Low Coordination Number Research Articles

Trigonal Planar Heteroleptic Lanthanide(III) Bis(silyl)amide Complexes Containing Aminoxyl Radicals and Anions.

Modulation of the crystal field (CF) in lanthanide (Ln) complexes can enhance optical and magnetic properties, and large CF splitting can be achieved with low coordination numbers in specific geometries. We previously reported that the homoleptic near-linear Sm2+ complex [SmII{N(SiiPr3)2}2] (1-Sm) is oxidized by the 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO•) radical to give the heteroleptic, approximately trigonal planar Sm3+ complex, [SmIII{N(SiiPr3)2}2(TEMPO-)] (2-Sm). Here, we report the synthesis of homologous [LnIII{N(SiiPr3)2}2(TEMPO-)] (2-Ln; Ln = Tm, Yb) complexes by the oxidation of the parent [Ln{N(SiiPr3)2}2] (1-Ln; Ln = Tm, Yb) with TEMPO•; complexes 2-Ln all contain TEMPO- anions. The homoleptic bent Ln3+ complexes [LnIII{N(SiiPr3)2}2][B(C6F5)4] (3-Ln; Ln = Sm, Tm, Yb) were also treated with TEMPO• to yield the heteroleptic, approximately trigonal planar Ln3+ complexes [LnIII{N(SiiPr3)2}2(TEMPO•)][B(C6F5)4] (4-Ln; Ln = Sm, Tm, Yb); the cations of 4-Ln all contain TEMPO• radicals. We have compared the electronic structures of the two geometrically similar families of Ln3+ complexes with the TEMPO- anion (2-Ln) or TEMPO• radical (4-Ln) using a combination of UV-vis-NIR and EPR spectroscopy, magnetic measurements, and ab initio calculations. These studies revealed no single-molecule magnet behavior for 2-Yb despite evidence for sizable CF splitting and a high degree of purity of the ground stabilized mJ = |±7/2⟩ state, while the radical TEMPO• in 4-Yb did not significantly improve performance.

Ideal Co-NiO solid solution with excellent low-temperature propene catalytic combustion performance

Doping engineering of transitional metal oxides offers a great opportunity to further optimize the performance of corresponding catalysts. Here, we presented a solid-state co-precipitation routine to synthesize the Co-NiO ideal solid solution, where Co atoms achieved nearly atomically isolation in the NiO lattice matrix. Remarkably a clear correlation was established between the reactivity for propene combustion and the Co dopant amounts, with the propene combustion rate increasing proportionally to the Co dopant amounts. The homogeneously dispersed Co single atoms or tiny CoOx nanoclusters ensure this linear relationship. More importantly, due to the emergence of Co single atoms and CoOx nanoclusters with a lower coordination number, significant propene adsorption and subsequent C = C bond dissociation were observed in this Co-doped NiO, which improved the propene combustion reaction rate. Therefore, this solid-state co-precipitation strategy provides an effective doping route for building an ideal doped solid solution.

Two α-SiO2-Related Deep-Ultraviolet Phase-Matchable Optical Nonlinear Beryllium Silicate Crystals Na2BeSiO4 and Li2BeSiO4 with Enhanced SHG Effect.

Deep-UV, (wavelength λ<200nm) nonlinear-optical (NLO) silicate crystals have long been troubled by weak second-harmonic-generation (SHG) effect and common non-phase-matchability, leading to the stagnation of silicate research, despite abundant reserves of silicates on the earth. Representative and simple α-SiO2 is an ideal structural prototype toward improving silicate NLO performance by exploring efficient strategies. Herein, through two-step structural modulations based on fundamental "distortion and superposition" principles of NLO response, two deep-UV NLO crystals taking α-SiO2 as a structural template, Na2BeSiO4 and Li2BeSiO4, are synthesized successively. By providing flexible coordination BeO4 tetrahedra for rigid tetrahedral SiO4 that induces distortion of SiO4, Na2BeSiO4 achieves significant enhancement of phase-matchable SHG effect of 15×α-SiO2. Further, by introducing a low coordination number of Li+ cations that stimulates uniform orientation of SiO4, Li2BeSiO4 exhibits the strongest phase-matchable SHG effect as large as 40×α-SiO2 among the universal SiO4-governed NLO silicates. Also, computational investigations support the rationality of the structural modulations well. Such efficient structural modulations can greatly promote the exploration and rational design of NLO silicates.

Low-Temperature Activation and Coupling of Methane on MgO Nanostructures Embedded in Cu2O/Cu(111).

The efficient conversion of methane into valuable hydrocarbons, such as ethane and ethylene, at relatively low temperatures without deactivation issues is crucial for advancing sustainable energy solutions. Herein, AP-XPS and STM studies show that MgO nanostructures (0.2-0.5 nm wide, 0.4-0.6 Å high) embedded in a Cu2O/Cu(111) substrate activate methane at room temperature, mainly dissociating it into CHx (x = 2 or 3) and H adatoms, with minimal conversion to C adatoms. These MgO nanostructures in contact with Cu2O/Cu(111) enable C-C coupling into ethane and ethylene at 500 K, a significantly lower temperature than that required for bulk MgO catalysts (>700 K), with negligible carbon deposition and no deactivation. DFT calculations corroborate these experimental findings. The CH4,gas → *CH3 + *H reaction is a downhill process on MgO/Cu2O/Cu(111) surfaces. The activation of methane is facilitated by electron transfer from copper to MgO and the existence of Mg and O atoms with a low coordination number in the oxide nanostructures. The formation of O-CH3 and O-H bonds overcomes the energy necessary for the cleavage of a C-H bond in methane. DFT studies reveal that smaller Mg2O2 model clusters provide stronger binding and lower activation barriers for C-H dissociation in CH4, while larger Mg3O3 clusters promote C-C coupling due to weaker *CH3 binding. All of these results emphasize the importance of size when optimizing the catalytic performance of MgO nanostructures in the selective conversion of methane.

Tuning solvation behavior within electric double layer via halogenated MXene for reliable lithium metal batteries

Solid electrolyte interphase (SEI)/electrolyte interface is critical in determining the lithium (Li) plating/stripping behavior. The solvation structure of Li-ion is well understood in the bulk electrolyte. Still, the mechanism of how SEI components affect the Li-ion solvation structure and desolvation energy barrier at the SEI/electrolyte interface is still unclear. Herein, Ti3C2 Maxine with single halogenated terminations (−Cl, −Br, −I) are synthesized and used as a model system, because their surface terminations induce a double halide-rich SEI formation (LiF and LiCl/LiBr/LiI). We examine the influence of the interaction strength between different Li halides and Li-ion on coordination number of Li ions and distribution of Li ions within the inner Helmholtz plane (IHP). A solvation sheath with a low solvent coordination number forms near the IHP of the LiBr interphase, improving the kinetics of Li deposition. Accordingly, half-cells utilising Li-carbon fiber/Ti3C2Br2 electrodes exhibit a long lifespan of 12,000 h (1 mA cm−2, 1 mAh cm−2). A pouch cell comprising Li-carbon fiber/Ti3C2Br2 anode and LiFePO4 cathode displays a capacity retention rate of 97 % after 300 cycles even at a low negative to positive electrode capacity ratio of 2.26. Our research provides crucial principles for the design of SEI components in Li metal batteries.

Highly-Branched PtCu Nanocrystals with Low-Coordination for Enhanced Oxygen Reduction Catalysis.

Low-coordination platinum-based nanocrystals emanate great potential for catalyzing the oxygen reduction reactions (ORR) in fuel cells, but are not widely applied owing to poor structural stability. Here, several PtCu nanocrystals (PtCu NCs) with low coordination numbers were prepared via a facile one-step method, while the desirable catalyst structures were easily obtained by adjusting the reaction parameters. Wherein, the Pt1Cu1 NCs catalyst with abundant twin boundaries and high-index facets displays 15.25 times mass activity (1.647 A mgPt -1 at 0.9 VRHE) of Pt/C owing to the abundant effective active sites, low-coordination numbers and appropriate compressive strain. More importantly, the core-shell and highly developed dendritic structures in Pt1Cu1 NCs catalyst give it an extremely high stability with only 17.2% attenuation of mass activity while 61.1% for Pt/C after the durability tests (30 000 cycles). In H2-O2 fuel cells, Pt1Cu1 NCs cathode also exhibits a higher peak power density and a longer-term lifetime than Pt/C cathode. Moreover, theoretical calculations imply that the weaker adsorption of intermediate products and the lower formation energy barrier of OOH* in Pt1Cu1 NCs collaboratively boost the ORR process. This work offers a morphology tuning approach to prepare and stabilize the low-coordination platinum-based nanocrystals for efficient and stable ORR.

Comparative study of CO adsorption on Au, Cu, MoO2 and MoS2 2D Nanoparticles

This study focuses on a comparative analysis of the electronic properties of triangular, irregular hexagonal, and octagonal 2D nanoparticles containing 10, 12, and 14 motifs, made of Au, Cu, MoO2, and MoS2. The investigation was carried out using density functional theory. The formation energies and vibrational frequencies demonstrate that the 2D nanostructure configurations can exist as stable structures. Edge atoms with lower coordination numbers than central atoms, are the preferred sites for CO adsorption. Using orbital-weighting dual descriptors calculated from Fukui functions enabled the identification of a majority nucleophilic attack sites in Au and Cu nanoparticles, while MoO2 and MoS2-based nanoparticles present almost as many electrophilic sites as nucleophilic sites. The charge transferred between the nanostructures and the CO molecule and the redistribution of the projected density of states were used to assess the strength of interfacial bonds and the nature of the fundamental interaction involved in the bonding.

In Search of Covalency Measure of Gd(III)-Ligand Interactions.

Experimental electron density distribution of the [C(NH2)3]3[Gd(EDTA)F2]·H2O crystal was determined. The derived experimental and theoretical (DFT) topological parameters such as ∇2ρc, ρc, bond degree (BD), kinetics, and potential energy were used to study the nature of Gd-O, Gd-F, and Gd-N interactions. The natural charge of the Gd is 1.86; the natural configuration of the cation is [Xe]6s0.134f7.105d0.83, and the covalency of the Gd-L bond is mainly connected with the transfer of charge from the spx ligand orbitals onto the 5d orbitals of the Gd cation. Simultaneously, the donation of charge onto the 6s and 4f orbitals occurs to a lesser extent. Moreover it was found that the donation of the ligand charges onto the Gd(III) is larger for compounds with a lower coordination number. The obtained topological parameters were analyzed in the context of the Gd(III) f-f transition properties, i.e., energy of the excited 2S+1LJ states, Judd-Ofelt intensity parameters, and luminescence lifetimes, of 18 Gd(III) compounds with various O, N, and F donor ligands (DOTA, EDTA, CDTA, DTPA, NTA, EGTA, ODA, F-, H2O, and CO32-). The calculated nephelauxetic β parameter may reflect the penetration degree of electron lone pairs of ligands inside the metal basin. Finally, it was found for the first time that the sum of the Gd(III)-L bond energy (∑EGdL) is correlated with the position of the gravity center of the 8S7/2 → 2S+1LJ transitions and increase of covalency of the Gd(III)-L bonds is associated with decrease of their bond energy. The obtained results may shed light on chemical bonding in systems containing f-elements. Such subtle differences in the covalent contribution to the Ln-L or An-L bond may tune the selectivity of the partitioning processes of lanthanides and actinides.

Synthesis, Reactivity, and Bonding Analysis of a Tetracoordinated Nickel Carbene.

Nickel carbenes are key reactive intermediates in the catalytic cyclopropanation of olefins and other reactions, but isolated examples are scarce and generally rely on low coordination numbers (≤ 3) to stabilize the metal-ligand multiple bond. Here we report the isolation and characterization of a stable tetracoordinated nickel carbene bearing a triphosphine pincer ligand. Its nucleophilic character is evidenced by reaction with acids, and it can transfer the carbene fragment to CO to form a ketene. A computational study of the Ni=C chemical bond sheds light on the role of the third phosphine in the pincer framework to the stabilization of the nickel carbene fragment.

Insight into the initiation and propagation mechanism of desiccation cracking in clayey soil from DEM simulations

Desiccation cracking, a common natural phenomenon, significantly affects the mechanical and hydraulic properties of clayey soils. This study employs 3D Discrete Element Method (DEM) to investigate the initiation and propagation mechanisms of soil desiccation cracking. By integrating water evaporation at the soil surface and water transportation between soil grains into a traditional DEM model, we unveil a sequential and hierarchical pattern in the development of desiccation cracks. Initially, micro cracks proliferate and coalesce in regions of soil defects characterized by the lowest coordination numbers, leading to the genesis of primary cracks. Subsequently, a complex network of cracks propagates, governed by the interplay between cracking and the redistribution of the tensile stress field. As desiccation advances, the detachment of soil from the bottom wall and an increase in soil strength contribute to the stabilization of the crack network. Notably, the hierarchical nature of desiccation cracking is predominantly shaped by initial soil defects and subsequently refined by stress concentration within the soil clods, correlating with changes in the length-to-height ratio of the soil clods.

Surface‐Like Diffusion of Fast Ions in Framework Energy Materials for Li‐ and Na‐Ion Batteries

AbstractThe rate performance, power density, and energy efficiency of electrochemical devices are often limited by ionic conductivities in electrolyte and electrode materials. Framework Prussian blue analogs and dense niobium oxides have been identified as high‐rate electrodes for sodium‐ and lithium‐ion batteries, respectively, yet the origin of the extremely high solid‐state Na+/Li+ transport is not fully understood. Of critical importance is the fact that their ultra‐low activation energy and anomalous pre‐exponent factor cannot be satisfactorily rationalized from conventional theory of solid‐state diffusion in the crystal lattice. Here, assisted by density‐functional‐theory calculations, we argued that the true origin is a unique surface‐like diffusion mechanism of the intercalation ions. In a surface‐like migration event, a mobile ion moves along the channel wall via a low coordination number and low migration barrier experiencing minimal steric hindrance. It is similar to surface diffusion in the conventional picture and contrasts with lattice diffusion from one interstitial/vacancy site to another one with high coordination number, crowded saddle‐point geometry and high migration barrier. We found that the shifting from solid‐state lattice diffusion to surface‐like diffusion is determined by the size difference between the mobile ion and the diffusion channel, and a lowest migration energy barrier can be reached by mediating the channel size. The analogy to gas diffusion in molecular sieves shall be discussed. Additionally, the effects of defects and crystal water in Prussian blue analogs were also discussed for better understanding their rate performances in experimental scenarios.

Surface-Like Diffusion of Fast Ions in Framework Energy Materials for Li- and Na-Ion Batteries.

The rate performance, power density, and energy efficiency of electrochemical devices are often limited by ionic conductivities in electrolyte and electrode materials. Framework Prussian blue analogs and dense niobium oxides have been identified as high-rate electrodes for sodium- and lithium-ion batteries, respectively, yet the origin of the extremely high solid-state Na+/Li+ transport is not fully understood. Of critical importance is the fact that their ultra-low activation energy and anomalous pre-exponent factor cannot be satisfactorily rationalized from conventional theory of solid-state diffusion in the crystal lattice. Here, assisted by density-functional-theory calculations, we argued that the true origin is a unique surface-like diffusion mechanism of the intercalation ions. In a surface-like migration event, a mobile ion moves along the channel wall via a low coordination number and low migration barrier experiencing minimal steric hindrance. It is similar to surface diffusion in the conventional picture and contrasts with lattice diffusion from one interstitial/vacancy site to another one with high coordination number, crowded saddle-point geometry and high migration barrier. We found that the shifting from solid-state lattice diffusion to surface-like diffusion is determined by the size difference between the mobile ion and the diffusion channel, and a lowest migration energy barrier can be reached by mediating the channel size. The analogy to gas diffusion in molecular sieves shall be discussed. Additionally, the effects of defects and crystal water in Prussian blue analogs were also discussed for better understanding their rate performances in experimental scenarios.

The structure of CaO–MgO–Al2O3–SiO2 melts and glasses doped with FeOX–NiO

AbstractNeutron and x‐ray diffraction measurements have been performed on CaO–MgO–Al2O3–SiO2 (CMAS) glasses doped with NiO–FeXO at room temperature, along with x‐ray measurements on aerodynamically levitated liquids at ≥2000 K. The disordered structures have been modeled using empirical potential structure refinement to investigate the relation between the aluminosilicate network and the modifying cations. The SiO4 and AlO4 tetrahedra are found to have wider Si–O and Al–O bond distance distributions in the glass, and the first Ca–On coordination shell is highly distorted, redistributing different populations of long and short bonds between the liquid and the glass. The addition of Fe and Ni at low aluminosilicate content increases the number of free oxygens not bonded to AlO4 or SiO4. Mg–O and Fe–O are both found to be predominantly fourfold and fivefold in the liquid and glassy states. Despite these low coordination numbers, their bond angle distributions indicate that they are predominantly in nontetrahedral‐type geometries, with ferrous and ferric iron possessing similar coordination environments. The Ca–O and Mg–O average coordination numbers and enthalpies of solution are consistent with their higher reactivity within relatively acidic aluminosilicate melts.

Diborane Reductions of CO2 and CS2 Mediated by Dicopper μ-Boryl Complexes of a Robust Bis(phosphino)-1,8-naphthyridine Ligand.

A dinucleating 1,8-naphthyridine ligand featuring fluorene-9,9-diyl-linked phosphino side arms (PNNPFlu) was synthesized and used to obtain the cationic dicopper complexes 2, [(PNNPFlu)Cu2(μ-Ph)][NTf2]; [NTf2] = bis(trifluoromethane)sulfonimide, 6, [(PNNPFlu)Cu2(μ-CCPh)][NTf2], and 3, [(PNNPFlu)Cu2(μ-OtBu)][NTf2]. Complex 3 reacted with diboranes to afford dicopper μ-boryl species (4, with μ-Bcat; cat = catecholate and 5, with μ-Bpin; pin = pinacolate) that are more reactive in C(sp)-H bond activations and toward activations of CO2 and CS2, compared to dicopper μ-boryl complexes supported by a 1,8-naphthyridine-based ligand with di(pyridyl) side arms. The solid-state structures and DFT analysis indicate that the higher reactivities of 4 and 5 relate to changes in the coordination sphere of copper, rather than to perturbations on the Cu-B bonding interactions. Addition of xylyl isocyanide (CNXyl) to 4 gave 7, [(PNNPFlu)Cu2(μ-Bcat)(CNXyl)][NTf2], demonstrating that the lower coordination number at copper is chemically significant. Reactions of 4 and 5 with CO2 yielded the corresponding dicopper borate complexes (8, [(PNNPFlu)Cu2(μ-OBcat)][NTf2]; 9, [(PNNPFlu)Cu2(μ-OBpin)][NTf2]), with 4 demonstrating catalytic reduction in the presence of excess diborane. Related reactions of 4 and 5 with CS2 provided insertion products 10, {[(PNNPFlu)Cu2]2[μ-S2C(Bcat)2]}[NTf2]2, and 11, [(PNNPFlu)Cu2(μ,κ2-S2CBpin)][NTf2], respectively. These products feature Cu-S-C-B linkages analogous to those of proposed CO2 insertion intermediate.

A Fully Methylated Cyclic Ether Solvent Enables Graphite Anode Cycling at Low Temperatures.

Graphite anode suffers from great capacity loss and larger cell polarization under low-temperature conditions in lithium-ion batteries (LIBs), which are mainly caused by the high energy barrier for the Li+ desolvation process and sluggish Li+ transfer rate across the solid electrolyte interface (SEI). Regulating an electrolyte with an anion-dominated solvation structure could synchronously stabilize the interface and boost the reaction kinetics of the graphite anode. Herein, a highly ionic conductive electrolyte consisting of a fully methylated cyclic ether solvent of 2,2,4,4,5,5-hexamethyl-1,3-dioxolane (HMD) and fluoroethylene carbonate (FEC) cosolvent was designed. The high electron-donating effect and steric hindrance of -(CH3)2 in HMD endow the HMD-based electrolyte with high ionic conductivity but lower coordination numbers with Li+, and an anion-dominated solvation structure was formed. Such configuration can accelerate the desolvation process and induce the forming of a LiF-rich SEI film on the anode, avoiding the solvent coembedding into graphite and enhancing the ion migration rate under low temperatures. The assembled Li||graphite cell with the tame electrolyte outperformed the conventional carbonates-based cell, showing 93.8% capacity retention after 227 cycles for the DF-based cell compared to 64.7% after 150 cycles. It also exhibited a prolonged cycle life for 200 rounds with 81% capacity retention under -20 °C. Therefore, this work offers a valuable thought for solvent design and provides approaches to electrolyte design for low-temperature LIBs.

Spatially Confined π-Complexation within Pore-Space-Partitioned Metal-Organic Frameworks for Enhanced Light Hydrocarbon Separation and Purification.

Ultramicroporous metal-organic frameworks (MOFs) are demonstrated to be advantageous for the separation and purification of light hydrocarbons such as C2H2, C2H4, and CH4. The introduction of transition metal sites with strong π-complexation affinity into MOFs is more effective than other adsorption sites for the selective adsorption of π-electron-rich unsaturated hydrocarbon gases from their mixtures. However, lower coordination numbers make it challenging to produce robust MOFs directly utilizing metal ions with π-coordination activity, such as Cu+, Ag+, and Pd2+. Herein, a series of novel π-complexing MOFs (SNNU-33s) with a pore size of 4.6Å are precisely constructed by cleverly introducing symmetrically matched C3-type [Cu(pyz)3] (pyz = pyrazine) coordinated fragments into 1D hexagonal channels of MIL-88 prototype frameworks. Benifit from the spatial confinement combined with π-complex-active Cu+ of [Cu(pyz)3], pore-space-partitioned SNNU-33 MOFs all present excellent C2H2/CH4, C2H4/CH4, and CO2/CH4 separation ability. Notably, the optimized SNNU-33b adsorbent demonstrates top-level IAST selectivity values for C2H2/CH4 (597.4) and C2H4/CH4 (69.8), as well as excellent breakthrough performance. Theoretical calculations further reveal that such benchmark light hydrocarbon separation and purification ability is mainly ascribed to the extra-strong binding affinity between Cu+ and π-electron donor molecules via a spatially confined π-complexation process.

Thermal Expansion of Metal Oxides in Silicate Melts: A Simple Theoretical Analysis

The isobaric, isochemical coefficient of thermal expansion ( α) is the proportionality constant relating ∂V/V and ∂T. Noting that ∂V/V equals ∂lnV at constant pressure and composition (i.e., P and X): α=(∂VV∂T)P,X=(∂lnV∂T)P,X A polynomial expression for the temperature dependence of lnV yields direct and accurate calculation of α of melts and glasses. Using the approach, αG of Na-silicate glasses is shown to be constant between 300 and ∼650 K (P and X constant), but it increases linearly with Na2O content, indicating that α is controlled mostly by Na behaviour. Values of α for a melt or glass are necessarily (thermodynamically) related to the coefficients of thermal expansion of its ‘N’ melt components ( αN) by: α=α1θ1+α2θ2+α3θ3+⋯+αNθN where θ represents volume fraction of a component. Calculated αNa2O and αSiO2 values compare satisfactorily with reported values for melts containing ∼40–60 mole% Na2O but are less satisfactory for highly siliceous melts, implying need for refinement of α values. The Coulombic force of attraction between cation and anion is the primary determinant of the magnitude of α values of alkali and alkaline earths oxides. Their values represent a lower bound on α of 3d and 4f modifier oxides. Values larger than this lower bound likely result from a change in coordination number (CN) from higher to lower CN values of modifier cations. Experimental and molecular dynamics studies indicate that partial charges on NBO (O of Si-O-M moieties) and BO (O of Si-O-Si moieties) are about −0.96 and −0.64 respectively, thus NBOs should be incorporated into the first coordination spheres of modifier cations in preference to BOs. A simple mechanism is proposed whereby NBO-BO exchange occurs and CN of the modifier cation decreases with minimal topological adjustment or energetic cost to the melt.

Reconstructing Inorganic‐Rich Interphases by Nonflammable Electrolytes for High‐Voltage and Low‐Temperature LiNi0.5Mn1.5O4 Cathodes

AbstractCobalt‐free and spinel LiNi0.5Mn1.5O4 (LNMO) cathodes commonly suffer from undesirable solvent decomposition, serious transition‐metal dissolution, and unstable cathode electrolyte interphase (CEI) layers, incurring rapid capacity decay at high voltages and low temperatures. Herein, these issues are well addressed by utilizing fluorinated solvents with a low coordination number and ethyl propionate with a low melting point. A Li2CO3/LiF‐rich heterostructured CEI layer, which possesses good electron blocking capability of LiF, fast Li+ transport kinetics of Li2CO3 and good mechanical stability, is generated by the synergistic decomposition of hybrid solvents. The robust, homogeneous, and well‐balanced CEI layers subsequently prevent catalyzed parasitic side reactions, prohibit transition‐metal dissolution, and ensure fast interfacial reaction kinetics crossover to the LNMO cathode, thus improving its cycling stability. Consequently, the LNMO cathode delivers a high‐capacity retention of 95.8% over 500 cycles at 25 °C and 97.5% after 180 cycles at −20 °C. This work provides an encouraging alternative to design the high‐voltage and low‐temperature electrolyte for pushing the ongoing research to stabilize Co‐free LNMO materials toward practical applications.

Unravelling the role of work function difference on supported Ru nanoclusters for alkaline hydrogen evolution reaction

Fine tuning the work function difference (ΔΦ) between support and Ru which in turn affects the electron distribution of Ru is an effective method for the design of high-performance alkaline hydrogen evolution reaction (HER) catalysts. However, it remains a challenge to understand the intrinsic relationship between HER activity and ΔΦ at the atomic level. Herein, taking N doped graphene supported Ru nanoclusters (Ru/CxNy) as the theoretical model, we demonstrate that the HER activity can be correlated with the variation of ΔΦ. For Ru/C50 with smaller ΔΦ, we find that the Ru atoms located at the top layer of Ru nanoclusters (Ru-t) with lower coordination numbers are the main reaction sites. For Ru/C30N20 with larger ΔΦ, the stronger charge redistributions of Ru is observed, and the electron-deficient Ru atoms closing to the interface (Ru-i) are the main reaction sites with significant improvement HER activity. Our findings demonstrate the role of ΔΦ on Ru/CxNy systems for the alkaline HER, which can provide valuable theoretical guidance for the design of high efficient HER catalysts.

Atomically Precise Single-Site Catalysts via Exsolution in a Polyoxometalate-Metal-Organic-Framework Architecture.

Single-site catalysts (SSCs) achieve a high catalytic performance through atomically dispersed active sites. A challenge facing the development of SSCs is aggregation of active catalytic species. Reducing the loading of these sites to very low levels is a common strategy to mitigate aggregation and sintering; however, this limits the tools that can be used to characterize the SSCs. Here we report a sintering-resistant SSC with high loading that is achieved by incorporating Anderson-Evans polyoxometalate clusters (POMs, MMo6O24, M = Rh/Pt) within NU-1000, a Zr-based metal-organic framework (MOF). The dual confinement provided by isolating the active site within the POM, then isolating the POMs within the MOF, facilitates the formation of isolated noble metal sites with low coordination numbers via exsolution from the POM during activation. The high loading (up to 3.2 wt %) that can be achieved without sintering allowed the local structure transformation in the POM cluster and the surrounding MOF to be evaluated using in situ X-ray scattering with pair distribution function (PDF) analysis. Notably, the Rh/Pt···Mo distance in the active catalyst is shorter than the M···M bond lengths in the respective bulk metals. Models of the active cluster structure were identified based on the PDF data with complementary computation and X-ray absorption spectroscopy analysis.