Insulator-transition-induced Degradation of Pyrochlore Ruthenates in Electrocatalytic Oxygen Evolution and Stabilization through Doping.

Ru-based pyrochlores (e.g., Y2Ru2O7-d) are promised to replace IrO2 in polymer electrolyte membrane (PEM) electrolyzers. It is significant to reveal the cliff attenuation on the oxygen evolution reaction (OER) performance of these pyrochlores. In this work, we monitor the structure changes and electrochemical behavior of Y2Ru2O7-d over the OER process, and it is found that the reason of decisive OER inactivation is derived from an insulator transition occurred within Y2Ru2O7-d due to its inner ²perfecting² lattice induced by continuous atom rearrangement. Therefore, a stabilization strategy of the Ir-substituted Y2Ru2O7-d is proposed to alleviate this undesirable behavior. The double-exchange interaction between Ru and Ir in [RuO6] and [IrO6] octahedra leads the charge redistribution with simultaneous spin configuration adjustment. The electronic state in newly formed octahedrons centered with Ru 4d3 (with the state of eg'2--a1g-1 eg0) and Ir 5d6 (eg'4a1g-2 eg0) relieves the uneven electron distributions in [RuO6] orbital. The attenuated Jahn-Teller effect alleviates atom rearrangement, represented as the mitigation of insulator transition, surface reconstruction, and metal dissolution. As results, the Ir-substituted Y2Ru2O7-d presents the greatly improved OER stability and PEM durability. This study unveils the OER degradation mechanism and stabilization strategy for material design of Ru-based OER catalysts for electrochemical applications.

Enhanced Antifouling Feed Spacer Made from a Carbon Nanotube-Polypropylene Nanocomposite.

Spacers are widely used in membrane technologies to reduce fouling and concentration polarization. Fouling can start from the spacer surface and grow, thereby reducing flux, selectivity, and operation lifetime. Fluorescein isothiocyanate labeled bovine serum albumin was used for fouling studies and observed during cross-flow filtration operation for up to 144 h. Here, we mixed carbon nanotubes (CNTs) and polypropylene (PP) to make a spacer with better antifouling than plain PP spacers. The fouling process was observed by scanning electron microscopy and monitored in situ by fluorescence microscopy. Molecular dynamics simulations show that bovine serum albumin has a lower interaction energy with the nanocomposite CNTs/PP spacer than with the plain PP. The findings are relevant for the development of spacers to improve the operation lifetime of membranes in filtration technologies.

Graphite Whiskers Derived from Waste Coffee Grounds Treated at High Temperature.

Graphite whiskers (GWs) are obtained from coffee grounds (CGs) treated at 2500 °C for 1 h in the presence of Ar gas at 1 atm. The majority of the GWs formed inside the CGs shell are rod-like with a conical tip with diameter and length in the range between 1 to 3 µm and 4 to 10 µm, respectively. At first, the carbon layer might be grown in a turbostratic manner, and then progressively graphitized at higher temperature. The strong G' peak intensity might be induced by the disclination of graphitized carbon layers.

Nitrogen self-doped activated carbons via the direct activation of Samanea saman leaves for high energy density supercapacitors.

In this study, nitrogen self-doped activated carbons (ACs) obtained via the direct activation of Samanea saman green leaves (SSLs) for high energy density supercapacitors were investigated. The SSL-derived direct-activated carbons (hereinafter referred to SD-ACs) were synthesized by impregnating sodium hydroxide as an activating agent and heating up to 720 °C without a hydrothermal carbonization or pyrolysis step. The optimum condition was investigated by varying the weight ratio of raw SSLs to NaOH. Surpassing the ACs derived from the two-step convention method, SD-ACs showed superior properties, including a higher surface area (2930 m2 g-1), total pore volume (1.37 cm3 g-1) and nitrogen content (4.6 at%). Moreover, SD-ACs exhibited enhanced electrochemical properties with specific gravimetric and volumetric capacitances of 179 F g-1 and 88 F cm-3 in an organic electrolyte, respectively, a high capacitance retention of approximately 87% at a current density of 0.5 A g-1 and excellent cycling stability of 97.5% after 3000 cycles at a current density of 5 A g-1. Moreover, the potential window of the supercapacitor cell was extended to 3.5 V with a significantly enhanced energy density of up to 79 W h kg-1. These results demonstrate that the direct activation of nitrogen-enriched SSLs offers advantages in terms of simplicity, low-cost and sustainable synthetic route to achieve nitrogen self-doped ACs for high energy density supercapacitors, which exhibit superior properties to that of ACs prepared via the conventional method.

Preparation and electrochemical performance of nitrogen-enriched activated carbon derived from silkworm pupae waste.

In this study, nitrogen-enriched activated carbon from silkworm pupae waste (P-AC) was successfully prepared and its electrochemical performances in aqueous and organic electrolytes were investigated. Silkworm pupae waste is beneficial because it is a nitrogen-enriched, inexpensive, and locally available material. The preparation process includes hydrothermal treatment of the silkworm pupae waste at 200 °C, and chemical activation using zinc chloride at activation temperatures of 700, 800 and 900 °C (P700, P800, and P900, respectively). The nitrogen content in the P-ACs was approximately 3.8-6.4 at%, decreasing with activation temperature, while the surface area was approximately 1062-1267 m2 g-1, increasing with activation temperature. Compared to a commercial AC, the P-ACs show higher nitrogen content but lower surface area. Furthermore, the P800 exhibited superior specific capacitance (154.6 and 91.6 F g-1 in aqueous and organic electrolytes) compared to a commercial AC despite possessing smaller surface area. The high nitrogen content enhanced the pseudocapacitance and improved the electrical conductivity of the P-ACs. These properties were confirmed by relatively low series and charge transfer resistances, a capacity retention higher than 88% at a current density of 0.5 A g-1 and excellent cycling stability demonstrated by maintaining 97.6% of its capacitance after 3000 cycles. These results demonstrate that silkworm pupae waste is a viable source of nitrogen-enriched AC for application in supercapacitors.