Geometric Tuning of Single-Atom FeN4 Sites via Edge-Generation Enhances Multi-Enzymatic Properties.

Single-atom nanozymes (SAzymes) are considered promising alternatives to natural enzymes. The catalytic performance of SAzymes featuring homogeneous, well-defined active structures can be enhanced through elucidating structure-activity relationship and tailoring physicochemical properties. However, manipulating enzymatic properties through structural variation is an underdeveloped approach. Herein, the synthesis of edge-rich Fe single-atom nanozymes (FeNC-edge) via an H2 O2 -mediated edge generation is reported. By controlling the number of edge sites, the peroxidase (POD)- and oxidase (OXD)-like performance is significantly enhanced. The activity enhancement results from the presence of abundant edges, which provide new anchoring sites to mononuclear Fe. Experimental results combined with density functional theory (DFT) calculations reveal that FeN4 moieties in the edge sites display high electron density of Fe atoms and open N atoms. Finally, it is demonstrated that FeNC-edge nanozyme effectively inhibits tumor growth both in vitro and in vivo, suggesting that edge-tailoring is an efficient strategy for developing artificial enzymes as novel catalytic therapeutics.

Designing Atomically Dispersed Au on Tensile-Strained Pd for Efficient CO2 Electroreduction to Formate.

Pd is one of the most effective catalysts for the electrochemical reduction of CO2 to formate, a valuable liquid product, at low overpotential. However, the intrinsically high CO affinity of Pd makes the surface vulnerable to CO poisoning, resulting in rapid catalyst deactivation during CO2 electroreduction. Herein, we utilize the interaction between metals and metal-organic frameworks to synthesize atomically dispersed Au on tensile-strained Pd nanoparticles showing significantly improved formate production activity, selectivity, and stability with high CO tolerance. We found that the tensile strain stabilizes all reaction intermediates on the Pd surface, whereas the atomically dispersed Au selectively destabilizes CO* without affecting other adsorbates. As a result, the conventional COOH* versus CO* scaling relation is broken, and our catalyst exhibits 26- and 31-fold enhancement in partial current density and mass activity toward electrocatalytic formate production with over 99% faradaic efficiency, compared to Pd/C at -0.25 V versus RHE.

Enhanced Desalination Performance of Capacitive Deionization Using Nanoporous Carbon Derived from ZIF-67 Metal Organic Frameworks and CNTs.

Capacitive deionization (CDI) based on ion electrosorption has recently emerged as a promising desalination technology due to its low energy consumption and environmental friendliness compared to conventional purification technologies. Carbon-based materials, including activated carbon (AC), carbon aerogel, carbon cloth, and carbon fiber, have been mostly used in CDI electrodes due their high surface area, electrochemical stability, and abundance. However, the low electrical conductivity and non-regular pore shape and size distribution of carbon-based electrodes limits the maximization of the salt removal performance of a CDI desalination system using such electrodes. Metal-organic frameworks (MOFs) are novel porous materials with periodic three-dimensional structures consisting of metal center and organic ligands. MOFs have received substantial attention due to their high surface area, adjustable pore size, periodical unsaturated pores of metal center, and high thermal and chemical stabilities. In this study, we have synthesized ZIF-67 using CNTs as a substrate to fully utilize the unique advantages of both MOF and nanocarbon materials. Such synthesis of ZIF-67 carbon nanostructures was confirmed by TEM, SEM, and XRD. The results showed that the 3D-connected ZIF-67 nanostructures bridging by CNTs were successfully prepared. We applied this nanostructured ZIF-67@CNT to CDI electrodes for desalination. We found that the salt removal performance was significantly enhanced by 88% for 30% ZIF-67@CNTs-included electrodes as compared with pristine AC electrodes. This increase in salt removal behavior was analyzed by electrochemical analysis such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements, and the results indicate reduced electrical impedance and enhanced electrode capacitance in the presence of ZIF-67@CNTs.

Direct Synthesis of Intermetallic Platinum-Alloy Nanoparticles Highly Loaded on Carbon Supports for Efficient Electrocatalysis.

Compared to nanostructured platinum (Pt) catalysts, ordered Pt-based intermetallic nanoparticles supported on a carbon substrate exhibit much enhanced catalytic performance, especially in fuel cell electrocatalysis. However, direct synthesis of homogeneous intermetallic alloy nanocatalysts on carbonaceous supports with high loading is still challenging. Herein, we report a novel synthetic strategy to directly produce highly dispersed MPt alloy nanoparticles (M = Fe, Co, or Ni) on various carbon supports with high catalyst loading. Importantly, a unique bimetallic compound, composed of [M(bpy)3]2+ cation (bpy = 2,2'-bipyridine) and [PtCl6]2- anion, evenly decomposes on carbon surface and forms uniformly sized intermetallic nanoparticles with a nitrogen-doped carbon protection layer. The excellent oxygen reduction reaction (ORR) activity and stability of the representative reduced graphene oxide (rGO)-supported L10-FePt catalyst (37 wt %-FePt/rGO), exhibiting 18.8 times higher specific activity than commercial Pt/C catalyst without degradation over 20 000 cycles, well demonstrate the effectiveness of our synthetic approach toward uniformly alloyed nanoparticles with high homogeneity.

Operando Identification of the Chemical and Structural Origin of Li-Ion Battery Aging at Near-Ambient Temperature.

Integrated with heat-generating devices, a Li-ion battery (LIB) often operates at 20-40 °C higher than the ordinary working temperature. Although macroscopic investigation of the thermal contribution has shown a significant reduction in the LIB performance, the molecular level structural and chemical origin of battery aging in a mild thermal environment has not been elucidated. On the basis of the combined experiments of the electrochemical measurements, Cs-corrected electron microscopy, and in situ analyses, we herein provide operando structural and chemical insights on how a mild thermal environment affects the overall battery performance using anatase TiO2 as a model intercalation compound. Interestingly, a mild thermal condition induces excess lithium intercalation even at near-ambient temperature (45 °C), which does not occur at the ordinary working temperature. The anomalous intercalation enables excess lithium storage in the first few cycles but exerts severe intracrystal stress, consequently cracking the crystal that leads to battery aging. Importantly, this mild thermal effect is accumulated upon cycling, resulting in irreversible capacity loss even after the thermal condition is removed. Battery aging at a high working temperature is universal in nearly all intercalation compounds, and therefore, it is significant to understand how the thermal condition contributes to battery aging for designing intercalation compounds for advanced battery electrode materials.

Atomic-level tuning of Co-N-C catalyst for high-performance electrochemical H2O2 production.

Despite the growing demand for hydrogen peroxide it is almost exclusively manufactured by the energy-intensive anthraquinone process. Alternatively, H2O2 can be produced electrochemically via the two-electron oxygen reduction reaction, although the performance of the state-of-the-art electrocatalysts is insufficient to meet the demands for industrialization. Interestingly, guided by first-principles calculations, we found that the catalytic properties of the Co-N4 moiety can be tailored by fine-tuning its surrounding atomic configuration to resemble the structure-dependent catalytic properties of metalloenzymes. Using this principle, we designed and synthesized a single-atom electrocatalyst that comprises an optimized Co-N4 moiety incorporated in nitrogen-doped graphene for H2O2 production and exhibits a kinetic current density of 2.8 mA cm-2 (at 0.65 V versus the reversible hydrogen electrode) and a mass activity of 155 A g-1 (at 0.65 V versus the reversible hydrogen electrode) with negligible activity loss over 110 hours.

Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts.

The reversible and cooperative activation process, which includes electron transfer from surrounding redox mediators, the reversible valence change of cofactors and macroscopic functional/structural change, is one of the most important characteristics of biological enzymes, and has frequently been used in the design of homogeneous catalysts. However, there are virtually no reports on industrially important heterogeneous catalysts with these enzyme-like characteristics. Here, we report on the design and synthesis of highly active TiO2 photocatalysts incorporating site-specific single copper atoms (Cu/TiO2) that exhibit a reversible and cooperative photoactivation process. Our atomic-level design and synthetic strategy provide a platform that facilitates valence control of co-catalyst copper atoms, reversible modulation of the macroscopic optoelectronic properties of TiO2 and enhancement of photocatalytic hydrogen generation activity, extending the boundaries of conventional heterogeneous catalysts.

Synthesis of nanostructured P2-Na2/3MnO2 for high performance sodium-ion batteries.

We report a facile two-step method to synthesize nanostructured P2-Na2/3MnO2via ligand exchange and intercalation of sodium ions into ultrathin manganese oxide nanoplates. Sodium storage performance of the synthesized material shows a high capacity (170 mA h g-1) and an excellent rate performance.

Algorithmic lattice kirigami: A route to pluripotent materials.

We use a regular arrangement of kirigami elements to demonstrate an inverse design paradigm for folding a flat surface into complex target configurations. We first present a scheme using arrays of disclination defect pairs on the dual to the honeycomb lattice; by arranging these defect pairs properly with respect to each other and choosing an appropriate fold pattern a target stepped surface can be designed. We then present a more general method that specifies a fixed lattice of kirigami cuts to be performed on a flat sheet. This single pluripotent lattice of cuts permits a wide variety of target surfaces to be programmed into the sheet by varying the folding directions.

Self-assembly of monodisperse starburst carbon spheres into hierarchically organized nanostructured supercapacitor electrodes.

We report a three-dimensional (3D) porous carbon electrode containing both nanoscale and microscale porosity, which has been hierarchically organized to provide efficient ion and electron transport. The electrode organization is provided via the colloidal self-assembly of monodisperse starburst carbon spheres (MSCSs). The periodic close-packing of the MSCSs provides continuous pores inside the 3D structure that facilitate ion and electron transport (electrode electrical conductivity ∼0.35 S m(-1)), and the internal meso- and micropores of the MSCS provide a good specific capacitance. The capacitance of the 3D-ordered porous MSCS electrode is ∼58 F g(-1) at 0.58 A g(-1), 48% larger than that of disordered MSCS electrode at the same rate. At 1 A g(-1) the capacitance of the ordered electrode is 57 F g(-1) (95% of the 0.24 A g(-1) value), which is 64% greater than the capacitance of the disordered electrode at the same rate. The ordered electrode preserves 95% of its initial capacitance after 4000 charging/discharging cycles.

Making the cut: lattice kirigami rules.

In this Letter we explore and develop a simple set of rules that apply to cutting, pasting, and folding honeycomb lattices. We consider origami-like structures that are extrinsically flat away from zero-dimensional sources of Gaussian curvature and one-dimensional sources of mean curvature, and our cutting and pasting rules maintain the intrinsic bond lengths on both the lattice and its dual lattice. We find that a small set of rules is allowed providing a framework for exploring and building kirigami­folding, cutting, and pasting the edges of paper.