Modulating the Density of Catalytic Sites in Multiple-Component Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction.

It is generally assumed that the more metal atoms in covalent organic frameworks (COFs) contribute to higher activity toward electrocatalytic carbon dioxide reduction (CO2RR) and hindered us in exploring the correlation between the density of catalytic sites and catalytic performances. Herein, we have constructed quantitative density of catalytic sites in multiple COFs for CO2RR, in which the contents of phthalocyanine (H2Pc) and nickel phthalocyanine (NiPc) units were preciously controlled. With a molar ratio of 1/1 for the H2Pc and NiPc units in COFs, the catalyst achieved the highest selectivity with a carbon monoxide Faradaic efficiency (FECO) of 95.37% and activity with a turnover frequency (TOF) of 4713.53 h-1. In the multiple H2Pc/NiPc-COFs, the electron-donating features of the H2Pc units provide electron transport to the NiPc centers and thus improved the binding ability of CO2 and intermediates on the NiPc units. The theoretical calculation further confirmed that the H2Pc units donated their electrons to the NiPc units in the frameworks, enhanced the electron density of the Ni sites, and improved the binding ability with Lewis acidic CO2 molecules, thereby boosting the CO2RR performance. This study provides us with new insight into the design of highly active catalysts in electrocatalytic systems.

Half-Electrolysis of Water with the Aid of a Supercapacitor Electrode.

Half-electrolysis runs one desirable half-cell reaction with the aid of a counter supercapacitor electrode which replaces the other unwanted half-cell reaction occurred inevitably in conventional electrolysis. Herein, it is developed to complete the whole cell reaction of water electrolysis, in alternative steps, with a capacitive activated carbon (AC) electrode and an electrolysis Pt electrode. When positively charging the AC electrode, a hydrogen evolution reaction occurs at the Pt electrode. By reversing the current, the charge stored in the AC electrode is discharged to assist the oxygen evolution reaction on the same Pt electrode. Consecutive completion of the two processes realizes the overall reaction of water electrolysis. This strategy leads to stepwise production of H2 and O2 without the need of a diaphragm in the cell and hence results in a lower energy consumption compared with the practical conventional electrolysis.

Post-synthetic modification of covalent organic frameworks for CO2 electroreduction.

To achieve high-efficiency catalysts for CO2 reduction reaction, various catalytic metal centres and linker molecules have been assembled into covalent organic frameworks. The amine-linkages enhance the binding ability of CO2 molecules, and the ionic frameworks enable to improve the electronic conductivity and the charge transfer along the frameworks. However, directly synthesis of covalent organic frameworks with amine-linkages and ionic frameworks is hardly achieved due to the electrostatic repulsion and predicament for the strength of the linkage. Herein, we demonstrate covalent organic frameworks for CO2 reduction reaction by modulating the linkers and linkages of the template covalent organic framework to build the correlation between the catalytic performance and the structures of covalent organic frameworks. Through the double modifications, the CO2 binding ability and the electronic states are well tuned, resulting in controllable activity and selectivity for CO2 reduction reaction. Notably, the dual-functional covalent organic framework achieves high selectivity with a maximum CO Faradaic efficiency of 97.32% and the turnover frequencies value of 9922.68 h-1, which are higher than those of the base covalent organic framework and the single-modified covalent organic frameworks. Moreover, the theoretical calculations further reveal that the higher activity is attributed to the easier formation of immediate *CO from COOH*. This study provides insights into developing covalent organic frameworks for CO2 reduction reaction.

Synergistic Effects of 1-Octyl-3-Methylimidazolium Hexafluorophosphate and Cellulose Nanocrystals on Improving Polyacrylate Waterborne Anti-Corrosion Coatings.

In this study, three copolymers of poly(methyl methacrylate) and poly(butyl acrylate) (PMMA-co-PBA) latex containing 1-octyl-3 methylimidazolium hexafluorophosphate (C8mimPF6), cellulose nanocrystals (CNCs), and C8mimPF6-CNCs were successfully synthesized through mini emulsion polymerization. These novel composites were each coated on mild steel panels and tested for their anti-corrosion performance by immersion of the coated samples in 3.5 wt% sodium chloride (NaCl) solution over a certain period. The synergistic anti-corrosion effects of the C8mimPF6-CNCs sample led to the highest coating resistance, charge transfer resistance, and corrosion inhibition efficiency and the lowest diffusion coefficient and corrosion rate. The proposed synergistic mechanism revealed that CNCs enhanced the barrier effect of the coating while C8mimPF6 inhibited corrosion when released.

Nano-Scale Engineering of Heterojunction for Alkaline Water Electrolysis.

Alkaline water electrolysis is promising for low-cost and scalable hydrogen production. Renewable energy-driven alkaline water electrolysis requires highly effective electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). However, the most active electrocatalysts show orders of magnitude lower performance in alkaline electrolytes than that in acidic ones. To improve such catalysts, heterojunction engineering has been exploited as the most efficient strategy to overcome the activity limitations of the single component in the catalyst. In this review, the basic knowledge of alkaline water electrolysis and the catalytic mechanisms of heterojunctions are introduced. In the HER mechanisms, the ensemble effect emphasizes the multi-sites of different components to accelerate the various intermedium reactions, while the electronic effect refers to the d-band center theory associated with the adsorption and desorption energies of the intermediate products and catalyst. For the OER with multi-electron transfer, a scaling relation was established: the free energy difference between HOO* and HO* is 3.2 eV, which can be overcome by electrocatalysts with heterojunctions. The development of electrocatalysts with heterojunctions are summarized. Typically, Ni(OH)2/Pt, Ni/NiN3 and MoP/MoS2 are HER electrocatalysts, while Ir/Co(OH)2, NiFe(OH)x/FeS and Co9S8/Ni3S2 are OER ones. Last but not the least, the trend of future research is discussed, from an industry perspective, in terms of decreasing the number of noble metals, achieving more stable heterojunctions for longer service, adopting new craft technologies such as 3D printing and exploring revolutionary alternate alkaline water electrolysis.

CNT/PVDF Composite Coating Layer on Cu with a Synergy of Uniform Current Distribution and Stress Releasing for Improving Reversible Li Plating/Stripping.

The uncontrollable formation of polymorphous Li deposits, e.g., whiskers, mosses, or dendrites resulting from nonuniform interfacial current distribution and internal stress release in the upward direction on the conventional current collector (e.g., Cu foil) of Li metal rechargeable batteries with a lithium-metal-free negatrode (LMFRBs), leads to rapid performance degradation or serious safety problems. The 3D carbon nanotubes (CNTs) skeleton has been proven to effectively reduce the current density and eliminate the internal accumulated stress. However, remarkable electrolyte decomposition, inherent Li source consumption due to repeated SEI formation, and Li+ intercalation in CNTs limit the application of 3D CNTs skeleton. Thus, it is necessary to avoid the side effects of the 3D CNTs skeleton and retain uniform interfacial current distribution and stress mitigation. In this work, we integrate the CNTs network with a soft functional polymer polyvinylidene fluoride (PVDF) to form a relatively dense coating layer on Cu foil, which can shield the contact between the internal surface of the 3D CNTs framework and the electrolyte. Simultaneously, the Li-F-rich SEI resulting from the partial reduction of PVDF with deposited Li and the soft nature of the coating layer release the accumulation of internal stress in the horizontal direction, resulting in mosses/whisker-free Li deposition. Thus, improved Li deposition/dissolution and stable cycling performance of the LMFRBs can be achieved.

Current progress on catalytic oxidation of toluene: a review.

Toluene is one of the pollutants that are dangerous to the environment and human health and has been sorted into priority pollutants; hence, the control of its emission is necessary. Due to severe problems caused by toluene, different techniques for the abatement of toluene have been developed. Catalytic oxidation is one of the promising methods and effective technologies for toluene degradation as it oxidizes it to CO2 and does not deliver other pollutants to the environment. This paper highlights the recent progressive advancement of the catalysts for toluene oxidation. Five categories of catalysts, including noble metal catalysts, transition metal catalysts, perovskite catalysts, metal-organic frameworks (MOFs)-based catalysts, and spinel catalysts reported in the past half a decade (2015-2020), are reviewed. Various factors that influence their catalytic activities, such as morphology and structure, preparation methods, specific surface area, relative humidity, and coke formation, are discussed. Furthermore, the reaction mechanisms and kinetics for catalytic oxidation of toluene are also discussed.

Microfluidic formation of highly monodispersed multiple cored droplets using needle-based system in parallel mode.

Scale-up in droplet microfluidics achieved by increasing the number of devices running in parallel or increasing the droplet makers in the same device can compromise the narrow droplet-size distribution, or requires high fabrication cost, when glass- or polymer-based microdevices are used. This paper reports a novel way using parallelization of needle-based microfluidic systems to form highly monodispersed droplets with enhanced production rates yet in cost-effective way, even when forming higher order emulsions with complex inner structure. Parallelization of multiple needle-based devices could be realized by applying commercially available two-way connecters and 3D-printed four-way connectors. The production rates of droplets could be enhanced around fourfold (over 660 droplets/min) to eightfold (over 1300 droplets/min) by two-way connecters and four-way connectors, respectively, for the production of the same kind of droplets than a single droplet maker (160 droplets/min). Additionally, parallelization of four-needle sets with each needle specification ranging from 34G to 20G allows for simultaneous generation of four groups of PDMS microdroplets with each group having distinct size yet high monodispersity (CV < 3%). Up to six cores can be encapsulated in double emulsion using two parallelly connected devices via tuning the capillary number of middle phase in a range of 1.31 × 10-4 to 4.64 × 10-4 . This study leads to enhanced production yields of droplets and enables the formation of groups of droplets simultaneously to meet extensive needs of biomedical and environmental applications, such as microcapsules with variable dosages for drug delivery or drug screening, or microcapsules with wide range of absorbent loadings for water treatment.

Synergetic treatment of dye contaminated wastewater using microparticles functionalized with carbon nanotubes/titanium dioxide nanocomposites.

The highly efficient treatment of azo dye contaminated wastewater from the textile industry is an important but challenging problem. Herein, polydimethylsiloxane (PDMS) microparticles, incorporating multiple-walled carbon nanotubes/titanium dioxide (MWCNTs/TiO2) nanocomposites, were successfully synthesized to treat wastewater containing Rhodamine B (RhB) dyes in a synergetic approach, by combining sorption and photocatalytic degradation. The surfactant wrapping sol-gel method was applied to synthesize MWCNTs/TiO2 nanocomposites with TiO2 nanoparticles evenly distributed on the surface of the MWCNTs. The PDMS microparticles were fabricated with an oil-in-water (O/W) single emulsion template, using needle-based microfluidic devices. MWCNTs/TiO2 nanocomposites (at a weight ratio of 1%, and 2%, respectively) were mixed with the PDMS precursor as the dispersed phase, and an aqueous solution of polyvinyl alcohol (PVA) was used as the continuous phase. Highly monodispersed microparticles, with average diameters of 692.7 µm (Coefficient of Variation, CV = 0.74%) and 678.3 µm (CV = 1.04%), were formed at an applied flow rate of the dispersed and continuous phase of 30 and 200 µL min-1, respectively. The fabricated hybrid microparticles were employed for the treatment of RhB, involving a dark equilibrium for 5 hours and UV irradiation for 3 hours. The experimental conditions of applied PDMS type, mass loading amount, treatment duration, photodegradation kinetics, initial concentration of pollutants and environmental pH values were investigated in this work. The PDMS microparticles with 2 wt% MWCNTs/TiO2 nanocomposites can exhibit a removal efficiency of 85%. Remarkably, an efficiency of 70% can be retained after the microparticles have been recycled and reused for 3 cycles. The PDMS-MWCNTs/TiO2 microparticles possess a superior performance over conventional treatment approaches for dye contaminated wastewater, especially in recyclability and the prevention of secondary pollution. This work provides a feasible and eco-friendly route for developing an efficient and low-cost microfluidic method for treating complicated water environmental systems.

Cross-linked Ni(OH)2/CuCo2S4/Ni networks as binder-free electrodes for high performance supercapatteries.

The heterogeneous Ni(OH)2/CuCo2S4/Ni electrode is constructed by appropriately adjusting the time-dependent hydrothermal and electrodeposition process. A hybrid device exhibits 39.7 W h kg-1 of specific energy and 365.3 W kg-1 of specific power, with a good cycling stability of 88% capacity retention after 5000 cycles at 6 A g-1.

A Rechargeable High-Temperature Molten Salt Iron-Oxygen Battery.

The energy and power density of conventional batteries are far lower than their theoretical expectations, primarily because of slow reaction kinetics that are often observed under ambient conditions. Here we describe a low-cost and high-temperature rechargeable iron-oxygen battery containing a bi-phase electrolyte of molten carbonate and solid oxide. This new design merges the merits of a solid-oxide fuel cell and molten metal-air battery, offering significantly improved battery reaction kinetics and power capability without compromising the energy capacity. The as-fabricated battery prototype can be charged at high current density, and exhibits excellent stability and security in the highly charged state. It typically exhibits specific energy, specific power, energy density, and power density of 129.1 Wh kg-1 , 2.8 kW kg-1 , 388.1 Wh L-1 , and 21.0 kW L-1 , respectively, based on the mass and volume of the molten salt.