Ni single atoms on carbon nitride for visible-light-promoted full heterogeneous dual catalysis.

Visible-light-driven organic transformations are of great interest in synthesizing valuable fine chemicals under mild conditions. The merger of heterogeneous photocatalysts and transition metal catalysts has recently drawn much attention due to its versatility for organic transformations. However, these semi-heterogenous systems suffered several drawbacks, such as transition metal agglomeration on the heterogeneous surface, hindering further applications. Here, we introduce heterogeneous single Ni atoms supported on carbon nitride (NiSAC/CN) for visible-light-driven C-N functionalization with a broad substrate scope. Compared to a semi-heterogeneous system, high activity and stability were observed due to metal-support interactions. Furthermore, through systematic experimental mechanistic studies, we demonstrate that the stabilized single Ni atoms on CN effectively change their redox states, leading to a complete photoredox cycle for C-N coupling.

Recent Development of Flexible and Stretchable Supercapacitors Using Transition Metal Compounds as Electrode Materials.

Flexible and stretchable supercapacitors (FS-SCs) are promising energy storage devices for wearable electronics due to their versatile flexibility/stretchability, long cycle life, high power density, and safety. Transition metal compounds (TMCs) can deliver a high capacitance and energy density when applied as pseudocapacitive or battery-like electrode materials owing to their large theoretical capacitance and faradaic charge-storage mechanism. The recent development of TMCs (metal oxides/hydroxides, phosphides, sulfides, nitrides, and selenides) as electrode materials for FS-SCs are discussed here. First, fundamental energy-storage mechanisms of distinct TMCs, various flexible and stretchable substrates, and electrolytes for FS-SCs are presented. Then, the electrochemical performance and features of TMC-based electrodes for FS-SCs are categorically analyzed. The gravimetric, areal, and volumetric energy density of SC using TMC electrodes are summarized in Ragone plots. More importantly, several recent design strategies for achieving high-performance TMC-based electrodes are highlighted, including material composition, current collector design, nanostructure design, doping/intercalation, defect engineering, phase control, valence tuning, and surface coating. Integrated systems that combine wearable electronics with FS-SCs are introduced. Finally, a summary and outlook on TMCs as electrodes for FS-SCs are provided.

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.

Electrochemically exfoliated graphene as a novel microwave susceptor: the ultrafast microwave-assisted synthesis of carbon-coated silicon-graphene film as a lithium-ion battery anode.

Graphene nanocomposites have attracted much attention in many applications due to their superior properties. However, preparing graphene nanocomposites requires a time-consuming thermal treatment to reduce the graphene or synthesize nanomaterials, in most cases. We present an ultrafast synthesis of a carbon-coated silicon-graphene nanocomposite using a commercial microwave system. Electrochemically exfoliated graphene is used as a novel microwave susceptor to deliver efficient microwave energy conversion. Unlike graphene oxide, it does not require a time-consuming pre-thermal reduction or toxic chemical reduction to absorb microwave radiation efficiently. A carbon-coated silicon nanoparticle-electrochemically exfoliated graphene nanocomposite film was prepared by a few seconds' microwave irradiation. The sp2 domains of graphene absorb microwave radiation and generate heat to simultaneously reduce the graphene and carbonize the polydopamine carbon precursor. The as-prepared N-doped carbon-coated silicon-graphene film was used as a lithium-ion battery anode. The N-doped carbon coating decreases the contact resistance between silicon nanoparticles and graphene provides a wide range conductive network. Consequently, it exhibited a reversible capacity of 1744 mA h g-1 at a current density of 0.1 A g-1 and 662 mA h g-1 at 1.0 A g-1 after 200 cycles. This method can potentially be a general approach to prepare various graphene nanocomposites in an extremely short time.

A silver/graphene oxide nanocomposite film as a flexible SERS substrate for reliable quantitative analysis using high-speed spiral scanning spectrometry.

Excellent uniformity (∼1.5% RSD) in SERS signals was obtained from an Ag/GO decorated adhesive tape on a simple in-house cylindrical scanning system. The calibration curve for the quantitative analysis of CV shows reliable linearity ranging from 75 nM to 50 µM. This novel method is promising to be an adept tool for universal quantitative analysis and be used complementarily with the conventional Raman mapping method for a more time efficient and reliable analysis.