Phosphorous-Based Heterostructure for the Effective Catalysis of Polysulfide Reactions with Phase Changes in High-Sulfur-Loading Lithium-Sulfur Batteries.

High sulfur loading and long cycle life are the design targets of commercializable lithium-sulfur (Li-S) batteries. The sulfur electrochemical reactions from Li S to Li S, which account for 75% of the battery's theoretical capacity, involve liquid-to-solid and solid-to-solid phase changes in all Li-S battery electrolytes in use today. These are kinetically hindered processes that are exacerbated by a high sulfur loading.

Self-Decoupled Oxygen Electrocatalysis for Ultrastable Rechargeable Zn-Air Batteries with Mild-Acidic Electrolyte.

Rechargeable zinc-air batteries (ZABs) have been considered promising as next-generation sustainable energy storage devices; however, their large-scale deployment is hampered by the unsatisfactory cyclic lifespan. Employing neutral and mild-acidic electrolytes is effective in extending the cyclability, but the rapid performance degradation of the bifunctional catalysts owing to different microenvironmental requirements of the alternative oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is still a serious limitation of their cyclic life. Herein, we propose a "self-decoupling" strategy to significantly improve the stability of the bifunctional catalysts by constructing a smart interface in the bifunctional air electrode.

Fast Polysulfide Conversion Catalysis and Reversible Anode Operation by A Single Cathode Modifier in Li-Metal Anode-Free Lithium-Sulfur Batteries.

The two major issues confronting the commercialization of rechargeable lithium-sulfur (Li-S) batteries are the sluggish kinetics of the sulfur electrochemical reactions on the cathode and inadequate lithium deposition/stripping reversibility on the anode. They are commonly mitigated with additives designed specifically for the anode and the cathode individually. Here, we report the use of a single cathode modifier, In Se , which can effectively catalyse the polysulfide reactions on the cathode, and also improve the reversibility of Li deposition and removal on the anode through a LiInS /LiInSe containing solid electrolyte interface formed in situ by the Se and In ions dissolved in the electrolyte.

Dynamic-self-catalysis as an accelerated air-cathode for rechargeable near-neutral Zn-air batteries with ultrahigh energy efficiency.

Neutral/near-neutral electrolyte rechargeable zinc-air batteries (NN-ZABs) with long cycling lifetime are an evolutionary design of the conventional alkaline ZABs, but the extremely sluggish kinetics of oxygen electrocatalysis in mild pH solutions in the air-cathode has notably affected the energy efficiency of the NN-ZABs. Herein, we present a dynamic self-catalysis as the air-cathode chemistry to boost the energy efficiency of NN-ZABs, which is based on reversible generation of highly active electrocatalysts from the electrolyte during the discharge and charge operations of ZABs, respectively. Two reversible redox reactions of Cu(I)/Cu(II) and Mn(II)/Mn(IV) in the NHCl-ZnCl-based electrolyte are integrated with oxygen electrocatalysis in the air-cathode to generate Cu(I)-O-Cl deposits during discharging and Cu-MnO deposits during charging, which directly catalyze the subsequent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively.

Thermal Percolation of Antiperovskite Superionic Conductor into Porous MXene Scaffold for High-Capacity and Stable Lithium Metal Battery.

Lithium metal battery is considered an emerging energy storage technology due to its high theoretical capacity and low electrochemical potential. However, the practical exploitations of lithium metal batteries are not realized because of uncontrollable lithium deposition and severe dendrite formation. Herein, a thermal percolation strategy is developed to fabricate a dual-conductive framework using electronically conductive Ti C T MXene aerogels (MXAs) and Li OHCl antiperovskite superionic conductor.

Hydrophilic Cross-Linked Aliphatic Hydrocarbon Diblock Copolymer as Proton Exchange Membrane for Fuel Cells.

This study proposes a hydrophobic and hydrophilic aliphatic diblock copolymer wherein the hydrophobic block contains glycidyl methacrylate (GMA) units that are distanced by poly(acrylonitrile) (PAN) segments to fabricate a proton exchange membrane (PEM). This diblock copolymer also known as ionomer due to the hydrophilic block comprising 3-sulfopropyl methacrylate potassium salt (SPM) block. The diblock copolymer was synthesized in the one-pot atom transfer radical polymerization (ATRP) synthesis.

Plasmonic Oxygen-Deficient TiO Nanocrystals for Dual-Band Electrochromic Smart Windows with Efficient Energy Recycling.

Dual-band electrochromic smart windows capable of the spectrally selective modulation of visible (VIS) light and near-infrared (NIR) can regulate solar light and solar heat transmittance to reduce the building energy consumption. The development of these windows is however limited by the number of available dual-band electrochromic materials. Here, plasmonic oxygen-deficient TiO nanocrystals (NCs) are discovered to be an effective single-component dual-band electrochromic material, and that oxygen-vacancy creation is more effective than aliovalent substitutional doping to introduce dual-band properties to TiO NCs.

Stepwise Electrocatalysis as a Strategy against Polysulfide Shuttling in Li-S Batteries.

Most issues with Li-S batteries are caused by the slowness of the multielectron sulfur electrochemical reaction resulting in the loss of sulfur as soluble polysulfides to the electrolyte and the redox shuttling of polysulfides between the cathode and anode during battery charge and discharge. The acceleration of the polysulfide conversion reaction to their end products electrocatalysis has the appeal of a root-cause solution. However, the polysulfide electrocatalysts developed to date have rarely considered polysulfide conversion as a multistep reaction and, as such, were not optimized to target specific steps in the overall S ↔ LiS ↔ LiS conversion.

Dual-Band Electrochromic Devices with a Transparent Conductive Capacitive Charge-Balancing Anode.

Dual-band electrochromic devices (DBEDs), which can selectively modulate near-infrared (NIR) and visible (VIS) light transmittance through electrochromism, have gained increasing interest as a building energy saving technology. The technology is strongly dependent on the progress in electrochromic materials. Most current research has focused on the dual-band properties of the cathode materials, leaving the charge-balancing anode materials under-explored by comparison.

A Cathode-Integrated Sulfur-Deficient CoS Catalytic Interlayer for the Reutilization of "Lost" Polysulfides in Lithium-Sulfur Batteries.

Lithium-sulfur batteries, with their high theoretical energy density and the low material cost of sulfur, are highly promising as a post-lithium ion battery contender. Their current performance is however compromised by sulfur loss and polysulfide shuttle to result in low energy efficiency and poor cycle stability. Herein, a catalytic material (CoS/CNT, nanoparticles with a metallic CoS core and a sulfur-deficient shell on a CNT support) was applied as an interlayer on the sulfur cathode to retain migratory polysulfides and promote their reutilization.

Controlled Crumpling of Two-Dimensional Titanium Carbide (MXene) for Highly Stretchable, Bendable, Efficient Supercapacitors.

Two-dimensional MXene materials have demonstrated attractive electrical and electrochemical properties in energy storage applications. Adding stretchability to MXene remains challenging due to its high mechanical stiffness and weak intersheet interaction, so the assembling techniques for mechanically stable MXene architectures require further development. We report a simple fabrication by harnessing the interfacial instability to generate higher dimensional MXene nanocoatings capable of programmed crumpling/unfolding.

Probing the Qi of traditional Chinese herbal medicines by the biological synthesis of nano-Au.

Herbal medicines with different Qi properties (the primary proxy of their therapeutic effects) are used in traditional Chinese medicine to maintain the harmony of vital forces in a human body. In the Western medicinal practice, the classification of Qi into four major families ("Si Qi" in Chinese Pinyin) is a challenging endeavor, especially by a simple non-reductionist approach. The method presented here is however able to distinguish the Qi of herbal medicines based on the measurements of several Qi-related features in a biological synthesis of nano-Au in herbal extracts: solution color, surface plasmon resonance properties, reaction time and nano-Au morphology.

Revealing isoelectronic size conversion dynamics of metal nanoclusters by a noncrystallization approach.

Atom-by-atom engineering of nanomaterials requires atomic-level knowledge of the size evolution mechanism of nanoparticles, which remains one of the greatest mysteries in nanochemistry. Here we reveal atomic-level dynamics of size evolution reaction of molecular-like nanoparticles, i.e.

Electronic Coupling of Cobalt Nanoparticles to Nitrogen-Doped Graphene for Oxygen Reduction and Evolution Reactions.

The rational design of nonprecious-metal electrocatalysts with activities comparable to or greater than that of platinum is extremely valuable to the development of high energy density metal-air batteries. Herein, the two-step preparation of a highly active oxygen electrocatalyst based on ultrasmall cobalt nanoparticles stabilized in a nitrogen-doped graphene matrix is reported. The catalyst performs as well as the commercial Pt/C catalyst in the oxygen reduction reaction, and better than the Pt/C catalyst in the oxygen evolution reaction.

An Effective Design of Electrically Conducting Thin-Film Composite (TFC) Membranes for Bio and Organic Fouling Control in Forward Osmosis (FO).

The organic foulants and bacteria in secondary wastewater treatment can seriously impair the membrane performance in a water treatment plant. The embedded electrode approach using an externally applied potential to repel organic foulants and inhibit bacterial adhesion can effectively reduce the frequency of membrane replacement. Electrode embedment in membranes is often carried out by dispensing a conductor (e.

Hydrophilic Mineral Coating of Membrane Substrate for Reducing Internal Concentration Polarization (ICP) in Forward Osmosis.

Internal concentration polarization (ICP) is a major issue in forward osmosis (FO) as it can significantly reduce the water flux in FO operations. It is known that a hydrophilic substrate and a smaller membrane structure parameter (S) are effective against ICP. This paper reports the development of a thin film composite (TFC) FO membrane with a hydrophilic mineral (CaCO3)-coated polyethersulfone (PES)-based substrate.

N-Co-O Triply Doped Highly Crystalline Porous Carbon: An Acid-Proof Nonprecious Metal Oxygen Evolution Catalyst.

In comparison with nonaqueous Li-air batteries, aqueous Li-air batteries are kinetically more facile and there is more variety of non-noble metal catalysts available for oxygen electrocatalysis, especially in alkaline solution. The alkaline battery environment is however vulnerable to electrolyte carbonation by atmospheric CO2 resulting in capacity loss over time. The acid aqueous solution is immune to carbonation but is limited by the lack of effective non-noble metal catalysts for the oxygen evolution reaction (OER).

Improving the Performance of Perovskite in Nonaqueous Oxygen Electrocatalysis.

Nanoparticle (NP) aggregates of lanthanum cobalt oxide perovskite (LCO) were compounded with reduced graphene oxide (rGO) nanosheets and used as the cathode catalyst for nonaqueous lithium-oxygen batteries (LOBs). The LCO NP aggregates were completely surrounded by rGO nanosheets in the composite with 10.5 wt % of rGO (LCO-rGO-10.

Enhancing the performance of catalytic AuPt nanoparticles in nonaqueous lithium-oxygen batteries.

The deposition of catalytic AuPt (1 : 1) nanoparticles (NPs) into hollow mesoporous nitrogen-doped carbon microspheres (HMCMS) was found to significantly improve the effectiveness of the catalysis of oxygen reactions in nonaqueous lithium-oxygen batteries (LOBs); surpassing the performance of unsupported AuPt NPs or HMCMS in discharge and charge overpotentials (lower), specific capacity and rate performance (higher), and cycle life (longer). Specifically at a typical current density of 100 mA g(-1), a LOB with the AuPt/HMCMS cathode catalyst could provide discharge and charge capacities of 6028 and 6000 mA h g(-1) respectively and a charge-discharge voltage gap of only 1.27 V.

Development of Cobalt Hydroxide as a Bifunctional Catalyst for Oxygen Electrocatalysis in Alkaline Solution.

Co(OH)2 in the form of hexagonal nanoplates synthesized by a simple hydrothermal reaction has shown even greater activity than cobalt oxides (CoO and Co3O4) in oxygen reduction and oxygen evolution reactions (ORR and OER) under alkaline conditions. The bifunctionality for oxygen electrocatalysis as shown by the OER-ORR potential difference (ΔE) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts, when the Co(OH)2 nanoplates were compounded with nitrogen-doped reduced graphene oxide (N-rGO).

Exploring metal nanoclusters for lithium-oxygen batteries.

α-MnO2 nanowires modified with dispersed poly(3,4-ethylenedioxythiophene)-protected Au and Ag nanoclusters (Au-MnO2 and Ag-MnO2) were used for the first time as hybrid oxygen electrocatalysts for nonaqueous lithium-oxygen batteries. The Au-MnO2 and Ag-MnO2 hybrid catalysts surpassed the performance of pristine α-MnO2 nanowires in full-cell tests in the following order: Au-MnO2 > Ag-MnO2 > pristine α-MnO2. Specifically, cells with the Au-MnO2 catalyst could reduce the discharge/charge overpotentials at 100 mA g(-1) to 0.

Introducing amphiphilicity to noble metal nanoclusters via phase-transfer driven ion-pairing reaction.

Amphiphilicity is a surface property that has yet to be explored for the noble metal nanoclusters (NCs). This article shows how amphiphilicity may be added to sub-2-nm metal NCs by patching hydrophilic NCs (e.g.

Counterion-assisted shaping of nanocluster supracrystals.

Ag44 (p-MBA)30 (4-) (p-MBA=para-mercaptobenzoic acid) nanocluster (NC) supracrystals (SCs) with customizable shapes can be obtained by simply altering the type and concentration of the counterions of the p-MBA ligands in the dimethylsulfoxide (DMSO)/water crystallization system. Changing the counterion of the p-MBA ligand from H(+) to Cs(+) eliminates the directional hydrogen bonds in the SCs, resulting in the packing of deprotonated Ag44 (p-MBA)30 (4-) NCs into octahedral SCs, which is in stark contrast to the rhombohedral SCs that were formed by the packing of protonated Ag44 (p-MBA)30 (4-) NCs in previous studies. Furthermore, the double layer of deprotonated Ag44 (p-MBA)30 (4-) NCs is sensitive to charge screening induced by increasing the Cs(+) concentration, thereby providing a means to regulate the precipitation kinetics of the Ag44 (p-MBA)30 (4-) NCs for SC shape engineering.

Architectural design of heterogeneous metallic nanocrystals--principles and processes.

CONSPECTUS: Heterogeneous metal nanocrystals (HMNCs) are a natural extension of simple metal nanocrystals (NCs), but as a research topic, they have been much less explored until recently. HMNCs are formed by integrating metal NCs of different compositions into a common entity, similar to the way atoms are bonded to form molecules. HMNCs can be built to exhibit an unprecedented architectural diversity and complexity by programming the arrangement of the NC building blocks ("unit NCs").