Electronic Regulation of Nickel Single Atoms by Confined Nickel Nanoparticles for Energy-Efficient CO2 Electroreduction.

Modulating the electronic structure of atomically dispersed active sites is promising to boost catalytic activity but is challenging to achieve. Here we show a cooperative Ni single-atom-on-nanoparticle catalyst (NiSA/NP) prepared via direct solid-state pyrolysis, where Ni nanoparticles donate electrons to Ni(i)-N-C sites via a network of carbon nanotubes, achieving a high CO current density of 346 mA cm-2 at -0.5 V vs RHE in an alkaline flow cell. When coupled with a NiFe-based anode in a zero-gap membrane electrolyzer, the catalyst delivers an industrially relevant CO current density of 310 mA cm-2 at a low cell voltage of -2.3 V, corresponding to an overall energy efficiency of 57 %. The superior CO2 electroreduction performance is attributed to the enhanced adsorption of key intermediate COOH* on the electron-rich Ni single atoms, as well as a high density of active sites.

Broadbill swordfish (Xiphias gladius) foraging and vertical movements in the north-west Atlantic.

The northern edge of Georges Bank is an important seasonal foraging habitat for swordfish (Xiphias gladius) in the North Atlantic, where aggregations support commercial pelagic longline and harpoon fisheries. Following a period of overfishing during the 1990s, the North Atlantic X. gladius stock underwent a period of recovery during the early 2000s and was considered rebuilt in 2009. We analysed stomach contents from X. gladius (n = 39) harvested by the Canadian harpoon fishery on Georges Bank in 2007 to characterize diet in this important foraging habitat. We used electronic tagging data from X. gladius (n = 6) on Georges Bank in 2005-2007 to assess vertical habitat preferences and associated prey composition within those zones. We also used stable isotope analysis (δ13 C and δ15 N) of X. gladius liver (n = 2) and common prey types (Paralepididae, Myctophidae, Merluccidae, Ommastrephidae) as a longer-term record of feeding. Stomach contents were co-dominated by Paralepididae [31.9% weight (W)] and Ommastrephidae (36.8%W) with secondary contributions from hake (Merluccidae, 6.5%W), Myctophidae (2.9%W) and Sebastidae (2.1%W). X. gladius displayed diel vertical migrations, descending to depths of 300-400 m during daytime followed by residence in surface waters at night. X. gladius liver δ15 N values were similar to or lower than values of primary stomach contents, likely due to bias of diet consumed in southerly waters with lower nitrogen isotope baselines prior to arrival on Georges Bank. Diet data are similar to results from historical studies from the late 1950s to the early 1980s. This apparent temporal stability to the underlying food web in this region may explain the high X. gladius site fidelity observed in electronic tagging studies and the consistent aggregation of these fish to this region.

Sulfur-Dopant-Promoted Electroreduction of CO2 over Coordinatively Unsaturated Ni-N2 Moieties.

Atomically dispersed nickel-nitrogen-carbon (Ni-N-C) moieties are promising for efficient electrochemical CO2 -to-CO conversion. To improve the intrinsic electrocatalytic activity, it is essential but challenging to steer the coordination environment of Ni centers for promoting the CO formation kinetics. Here, we introduce alien sulfur atoms to tune the local electronic density of unsaturated NiN2 species. A coordinated structure evolution is detected and S vacancies are generated at high overpotentials, as confirmed by X-ray absorption spectroscopy. The sulfur dopants enhance CO selectivity and activity over normal unsaturated NiN2 structure, reaching a high CO Faradaic efficiency of 97 % and a large CO current density of 40.3 mA cm-2 in a H-cell at -0.8 V and -0.9 V (vs. RHE), respectively. DFT calculations reveal both doped S atoms and evolved S vacancies in the NiN2 coordination environment contribute to the reduced energy barriers for CO2 electroreduction to CO.

Template-Directed Rapid Synthesis of Pd-Based Ultrathin Porous Intermetallic Nanosheets for Efficient Oxygen Reduction.

Atomically ordered intermetallic nanoparticles exhibit improved catalytic activity and durability relative to random alloy counterparts. However, conventional methods with time-consuming and high-temperature syntheses only have rudimentary capability in controlling the structure of intermetallic nanoparticles, hindering advances of intermetallic nanocatalysts. We report a template-directed strategy for rapid synthesis of Pd-based (PdM, M=Pb, Sn and Cd) ultrathin porous intermetallic nanosheets (UPINs) with tunable sizes. This strategy uses preformed seeds, which act as the template to control the deposition of foreign atoms and the subsequent interatomic diffusion. Using the oxygen reduction reaction (ORR) as a model reaction, the as-synthesized Pd3 Pb UPINs exhibit superior activity, durability, and methanol tolerance. The favored geometrical structure and interatomic interaction between Pd and Pb in Pd3 Pb UPINs are concluded to account for the enhanced ORR performance.

Intrinsic ORR Activity Enhancement of Pt Atomic Sites by Engineering the d-Band Center via Local Coordination Tuning.

A considerable amount of platinum (Pt) is required to ensure an adequate rate for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. Thus, the implementation of atomic Pt catalysts holds promise for minimizing the Pt content. In this contribution, atomic Pt sites with nitrogen (N) and phosphorus (P) co-coordination on a carbon matrix (PtNPC) are conceptually predicted and experimentally developed to alter the d-band center of Pt, thereby promoting the intrinsic ORR activity. PtNPC with a record-low Pt content (≈0.026 wt %) consequently shows a benchmark-comparable activity for ORR with an onset of 1.0 VRHE and half-wave potential of 0.85 VRHE . It also features a high stability in 15 000-cycle tests and a superior turnover frequency of 6.80 s-1 at 0.9 VRHE . Damjanovic kinetics analysis reveals a tuned ORR kinetics of PtNPC from a mixed 2/4-electron to a predominately 4-electron route. It is discovered that coordinated P species significantly shifts d-band center of Pt atoms, accounting for the exceptional performance of PtNPC.

Efficient Water Splitting Actualized through an Electrochemistry-Induced Hetero-Structured Antiperovskite/(Oxy)Hydroxide Hybrid.

Exploring active, stable, and low-cost bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is crucial for water splitting technology associated with renewable energy storage in the form of hydrogen fuel. Here, a newly designed antiperovskite-based hybrid composed of a conductive InNNi3 core and amorphous InNi(oxy)hydroxide shell is first reported as promising OER/HER bifunctional electrocatalyst. Prepared by a facile electrochemical oxidation strategy, such unique hybrid (denoted as EO-InNNi3 ) exhibits excellent OER and HER activities in alkaline media, benefiting from the inherent high-efficiency HER catalytic nature of InNNi3 antiperovskite and the promoting role of OER-active InNi(oxy)hydroxide thin film, which is confirmed by theoretical simulations and in situ Raman studies. Moreover, an alkaline electrolyzer integrated EO-InNNi3 as both anode and cathode delivers a low voltage of 1.64 V at 10 mA cm-2 , while maintaining excellent durability. This work demonstrates the application of antiperovskite-based materials in the field of overall water splitting and inspires insights into the development of advanced catalysts for various energy applications.

Surface Reconstruction of Ultrathin Palladium Nanosheets during Electrocatalytic CO2 Reduction.

A surface reconstructing phenomenon is discovered on a defect-rich ultrathin Pd nanosheet catalyst for aqueous CO2 electroreduction. The pristine nanosheets with dominant (111) facet sites are transformed into crumpled sheet-like structures prevalent in electrocatalytically active (100) sites. The reconstruction increases the density of active sites and reduces the CO binding strength on Pd surfaces, remarkably promoting the CO2 reduction to CO. A high CO Faradaic efficiency of 93 % is achieved with a site-specific activity of 6.6 mA cm-2 at a moderate overpotential of 590 mV on the reconstructed 50 nm Pd nanosheets. Experimental and theoretical studies suggest the CO intermediate as a key factor driving the structural transformation during CO2 reduction. This study highlights the dynamic nature of defective metal nanosheets under reaction conditions and suggests new opportunities in surface engineering of 2D metal nanostructures to tune their electrocatalytic performance.

Super-Exchange Interaction Induced Overall Optimization in Ferromagnetic Perovskite Oxides Enables Ultrafast Water Oxidation.

Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal-air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super-exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition-dependent OER activity in SrCo1 x Rux O3- δ (denoted as SCRx) (x = 0.0-1.0) perovskite is displayed with special attention on the role of super-exchange interaction between high spin (HS) Co3+ and Ru5+ ions. Induced by the unique Co3+ -O-Ru5+ super-exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co3+ /Co4+ , Ru5+ , and O2 2- /O- , high electrical conductivity, and metal-oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm-2 , which exceeds the benchmark RuO2 and most well-known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.

Processable Surface Modification of Nickel-Heteroatom (N, S) Bridge Sites for Promoted Alkaline Hydrogen Evolution.

Nickel-heteroatoms bridge sites are important reaction descriptors for many catalytic and electrochemical processes. Herein we report the controllable surface modification of nickel-nitrogen (Ni-N) bridge sites on metallic Ni particles via a simplified vapor-assisted treatment approach. X-ray absorption spectroscopy (XAS) and Operando Raman spectroscopy verifies the interaction between Ni and surface-anchored N, which leads to distorted Ni lattice structure with improved wettability. The Ni-N bridge sites with appropriate N coverage level plays a critical role in the enhanced hydrogen evolution reaction (HER) and the optimized electrode (Ni-N0.19 ) has demonstrated superior HER performances with low overpotential merely of 42 mV for achieving a current density of 10 mA cm-2 , as well as favorable reaction kinetics and excellent durability in alkaline electrolyte. DFT calculations revealed that the appropriate N-coverage level can lead to the most favorable ΔGH* kinetics for both adsorption of H* and release of H2 , while high N coverage (Ni-N0.59 ) results in weaker H* adsorption, thus a decreased HER activity, corresponding well to our experimental observations. Furthermore, this generic synthetic approach can also be applied to prepare S-modified Ni HER catalyst by generating hydrogen sulfide vapor.

Isolated Diatomic Ni-Fe Metal-Nitrogen Sites for Synergistic Electroreduction of CO2.

Polynary single-atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces. However, the fabrication and identification of such an active-site prototype remain elusive. Here we report isolated diatomic Ni-Fe sites anchored on nitrogenated carbon as an efficient electrocatalyst for CO2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 % over a wide potential range from -0.5 to -0.9 V (98 % at -0.7 V), and robust durability, retaining 99 % of its initial selectivity after 30 hours of electrolysis. Density functional theory studies reveal that the neighboring Ni-Fe centers not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO, but also undergo distinct structural evolution into a CO-adsorbed moiety upon CO2 uptake.

Binding and Release between Polymeric Carrier and Protein Drug: pH-Mediated Interplay of Coulomb Forces, Hydrogen Bonding, van der Waals Interactions, and Entropy.

The accelerating search for new types of drugs and delivery strategies poses challenge to understanding the mechanism of delivery. To this end, a detailed atomistic picture of binding between the drug and carrier is quintessential. Although many studies focus on the electrostatics of drug-vector interactions, it has also been pointed out that entropic factors relating to water and counterions can play an important role. By carrying out extensive molecular dynamics simulations and subsequently validating with experiments, we shed light herein on the binding in aqueous solution between a protein drug and polymeric carrier. We examined the complexation between the polymer poly(ethylene glycol) methyl ether acrylate-b-poly(carboxyethyl acrylate (PEGMEA-b-PCEA) and the protein egg white lysozyme, a system that acts as a model for polymer-vector/protein-drug delivery systems. The complexation has been visualized and characterized using contact maps and hydrogen bonding analyses for five independent simulations of the complex, each running over 100 ns. Binding at physiological pH is, as expected, mediated by Coulombic attraction between the positively charged protein and negatively charged carboxylate groups on the polymer. However, we find that consideration of electrostatics alone is insufficient to explain the complexation behavior at low pH. Intracomplex hydrogen bonds, van der Waals interactions, as well as water-water interactions dictate that the polymer does not release the protein at pH 4.8 or indeed at pH 3.2 even though the Coulombic attractions are largely removed as carboxylate groups on the polymer become titrated. Experiments in aqueous solution carried out at pH 7.0, 4.5, and 3.0 confirm the veracity of the computed binding behavior. Overall, these combined simulation and experimental results illustrate that coulomb interactions need to be complemented with consideration of other entropic forces, mediated by van der Waals interactions and hydrogen bonding, to search for adequate descriptors to predict binding and release properties of polymer-protein complexes. Advances in computational power over the past decade make atomistic molecular dynamics simulations such as implemented here one of the few avenues currently available to elucidate the complexity of these interactions and provide insights toward finding adequate descriptors. Thus, there remains much room for improvement of design principles for efficient capture and release delivery systems.

The mechanism of oxidation in chromophore maturation of wild-type green fluorescent protein: a theoretical study.

Oxidation is viewed as the second and rate-limiting step in the chromophore maturation process of the wild-type green fluorescent protein (GFP) under aerobic conditions. Molecular oxygen is the necessary oxidant for GFP chromophore biosynthesis. In this study, density functional theory (DFT) calculations were employed to study the mechanism of oxidation. Our results indicate that the deprotonation of the Tyr66 α-carbon is probably the rate-limiting step in the oxidation step. Electron transfer from the enolate form of the five-membered heterocycle (EFMH) to molecular oxygen, generating the triplet radical complex [EFMH˙O2-˙]T, is an important step. This complex undergoes intersystem crossing to form an open-shell singlet diradical complex before it forms the closed-shell singlet hydroperoxy adduct. The formation of the hydroperoxy adduct is a proton-coupled electron transfer process. The energy barrier of H2O2 elimination is 16.5 kcal mol-1. The oxidation product IFMHH2O2 that we discovered is a hydroxylated cyclic imine structure, which is consistent with the crystal structure trapped in the colorless Y66L variant. The relative energy of the oxidation product is -48.7 kcal mol-1, which is in accordance with the experimental observation that the thermodynamically unfavourable cyclized product is trapped by oxidation. The results herein support the cyclization-oxidation-dehydration mechanism for the chromophore maturation of GFP.

Interfacing BiVO4 with Reduced Graphene Oxide for Enhanced Photoactivity: A Tale of Facet Dependence of Electron Shuttling.

Efficient interfacial charge transfer is essential in graphene-based semiconductors to realize their superior photoactivity. However, little is known about the factors (for example, semiconductor morphology) governing the charge interaction. Here, it is demonstrated that the electron transfer efficacy in reduced graphene oxide-bismuth oxide (RGO/BiVO4 ) composite is improved as the relative exposure extent of {010}/{110} facets on BiVO4 increases, indicated by the greater extent of photocurrent enhancement. The dependence of charge transfer ability on the exposure degree of {010} relative to {110} is revealed to arise due to the difference in electronic structures of the graphene/BiVO4 {010} and graphene/BiVO4 {110} interfaces, as evidenced by the density functional theory calculations. The former interface is found to be metallic with higher binding energy and smaller Schottky barrier than that of the latter semiconducting interface. The facet-dependent charge interaction elucidated in this study provides new aspect for design of graphene-based semiconductor photocatalyst useful in manifold applications.

New Family of Quantum Spin Hall Insulators in Two-dimensional Transition-Metal Halide with Large Nontrivial Band Gaps.

Topological insulators (TIs) are promising for achieving dissipationless transport devices due to the robust gapless states inside the insulating bulk gap. However, currently realized two-dimensional (2D) TIs, quantum spin Hall (QSH) insulators, suffer from ultrahigh vacuum and extremely low temperature. Thus, seeking for desirable QSH insulators with high feasibility of experimental preparation and large nontrivial gap is of great importance for wide applications in spintronics. On the basis of the first-principles calculations, we predict a novel family of 2D QSH insulators in transition-metal halide MX (M = Zr, Hf; X = Cl, Br, and I) monolayers, especially, which is the first case based on transition-metal halide-based QSH insulators. MX family has the large nontrivial gaps of 0.12-0.4 eV, comparable with bismuth (111) bilayer (0.2 eV), stanene (0.3 eV), and larger than ZrTe5 (0.1 eV) monolayers and graphene-based sandwiched heterstructures (30-70 meV). Their corresponding 3D bulk materials are weak topological insulators from stacking QSH layers, and some of bulk compounds have already been synthesized in experiment. The mechanism for 2D QSH effect in this system originates from a novel d-d band inversion, significantly different from conventional band inversion between s-p, p-p, or d-p orbitals. The realization of pure layered MX monolayers may be prepared by exfoliation from their 3D bulk phases, thus holding great promise for nanoscale device applications and stimulating further efforts on transition metal-based QSH materials.

Lithium intercalation in two-dimensional penta-NiN2: insights from NiN2/NiN2 homostructure and G/NiN2 heterostructure.

High-energy-density lithium-ion batteries (LIBs) are essential to meet the requirements of emerging technologies for advanced power storage and enhanced device performance. The next generation of LIBs will require high-capacity anode materials that move beyond the lithium intercalation chemistry of conventional graphite electrodes. The use of two-dimensional (2D) bilayer structures offers immediate advantages in the development of LIBs. Herein, motivated by the recently synthesized 2D Cairo pentagon nickel diazenide (NiN2) material, we conduct a scrutiny of the intercalation process of lithium atoms in the interlayer gap of NiN2/NiN2 homostructure. Based on density functional theory (DFT), we demonstrate that the diffusion energy barrier of lithium move across the NiN2/NiN2 anode is relatively low, ranging from 0.058 to 0.52 eV, and the corresponding reversible capacity reaches a remarkable value of 499.0927 mA h g-1 per formula unit, surpassing that of graphite (372 mA h g-1). Furthermore, we investigate a 2D van der Waals (vdW) heterostructure composed of pre-strained structures of graphene and NiN2 for use as an anode material in LIBs. It is found that the introduction of graphene leads to improvements in both electrochemical activity and deformation characteristics. The presented results provide theoretical support for the potential of bilayer structures combining NiN2, suggesting them as promising candidates for the development of high-performance anode materials.

Ab initio investigation of hot electron transfer in CO2 plasmonic photocatalysis in the presence of hydroxyl adsorbate.

Photoreduction of carbon dioxide (CO2) on plasmonic structures is of great interest in photocatalysis to aid selectivity. While species commonly found in reaction environments and associated intermediates can steer the reaction down different pathways by altering the potential energy landscape of the system, they are often not addressed when designing efficient plasmonic catalysts. Here, we perform an atomistic study of the effect of the hydroxyl group (OH) on CO2 activation and hot electron generation and transfer using first-principles calculations. We show that the presence of OH is essential in breaking the linear symmetry of CO2, which leads to a charge redistribution and a decrease in the OCO angle to 134°, thereby activating CO2. Analysis of the partial density of states (pDOS) demonstrates that the OH group mediates the orbital hybridization between Au and CO2 resulting in more accessible states, thus facilitating charge transfer. By employing time-dependent density functional theory (TDDFT), we quantify the fraction of hot electrons directly generated into hybridized molecular states at resonance, demonstrating a broader energy distribution and an 11% increase in charge-transfer in the presence of OH groups. We further show that the spectral overlap between excitation energy and plasmon resonance plays a critical role in efficiently modulating electron transfer processes. These findings contribute to the mechanistic understanding of plasmon-mediated reactions and demonstrate the importance of co-adsorbed species in tailoring the electron transfer processes, opening new avenues for enhancing selectivity.

High density electron doping in boron-doped twisted bilayer graphene: a ladder to extended flat-band.

Realizing Von Hove singularity (VHS) and extended flat bands of graphene near the Fermi level (EF) is of great significance to explore many-body interactions, with a high tendency towards superconductivity. In this study, we report that the VHS of π* bands near EF can be realized by high-density lithium intercalation in p-type doped twisted bilayer graphene (tBLG). First, a method to predict the highest lithium intercalation in tBLG systems with arbitrary twist angle was established which proves that the interlayer twisting leads to the clustering of lithium ions in the AA-region but reduces the overall concentration. Second, we show that the p-type doping (1.35% boron) in tBLGs enhances their electron acceptance capability by increasing lithium intercalation up to 47%. In this situation, the electron doping by lithium intercalation is sufficient to shift EF near the VHS which offers a strategic path to realize extended flat bands, and to investigate the strong correlations in the tBLG systems.

Surface-induced orientation control of CuPc molecules for the epitaxial growth of highly ordered organic crystals on graphene.

The epitaxial growth and preferred molecular orientation of copper phthalocyanine (CuPc) molecules on graphene has been systematically investigated and compared with growth on Si substrates, demonstrating the role of surface-mediated interactions in determining molecular orientation. X-ray scattering and diffraction, scanning tunneling microscopy, scanning electron microscopy, and first-principles theoretical calculations were used to show that the nucleation, orientation, and packing of CuPc molecules on films of graphene are fundamentally different compared to those grown on Si substrates. Interfacial dipole interactions induced by charge transfer between CuPc molecules and graphene are shown to epitaxially align the CuPc molecules in a face-on orientation in a series of ordered superstructures. At high temperatures, CuPc molecules lie flat with respect to the graphene substrate to form strip-like CuPc crystals with micrometer sizes containing monocrystalline grains. Such large epitaxial crystals may potentially enable improvement in the device performance of organic thin films, wherein charge transport, exciton diffusion, and dissociation are currently limited by grain size effects and molecular orientation.

Charge-dependent dynamics of a polyelectrolyte dendrimer and its correlation with invasive water.

Atomistic molecular dynamics (MD) simulations were carried out to investigate the local dynamics of polyelectrolyte dendrimers dissolved in deuterium oxide (D2O) and its dependence on molecular charge. Enhanced segmental dynamics upon increase in molecular charge is observed, consistent with quasielastic neutron scattering (QENS) measurements. A strong coupling between the intradendrimer local hydration level and segmental dynamics is also revealed. Compelling evidence shows these findings originate from the electrostatic interaction between the hydrocarbon components of a dendrimer and the invasive water. This combined study provides fundamental insight into the dynamics of charged polyelectrolytes and the solvating water molecules.

Modelling carbon membranes for gas and isotope separation.

Molecular modelling has become a useful and widely applied tool to investigate separation and diffusion behavior of gas molecules through nano-porous low dimensional carbon materials, including quasi-1D carbon nanotubes and 2D graphene-like carbon allotropes. These simulations provide detailed, molecular level information about the carbon framework structure as well as dynamics and mechanistic insights, i.e. size sieving, quantum sieving, and chemical affinity sieving. In this perspective, we revisit recent advances in this field and summarize separation mechanisms for multicomponent systems from kinetic and equilibrium molecular simulations, elucidating also anomalous diffusion effects induced by the confining pore structure and outlining perspectives for future directions in this field.