Constrained C2 adsorbate orientation enables CO-to-acetate electroreduction.

The carbon dioxide and carbon monoxide electroreduction reactions, when powered using low-carbon electricity, offer pathways to the decarbonization of chemical manufacture1,2. Copper (Cu) is relied on today for carbon-carbon coupling, in which it produces mixtures of more than ten C2+ chemicals3-6: a long-standing challenge lies in achieving selectivity to a single principal C2+ product7-9. Acetate is one such C2 compound on the path to the large but fossil-derived acetic acid market. Here we pursued dispersing a low concentration of Cu atoms in a host metal to favour the stabilization of ketenes10-chemical intermediates that are bound in monodentate fashion to the electrocatalyst. We synthesize Cu-in-Ag dilute (about 1 atomic per cent of Cu) alloy materials that we find to be highly selective for acetate electrosynthesis from CO at high *CO coverage, implemented at 10 atm pressure. Operando X-ray absorption spectroscopy indicates in situ-generated Cu clusters consisting of <4 atoms as active sites. We report a 12:1 ratio, an order of magnitude increase compared to the best previous reports, in the selectivity for acetate relative to all other products observed from the carbon monoxide electroreduction reaction. Combining catalyst design and reactor engineering, we achieve a CO-to-acetate Faradaic efficiency of 91% and report a Faradaic efficiency of 85% with an 820-h operating time. High selectivity benefits energy efficiency and downstream separation across all carbon-based electrochemical transformations, highlighting the importance of maximizing the Faradaic efficiency towards a single C2+ product11.

Ultra-High Proportion of Grain Boundaries in Zinc Metal Anode Spontaneously Inhibiting Dendrites Growth.

Aqueous Zn-ion batteries are an attractive electrochemical energy storage solution for their budget and safe properties. However, dendrites and uncontrolled side reactions in anodes detract the cycle life and energy density of the batteries.Grain boundaries in metals are generally considered as the source of the above problems but we present a diverse result. This study introduces an ultra-high proportion of grain boundaries on zinc electrodes through femtosecond laser bombardment to enhance stability of zinc metal/electrolyte interface.The ultra-high proportion of grain boundaries promotes the homogenization of zinc growth potential, to achieve uniform nucleation and growth, thereby suppressing dendrite formation. Additionally, the abundant active sites mitigate the side reactions during the electrochemical process. Consequently, the 15-µm-Fs-Zn||MnO2 pouch cell achieves an energy density of 249.4 Wh kg-1 and  operates for over 60 cycles at a depth-of-discharge of 23%. The recognition of the favorable influence exerted by UP-GBs paves a new way for other metal batteries.

Fabrication of bio-based biodegradable poly(lactic acid) (PLA) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) composite foams for highly efficient oil-water separation.

The open-cell bio-based biodegradable polymer foams show good application prospect in dealing with the serious environmental issue caused by oil spill and organic solvents spills, while the cell structures and hydrophobic properties of the foams limit their performance. In this work, the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was selected to help prepare bio-based biodegradable poly(lactic acid) (PLA) foams. Based on a two-step foaming method, the crystallization ability of different samples was regulated by the "original crystals" together with PHBV in the foaming process, where skeleton structures were provided to facilitate the open-cell structures and promote their mechanical property. As illustrated, PHBV facilitated the formation of open-cell PLA foams, where the foams displayed superior oil-water separation capacity. The maximum volume expansion ratio of the foams was 80.08, the contact angle of deionized water reached to 134.5°, the adsorption capacity for oil or organic solvents was 10.8 g/g-51.8 g/g, and the adsorption capacity for CCl4 can still maintained 83.5 % of the initial value after 10 adsorption-desorption cycles. This work not only clarified the foaming mechanism of open-cell foams, but also provided a green and simple method for preparing bio-based biodegradable foams possessing excellent oil-water separation performance.

Bicontinuous RuO2 nanoreactors for acidic water oxidation.

Improving activity and stability of Ruthenium (Ru)-based catalysts in acidic environments is eager to replace more expensive Iridium (Ir)-based materials as practical anode catalyst for proton-exchange membrane water electrolyzers (PEMWEs). Here, a bicontinuous nanoreactor composed of multiscale defective RuO2 nanomonomers (MD-RuO2-BN) is conceived and confirmed by three-dimensional tomograph reconstruction technology. The unique bicontinuous nanoreactor structure provides abundant active sites and rapid mass transfer capability through a cavity confinement effect. Besides, existing vacancies and grain boundaries endow MD-RuO2-BN with generous low-coordination Ru atoms and weakened Ru-O interaction, inhibiting the oxidation of lattice oxygen and dissolution of high-valence Ru. Consequently, in acidic media, the electron- and micro-structure synchronously optimized MD-RuO2-BN achieves hyper water oxidation activity (196 mV @ 10 mA cm-2) and an ultralow degradation rate of 1.2 mV h-1. A homemade PEMWE using MD-RuO2-BN as anode also conveys high water splitting performance (1.64 V @ 1 A cm-2). Theoretical calculations and in-situ Raman spectra further unveil the electronic structure of MD-RuO2-BN and the mechanism of water oxidation processes, rationalizing the enhanced performance by the synergistic effect of multiscale defects and protected active Ru sites.

Fabrication of poly(lactic acid) foam with high expansion ratio and oriented cellular structure by restricting cold crystallization.

The foaming behavior of semi-crystalline polymers is significantly affected by their crystallization. To achieve high expansion ratio of poly(lactic acid) (PLA) foams, we thought its cold crystallization should be restricted. Therefore, we used a short soaking time of CO2 to fabricate high-expansion PLA foams. Dynamic mechanical analysis of unfoamed PLA showed that only one rubbery plateau was observed owing to complete cold crystallization under a soaking time of 40 min at 10 MPa. The crystal morphology demonstrated that a short soaking time of 3 min could restrict the cold crystallization of PLA. Owing to plasticization of CO2, PLA crystallization of was accelerated at low temperatures (40-80 °C) but hindered at high temperatures (80-130 °C) at 10 MPa. Foaming results showed that under a soaking time of 3 min, a high expansion ratio exceeding 10 was achievable over a wide foaming temperature range of 90 to 115 °C because more amorphous regions were preserved at 10 MPa. In addition, the prepared foams presented an oriented cellular structure. Compared with the isotropic foam, the anisotropic foam exhibited higher compressive strength and heat resistance. The prepared PLA foams have good application prospects in the fields such as cushioning, packaging, and construction.

Lightweight ZnO/Carbonated Cotton Fiber Nanocomposites for Electromagnetic Interference Applications: Preparation and Properties.

Electromagnetic wave pollution has become a significant harm posed to human health and precision instruments. To shelter such instruments from electromagnetic radiation, high-frequency electromagnetic interference (EMI) shielding materials are extremely desirable. The focus of this research is lightweight, high-absorption EMI shielding composites. Simple aqueous dispersion and drying procedures were used to prepare cotton fiber (CF)-based sheets combined with various zinc oxide (ZnO) contents. These composites were carbonated in a high-temperature furnace at 800 °C for two hours. The obtained CF/ZnO samples have densities of 1.02-1.08 g/cm3. The EMI shielding effectiveness of CF-30% ZnO, CF-50% ZnO, and CF-70% ZnO reached 32.06, 38.08, and 34.69 dB, respectively, to which more than 80% of absorption is attributed. The synergetic effects of carbon networks and surface structures are responsible for the high EMI shielding performance; various reflections inside the interconnected networks may also help in improving their EMI shielding performance.

Mg2+ Ion Pre-Insertion Boosting Reaction Kinetics and Structural Stability of Ammonium Vanadates for High-Performance Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) attract much attention owing to their high safety, environmentally friendliness and low cost. However, the unsatisfactory performance of cathode materials is one of the unsolved important factors for their widespread application. Herein, we report NH4 V4 O10 nanorods with Mg2+ ion preinsertion (Mg-NHVO) as a high-performance cathode material for AZIBs. The preinserted Mg2+ ions effectively improve the reaction kinetics and structural stability of NH4 V4 O10 (NHVO), which are confirmed by electrochemical analysis and density functional theory calculations. Compared with pristine NHVO, the intrinsic conductivity of Mg-NHVO is improved by 5 times based on the test results of a single nanorod device. Besides, Mg-NHVO could maintain a high specific capacity of 152.3 mAh g-1 after 6000 cycles at the current density of 5 A g-1 , which is larger than that of NHVO (only exhibits a low specific capacity of 30.5 mAh g-1 at the same condition). Moreover, the two-phase crystal structure evolution process of Mg-NHVO in AZIBs is revealed. This work provides a simple and efficient method to improve the electrochemical performance of ammonium vanadates and enhances the understanding about the reaction mechanism of layered vanadium-based materials in AZIBs.

Tuning Active Metal Atomic Spacing by Filling of Light Atoms and Resulting Reversed Hydrogen Adsorption-Distance Relationship for Efficient Catalysis.

Precisely tuning the spacing of the active centers on the atomic scale is of great significance to improve the catalytic activity and deepen the understanding of the catalytic mechanism, but still remains a challenge. Here, we develop a strategy to dilute catalytically active metal interatomic spacing (dM-M) with light atoms and discover the unusual adsorption patterns. For example, by elevating the content of boron as interstitial atoms, the atomic spacing of osmium (dOs-Os) gradually increases from 2.73 to 2.96 Å. More importantly, we find that, with the increase in dOs-Os, the hydrogen adsorption-distance relationship is reversed via downshifting d-band states, which breaks the traditional cognition, thereby optimizing the H adsorption and H2O dissociation on the electrode surface during the catalytic process; this finally leads to a nearly linear increase in hydrogen evolution reaction activity. Namely, the maximum dOs-Os of 2.96 Å presents the optimal HER activity (8 mV @ 10 mA cm-2) in alkaline media as well as suppressed O adsorption and thus promoted stability. It is believed that this novel atomic-level distance modulation strategy of catalytic sites and the reversed hydrogen adsorption-distance relationship can shew new insights for optimal design of highly efficient catalysts.

Lightweight electromagnetic interference shielding poly(L-lactic acid)/poly(D-lactic acid)/carbon nanotubes composite foams prepared by supercritical CO2 foaming.

Lightweight and biodegradable polymer composites with efficient electromagnetic interference (EMI) shielding performance are of great significance for controlling pollution caused by plastic waste and electromagnetic radiation. Herein, poly(lactic acid) (PLA)/carbon nanotubes (CNTs) composites were prepared through a melt blending method. By adding a small amount of poly(D-lactic acid) to poly(L-lactic acid) (PLLA), the EMI shielding performance of the composites was improved because an enhanced viscoelasticity and suitable crystallinity could help to construct fine CNT conductive networks. When the PDLA content was 2 wt%, the EMI shielding effectiveness (SE) of the PLLA-2PDLA-10CNTs reached 27.1 dB at 26.5 GHz. Based on these findings, a green supercritical CO2 foaming method was employed to prepare lightweight PLLA/PDLA/CNTs composites. For the PLLA-2PDLA-10CNTs foams, when the expansion ratio was 1.24, the EMI SE was 20.1 dB at 26.5 GHz. In addition, the EMI shielding mechanism of the foams was dominated by absorption. This paper provides a facile way to prepare lightweight and environmentally friendly materials for EMI shielding applications.

Mechanism of Heterogeneous Bubble Nucleation in Polymer Blend Foaming.

A three-dimensional heterogeneous bubble nucleation model is constructed to provide a reasonable explanation at the molecular level for the foaming mechanism of polypropylene (PP) and polystyrene (PS) blends. CO2 solubilities and supersaturation rations are quantitatively calculated to help interpret the contribution of each phase of the blend in the CO2 dissolution stage. The spatial density profiles of polymer/CO2 binary melt around different polymer chains are presented to give an intuitive perspective to the thermodynamic driving force. The predicted interfacial tension and contact angles of critical bubbles provide valid evidence to distinguish the wettability of CO2 in different regions. The values of predicted free-energy barriers, critical radii, and nucleation number densities imply that bubbles that nucleate in the PP and PS blend interfacial region attached to the PS-rich phase achieve the smallest size and largest number density. The reliability of the theoretical model has been tested by partial available experimental data.