Covalent organic frameworks derived Single-Atom cobalt catalysts for boosting oxygen reduction reaction in rechargeable Zn-Air batteries.

The design and development of high-performance and long-life Pt-free catalysts for the oxygen reduction reaction (ORR) is of great important with respect to metal-air batteries and fuel cells. Herein, a new low-cost covalent organic frameworks (COFs)-derived CoNC single-atoms catalyst (SAC) is fabricated and compared with the engineered nanoparticle (NP) counterpart for ORR activity. The ORR performance of the SAC catalyst (CoSA@NC) surpasses the NP counterpart (CoNP-NC) under the same operation condition. CoSA@NC also achieves improved long-term durability and better methanol tolerance compared with the Pt/C. The zinc-air battery assembled by the CoSA@NC cathode delivers a higher power density and energy density than that of commercial Pt/C catalyst. Molecular dynamics (MD) is performed to explain the spontaneous evolution from clusters to single-atom metal configuration and density functional theory (DFT) calculations find that CoSA@NC possesses lower d-band center, resulting in weaker interaction between the surface and the O-containing intermediates. Consequently, the reductive desorption of OH*, the rate-determine step, is further accelerated.

Advanced Anti-Icing Strategies and Technologies by Macrostructured Photothermal Storage Superhydrophobic Surfaces.

Water is the source of life and civilization, but water icing causes catastrophic damage to human life and diverse industrial processes. Currently, superhydrophobic surfaces (inspired by the lotus effect) aided anti-icing attracts intensive attention due to their energy-free property. Here, recent advances in anti-icing by design and functionalization of superhydrophobic surfaces are reviewed. The mechanisms and advantages of conventional, macrostructured, and photothermal superhydrophobic surfaces are introduced in turn. Conventional superhydrophobic surfaces, as well as macrostructured ones, easily lose the icephobic property under extreme conditions, while photothermal superhydrophobic surfaces strongly rely on solar illumination. To address the above issues, a potentially smart strategy is found by developing macrostructured photothermal storage superhydrophobic (MPSS) surfaces, which integrate the functions of macrostructured superhydrophobic materials, photothermal materials, and phase change materials (PCMs), and are expected to achieve all-day anti-icing in various fields. Finally, the latest achievements in developing MPSS surfaces, showcasing their immense potential, are highlighted. Besides, the perspectives on the future development of MPSS surfaces are provided and the problems that need to be solved in their practical applications are proposed.

Efficient Photothermal Anti-/Deicing Enabled by 3D Cu2-x S Encapsulated Phase Change Materials Mixed Superhydrophobic Coatings.

Photothermal superhydrophobic surfaces are one of the most promising anti-/deicing materials, yet they are limited by the low energy density and intermittent nature of solar energy. Here, a coupling solution based on microencapsulated phase change materials (MPCMs) that integrates photothermal effect and phase change thermal storage is proposed. Dual-shell octahedral MPCMs with Cu2 O as the first layer and 3D Cu2-x S as the second layer for the first time is designed. By morphology and phase manipulation of the Cu2-x S shell, the local surface plasmonic heating modulation of MPCMs is realized, and the MPCM reveals full-spectrum high absorption with a photothermal conversion efficiency up to 96.1%. The phase change temperature and enthalpy remain in good consistency after 200 cycles. Multifunctional photothermal phase-change superhydrophobic composite coatings are fabricated by combining the hydrolyzed and polycondensation products of octadecyl trichlorosilane and the dual-shell MPCM. The multifunctional coatings exhibit excellent anti-/deicing performance under low temperature and high humidity conditions. This work not only provides a new approach for the design of high-performance MPCMs but also opens up an avenue for the anti-icing application of photothermal phase-change superhydrophobic composite coatings.

New insight into the synergistic reactions involved in the hydrothermal co-liquefaction of synthetic polymer wastes by molecular dynamics and DFT methods.

Coliquefying synthetic aliphatic and aromatic polymer wastes using supercritical water has drawn considerable research attention. However, the mechanisms of chemical reactions between different types of polymers are ambiguous. Herein, depolymerization mechanisms for individual polymers and reaction mechanisms for binary polymer mixtures were investigated using molecular dynamics and density functional theory (DFT). The innovative approach showed that the production of oil from individual polymers during HTL was hindered by (1) volatile C1-C4 molecules emitted from aliphatic polymers and (2) polycyclic aromatic hydrocarbons (PAHs) produced from aromatic polymers. Interestingly, synergistic reactions among these byproducts from different polymers could promote oil production during coliquefaction. Specifically, the synergistic radical-related reactions included (1) the ring-opening of PAHs caused by C2H2 molecules emitted from aliphatic polymers and (2) the recombination of PHA branches and short-chain aliphatics. A considerable synergy between aromatic polymers with higher benzene ring contents and aliphatic polymers with lower H/C atomic ratios was observed near the critical temperature of 649 K. This work provides new insights into the synergistic reactions involved in the coliquefaction of synthetic polymers and gives useful guidance for realizing efficient oil production from mixed organic wastes.

Estimation of the nucleation barrier in a multicomponent system with intermolecular potential.

The formation of a "critical nucleus" prior to phase change is a crucial step for new particle formation (NPF) in the atmosphere. However, the nucleation occurring below ∼1 nm is hard to observe directly. As an effective alternative, theoretical nucleation models have been widely studied. An energy barrier is involved in the nucleation and is the fundamental factor for the nucleation model. Typical atmospheric nucleation agents such as H2SO4, H2O and NH3 are dipole molecules, whose intermolecular interactions are non-ignorable. Herein, a dipole-dipole potential model is adopted to determine the interaction between molecules instead of the traditional hard sphere model, and graph theory is used to describe the structure of the cluster and the cluster-molecule interaction. The nucleation barriers (ΔEb) of H2SO4-H2SO4, H2SO4-H2O, H2SO4-NH3 and H2SO4-H2O-NH3 are derived and compared to each other. In the presence of H2O and NH3, the ΔEb value is decreased by 17-28% compared to that in the pure H2SO4 nucleation system. NH3 is identified to be a key factor for ternary nucleation based on an orthogonal test. Atmospheric concentrations of H2SO4, H2O and NH3 are considered to investigate the influence of [H2O + NH3]/[H2SO4] on ΔEb and the related effective collision coefficient (α). The α value in the ternary nucleation system reaches the range of (2.5-25) × 10-5, which is 3-4 orders of magnitude higher than that in the pure H2SO4 system. Due to a significant enhancement of α, NH3 and H2O should be focused on in future aerosol particle estimation and control.

Chemically Switchable n-Type and p-Type Conduction in Bismuth Selenide Nanoribbons for Thermoelectric Energy Harvesting.

Realizing switchable n-type and p-type conduction in bismuth selenide (Bi2Se3), a traditional thermoelectric material and a topological insulator, is highly beneficial for the development of thermoelectric devices and also of great interest for spintronics and quantum computing. In this work, switching between n-type and p-type conduction in single Bi2Se3 nanoribbons is achieved by a reversible copper (Cu) intercalation method. Density functional theory calculations reveal that such a switchable behavior arises from the electronic band structure distortion caused by the high-concentration Cu intercalation and the Cu substitution for Bi sites in the host lattice. A proof-of-concept in-plane thermoelectric generator is fabricated with one pair of the pristine n-type and intercalated p-type Bi2Se3 nanoribbons on a microfabricated device, which gives rise to an open-circuit voltage of 4.8 mV and a maximum output power of 0.3 nW under a temperature difference of 29.2 K. This work demonstrates switchable n-type and p-type electrical conduction in Bi2Se3 nanoribbons via a facile chemical approach and the practical application of nanoribbons in a thermoelectric device.

A high-rate and long-life organic-oxygen battery.

Alkali metal-oxygen batteries promise high gravimetric energy densities but suffer from low rate capability, poor cycle life and safety hazards associated with metal anodes. Here we describe a safe, high-rate and long-life oxygen battery that exploits a potassium biphenyl complex anode and a dimethylsulfoxide-mediated potassium superoxide cathode. The proposed potassium biphenyl complex-oxygen battery exhibits an unprecedented cycle life (3,000 cycles) with a superior average coulombic efficiency of more than 99.84% at a high current density of 4.0 mA cm-2. We further reduce the redox potential of biphenyl by adding the electron-donating methyl group to the benzene ring, which successfully achieved a redox potential of 0.14 V versus K/K+. This demonstrates the direction and opportunities to further improve the cell voltage and energy density of the alkali-metal organic-oxygen batteries.

Superoxide Stabilization and a Universal KO2 Growth Mechanism in Potassium-Oxygen Batteries.

Rechargeable potassium-oxygen (K-O2 ) batteries promise to provide higher round-trip efficiency and cycle life than other alkali-oxygen batteries with satisfactory gravimetric energy density (935 Wh kg-1 ). Exploiting a strong electron-donating solvent, for example, dimethyl sulfoxide (DMSO) strongly stabilizes the discharge product (KO2 ), resulting in significant improvement in electrode kinetics and chemical/electrochemical reversibility. The first DMSO-based K-O2 battery demonstrates a much higher energy efficiency and stability than the glyme-based electrolyte. A universal KO2 growth model is developed and it is demonstrated that the ideal solvent for K-O2 batteries should strongly stabilize superoxide (strong donor ability) to obtain high electrode kinetics and reversibility while providing fast oxygen diffusion to achieve high discharge capacity. This work elucidates key electrolyte properties that control the efficiency and reversibility of K-O2 batteries.

Synthesis of sub-nanosized Pt particles on mesoporous SBA-15 material and its application to the CO oxidation reaction.

In this work, we show that the size and shape of Pt nanoparticles in SBA-15 can be controlled through vacuum and air calcination. The vacuum-calcination/H2-reduction process is used to thermally treat a 0.2 wt% Pt(4+)/SBA-15 sample to obtain small 2D clusters and single atoms that can significantly increase Pt dispersion in SBA-15. Compared with thermal treatments involving air-calcination/H2-reduction, which result in ∼4.6 nm rod-like Pt particles, vacuum-calcination/H2-reduction can dramatically reduce the size of the Pt species to approximately 0.5-0.8 nm. The Pt particles undergoing air-calcination/H2-reduction have poor conversion efficiency because the fraction of terrace sites, the major sites for CO oxidation, on the rod-like Pt particles is small. In contrast, a large amount of low-coordinated Pt sites associated with 2D Pt species and single Pt atoms in SBA-15 is effectively generated through the vacuum-calcination/H2-reduction process, which may facilitate CO adsorption and induce strong reactivity toward CO oxidation. We investigated the effect of vacuum-calcination/H2-reduction on the formation of tiny 2D clusters and single atoms by characterizing the particles, elucidating the mechanism of formation, determining the active sites for CO oxidation and measuring the heat of CO adsorption.

Synergism through combination of chemotherapy and oxidative stress-induced autophagy in A549 lung cancer cells using redox-responsive nanohybrids: a new strategy for cancer therapy.

A combination of various therapeutic approaches has emerged as a promising strategy for cancer treatment. A safe and competent nano-delivery system is thus in urgent demand to facilitate the simultaneous transport of various therapeutic agents to cancer cells and a tumor region to achieve synergistic effect. Gold nanoparticles (GNPs) and mesoporous silica nanoparticle (MSNs) were fabricated herein as potential candidates for drug delivery. Serving as gatekeepers, GNPs (5 nm in diameter) were attached onto the amino-functionalized MSNs (denoted as NMSNs) via a relatively weak gold-nitrogen bonding. The resulting nanohybrids (denoted as GCMSNs) were uptaken by cells, and the detachment of GNPs and subsequent intracellular drug release from NMSNs were achieved by competitive binding of intracellular glutathione to GNPs. In addition to the function of gatekeeping, GNPs also play another role as the oxidative stress elicitor. Our in vitro studies revealed that GCMSNs induced higher oxidative stress in lung cancer cells (A549) than in normal cells (3T3-L1). This growth inhibitory effect found in the cancer cells was likely induced by mitochondria dysfunction originated from the GCMSN-induced, oxidative stress-triggered mitochondria-mediated autophagy. The redox-responsive nanohybrids were further loaded with camptothecin and the intensified synergistic therapeutic effects were observed associated with combined chemotherapy and oxidative stress strategy. The results clearly demonstrate that such unique nanohybrids hold great promise for selective and effective cancer treatments.

Trivalent galactosyl-functionalized mesoporous silica nanoparticles as a target-specific delivery system for boron neutron capture therapy.

A multi-functional mesoporous silica nanoparticle (MSN)-based boron neutron capture therapy (BNCT) agent, designated as T-Gal-B-Cy3@MSN, was synthesized with hydrophobic mesopores for incorporating a large amount of o-carborane (almost 60% (w/w) boron atoms per MSN), and the amines on the external surface were conjugated with trivalent galactosyl ligands and fluorescent dyes for cell targeting and imaging, respectively. The polar and hydrophilic galactosyl ligands enhance the water dispersibility of the BNCT agent and inhibit the possible leakage of o-carborane loaded in the MSN. Confocal microscopic images showed that T-Gal-B-Cy3@MSNs were endocytosed by cells and were then released from lysosomes into the cytoplasm of cells. Moreover, in comparison with the commonly used clinical BNCT agent, sodium borocaptate (BSH), T-Gal-B-Cy3@MSN provides a higher delivery efficiency (over 40-50 fold) of boron atoms and a better effect of BNCT in neutron irradiation experiments. MTT assays show a very low cytotoxicity for T-Gal-B-Cy3@MSN over a 2 h incubation time. The results are promising for the design of multifunctional MSNs as potential BNCT agents for clinical use.