Correction: Super-large dendrites composed of trigonal PbO2 nanoplates with enhanced performances for electrochemical devices.

Correction for 'Super-large dendrites composed of trigonal PbO2 nanoplates with enhanced performances for electrochemical devices' by Liang-Xin Ding et al., Chem. Commun., 2012, 1275-1277, DOI: 10.1039/C2CC15271A.

Correction: Cu2O template synthesis of high-performance PtCu alloy yolk-shell cube catalysts for direct methanol fuel cells.

Correction for 'Cu2O template synthesis of high-performance PtCu alloy yolk-shell cube catalysts for direct methanol fuel cells' by Sheng-Hua Ye et al., Chem. Commun., 2014, 50, 12337-12340, DOI: 10.1039/C4CC04108A.

Enhancing Catalytic Activity and Selectivity by Plasmon-Induced Hot Carriers.

Plasmon-assisted chemical transformation holds great potential for solar energy conversion. However, simultaneous enhancement of reactivity and selectivity is still challenging and the mechanism remains mysterious. Herein, we elucidate the localized surface plasmon resonance (LSPR)-induced principles underlying the enhanced activity (∼70%) and selectivity of photoelectrocatalytic redox of nitrobenzene (NB) on Au nanoparticles. Hot carriers selectively accelerate the conversion rate from NB to phenylhydroxylamine (PHA) by ∼14% but suppress the transformation rate from PHA to nitrosobenzene (NSB) by ∼13%. By adding an electron accepter, the as-observed suppression ratio is substantially enlarged up to 43%. Our experiments, supported by in situ surface-enhanced Raman spectroscopy and density functional theory simulations, reveal such particular hot-carrier-induced selectivity is conjointly contributed by the accelerated hot electron transfer and the corresponding residual hot holes. This work will help expand the applications of renewable sunlight in the directional production of value-added chemicals under mild conditions.

Enhanced catalytic activity of Au core Pd shell Pt cluster trimetallic nanorods for CO2 reduction.

Herein, Au core Pd shell Pt cluster nanorods (Au@Pd@Pt NRs) with enhanced catalytic activity were rationally designed for carbon dioxide (CO2) reduction. The surface composition and Pd-Pt ratios significantly influenced the catalytic activity, and the optimized structure had only a half-monolayer equivalent of Pt (θ Pt = 0.5) with 2 monolayers of Pd, which could enhance the catalytic activity for CO2 reduction by 6 fold as compared to the Pt surface at -1.5 V vs. SCE. A further increase in the loading of Pt actually reduced the catalytic activity; this inferred that a synergistic effect existed among the three different nanostructure components. Furthermore, these Au NRs could be employed to improve the photoelectrocatalytic activity by 30% at -1.5 V due to the surface plasmon resonance. An in situ SERS investigation inferred that the Au@Pd@Pt NRs (θ Pt = 0.5) were less likely to be poisoned by CO because of the Pd-Pt bimetal edge sites; due to this reason, the proposed structure exhibited highest catalytic activity. These results play an important role in the mechanistic studies of CO2 reduction and offer a new way to design new materials for the conversion of CO2 to liquid fuels.

Targeted reversal and phosphorescence lifetime imaging of cancer cell metabolism via a theranostic rhenium(I)-DCA conjugate.

Cancer cell metabolism is quite different from normal cells. Targeting cancer metabolism and untuning the tumor metabolic machine has emerged as a promising strategy for cancer therapy. We have developed a multi-functional Re-dca conjugate (Re-dca 2) by conjugating the metabolic modulator dichloroacetate (DCA) to mitochondria-targeted rhenium(I) complex, allowing its efficient penetration into cancer cells and selective accumulation in mitochondria, thus achieving the cancer cell metabolism reversal from glycolysis to glucose oxidation at pharmacologically relevant DCA doses. Mechanism studies confirm the inhibition effect of Re-dca 2 on the activity of pyruvate dehydrogenase kinase (PDK) and capture the metabolic reversal window in Re-dca 2 treated NCI-1229 cells at the early stage of drug treatment, resulting in selective killing of malignant cells cocultured with normal cells, significant inhibition of cancer cell metastasis and invasion, as well as excellent anti-angiogenesis activities in zebrafish embryos. By comparison, DCA-free Re(I) analogue is also investigated under the same conditions. Although this analogue also exhibits cytotoxicity due to the Re(I) core, metabolic reversal is not induced by this analogue and its anti-metastasis activity is much lower than Re-dca 2, indicating the synergistic effect of Re(I) core and DCA moiety on cancer therapy. In vivo anti-cancer investigations also indicate that the mitochondria-targeted Re-dca 2 can effectively inhibit the tumor growth without affecting the body weight of nude mice, and the therapeutic effect is much better than the DCA-free Re(I) analogue 2a. Simultaneously, the O2-sensitive phosphorescent lifetimes of Re-dca 2 can be utilized for PLIM imaging of intracellular oxygen consumption, thus reflecting the Re-dca 2 induced glycolysis-to-glucose oxidation reversal at the early drug treatment stage. The excellent phosphorescence of Re-dca 2 can also be utilized for real-time tracking of mitochondrial morphological changes during treatment. In a word, rational design of phosphorescent metallodrug and metabolic modulator conjugates for synergistic treatment is a promising strategy for simultaneous untuning and tracking tumor metabolic machine, thus providing new clues for cancer therapy and mechanisms.

Porous Microrod Arrays Constructed by Carbon-Confined NiCo@NiCoO2 Core@Shell Nanoparticles as Efficient Electrocatalysts for Oxygen Evolution.

The study of cost-efficient and high-performance electrocatalysts for oxygen evolution reaction (OER) has attracted much attention. Here, porous microrod arrays constructed by carbon-confined NiCo@NiCoO2 core@shell nanoparticles (NiCo@NiCoO2 /C PMRAs) are fabricated by the reductive carbonization of bimetallic (Ni, Co) metal-organic framework microrod arrays (denoted as NiCo-MOF MRAs) and subsequent controlled oxidative calcination. They successfully combine the desired merits including large specific surface areas, high conductivity, and multiple electrocatalytic active sites for OER. In addition, the oxygen vacancies in NiCo@NiCoO2 /C PMRAs significantly improve the conductivity of NiCoO2 and accelerate the kinetics of OER. The above advantages obviously enhance the electrocatalytic performance of NiCo@NiCoO2 /C PMRAs. The experimental results demonstrate that the NiCo@NiCoO2 /C PMRAs as electrocatalysts exhibit high catalytic activity, low overpotential, and high stability for OER in alkaline media. The strategy reported will open up a new route for the fabrication of porous bimetallic composite electrocatalysts derived from MOFs with controllable morphology for electrochemical energy conversion devices.

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H+ and hamper the ability of H+ to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H+ from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

Recent Progress on MOF-Derived Heteroatom-Doped Carbon-Based Electrocatalysts for Oxygen Reduction Reaction.

The oxygen reduction reaction (ORR) is the core reaction of numerous sustainable energy-conversion technologies such as fuel cells and metal-air batteries. It is crucial to develop a cost-effective, highly active, and durable electrocatalysts for ORR to overcome the sluggish kinetics of four electrons pathway. In recent years, the carbon-based electrocatalysts derived from metal-organic frameworks (MOFs) have attracted tremendous attention and have been shown to exhibit superior catalytic activity and excellent intrinsic properties such as large surface area, large pore volume, uniform pore distribution, and tunable chemical structure. Here in this review, the development of MOF-derived heteroatom-doped carbon-based electrocatalysts, including non-metal (such as N, S, B, and P) and metal (such as Fe and Co) doped carbon materials, is summarized. It furthermore, it is demonstrated that the enhancement of ORR performance is associated with favorably well-designed porous structure, large surface area, and high-tensity active sites. Finally, the future perspectives of carbon-based electrocatalysts for ORR are provided with an emphasis on the development of a clear mechanism of MOF-derived non-metal-doped electrocatalysts and certain metal-doped electrocatalysts.

Activating CoOOH Porous Nanosheet Arrays by Partial Iron Substitution for Efficient Oxygen Evolution Reaction.

Iron-substituted CoOOH porous nanosheet arrays grown on carbon fiber cloth (denoted as Fex Co1-x OOH PNSAs/CFC, 0≤x≤0.33) with 3D hierarchical structures are synthesized by in situ anodic oxidation of α-Co(OH)2 NSAs/CFC in solution of 0.01 m (NH4 )2 Fe(SO4 )2 . X-ray absorption fine spectra (XAFS) demonstrate that CoO6 octahedral structure in CoOOH can be partially substituted by FeO6 octahedrons during the transformation from α-Co(OH)2 to Fex Co1-x OOH, and this is confirmed for the first time in this study. The content of Fe in Fex Co1-x OOH, no more than 1/3 of Co, can be controlled by adjusting the in situ anodic oxidation time. Fe0.33 Co0.67 OOH PNSAs/CFC shows superior OER electrocatalytic performance, with a low overpotential of 266 mV at 10 mA cm-2 , small Tafel slope of 30 mV dec-1 , and high durability.

Efficient Hydrogen Evolution on Cu Nanodots-Decorated Ni3S2 Nanotubes by Optimizing Atomic Hydrogen Adsorption and Desorption.

Low-cost transition-metal dichalcogenides (MS2) have attracted great interest as alternative catalysts for hydrogen evolution. However, a significant challenge is the formation of sulfur-hydrogen bonds on MS2 (S-Hads), which will severely suppress hydrogen evolution reaction (HER). Here we report Cu nanodots (NDs)-decorated Ni3S2 nanotubes (NTs) supported on carbon fibers (CFs) (Cu NDs/Ni3S2 NTs-CFs) as efficient electrocatalysts for HER in alkaline media. The electronic interactions between Cu and Ni3S2 result in Cu NDs that are positively charged and can promote water adsorption and activation. Meanwhile, Ni3S2 NTs are negatively charged and can weaken S-Hads bonds formed on catalyst surfaces. Therefore, the Cu/Ni3S2 hybrids can optimize H adsorption and desorption on electrocatalysts and can promote both Volmer and Heyrovsky steps of HER. The strong interactions between Cu and Ni3S2 cause the Cu NDs/Ni3S2 NTs-CFs electrocatalysts to exhibit the outstanding HER catalytic performance with low onset potential, high catalytic activity, and excellent stability.

Silica-Polypyrrole Hybrids as High-Performance Metal-Free Electrocatalysts for the Hydrogen Evolution Reaction in Neutral Media.

Constructing inorganic-organic hybrids with superior properties in terms of water adsorption and activation will lead to catalysts with significantly enhanced electrocatalytic activity in the hydrogen evolution reaction (HER) in environmentally benign neutral media. Herein, we report SiO2 -polypyrrole (PPy) hybrid nanotubes supported on carbon fibers (CFs) (SiO2 /PPy NTs-CFs) as inexpensive and high-performance electrocatalysts for the HER in neutral media. Because of the strong electronic interactions between SiO2 and PPy, the SiO2 uniquely serves as the centers for water adsorption and activation, and accordingly promotes the HER. The metal-free SiO2 /PPy NTs-CFs displayed high catalytic activity in the HER in neutral media, such as a low onset potential and small Tafel slope, as well as excellent long-term durability.