 127 to 72 mV/dec. The decreased b value reveals that the developed active sites hasten the reaction via a change in the rate-determining step from Volmer to Heyrovsky. The changes in the Mo oxidation states and the local coordination environment of Mo–O are monitored by advanced X-ray absorption spectroscopy, unfolding the emergence of active sites in MoO2 through a change of Mo–O coordination from octahedral (Oh) to the coordinatively unsaturated distorted Oh environment with a lowering of the Mo–O coordination number and oxidation states of Mo ions. The key thermodynamic and kinetic parameters, namely, the change in Gibbs free energy for hydrogen adsorption on the catalyst surface and the kinetic activation barrier related to the HER rate-determining step for both activated (MoO2–x) and pristine MoO2, have been simulated and rationalized with the experimental results.

Tuning the atomic configuration environment of MnN4 sites by Co cooperation for efficient oxygen reduction

Carbon-based N-coordinated Mn (Mn-Nx/C) single-atom electrocatalysts are considered as one of the most desirable non-precious oxygen reduction reaction (ORR) candidates due to their insignificant Fenton reactivity, high abundance, and intriguing electrocatalytic performance. However, current Mn-Nx/C single-atom electrocatalysts suffer from high overpotentials because of their low intrinsic activity and unsatisfactory chemical stability. Herein, through an in-situ polymerization-assisted pyrolysis, the Co as a second metal is introduced into the Mn-Nx/C system to construct Co, Mn-Nx dual-metallic sites, which atomically disperse in N-doped 1D carbon nanorods, denoted as Co, Mn-N/CNR and hereafter. Using electron microscopy and X-ray absorption spectroscopy (XAS) techniques, we verify the uniform dispersion of CoN4 and MnN4 atomic sites and confirm the effect of Co doping on the MnN4 electronic structure. Density functional theory (DFT) calculations further elucidate that the energy barrier of rate-determining step (*OH desorption) decreases over the 2 N-bridged MnCoN6 moieties related to the pure MnN4. This work provides an effective strategy to modulate the local coordination environment and electronic structure of MnN4 active sites for improving their ORR activity and stability.

Stacking Faults Inducing Oxygen Anion Activities in Li2 MnO3.

Controllable anionic redox for a transformational increase in the energy density is the pursuit of next generation Li-ion battery cathode materials. Its activation mechanism is coupled with the local coordination environment around O, which posts experimental challenges for control. Here, the tuning capability of anionic redox is shown by varying O local environment via experimentally controlling the density of stacking faults in Li2 MnO3 , the parent compound of Li-rich oxides. By combining computational analysis and spectroscopic study, it is quantitatively revealed that more stacking faults can trigger smaller LiOLi bond angles and larger LiO bond distance in local Li-rich environments and subsequently activate oxygen redox reactivity, which in turn enhances the reactivity of Mn upon the following reduction process. This study highlights the critical role of local structure environment in tuning the anionic reactivity, which provides guidance in designing high-capacity layered cathodes by appropriately adjusting stacking faults.