Anodization of Pd in H₂SO₄ Solutions: Influence of Potential, Polarization Time, and Electrolyte Concentration

The anodization of Pd in H2SO4 solutions has been investigated by electrochemical measurements, considering the effect of the applied potential, polarization time, and electrolyte concentration. The anodization and subsequent reduction result in the formation of Pd nanostructures on the electrode surface. Compared to the bulk Pd, the anodization of Pd in H2SO4 solutions leads to different cyclic voltammetry (CV) behaviors including well-separated adsorption/desorption peaks in the hydrogen region and relatively larger reduction peak areas. The improvement of electrochemically active surface areas (EASAs) of the anodized Pd samples is strongly dependent upon the electrolyte concentration, and the optimum H2SO4 concentration is 1.0 M. Both the applied potential and polarization time have a significant influence on the anodization process of Pd. For the given electrolyte concentration, there exist desirable applied potential and polarization time to achieve greater EASAs. The EASAs of the anodized Pd obtained under the optimum polarization conditions can reach as large as 890 times compared to its geometric area. In addition, the formation mechanism of Pd nanostructures on the electrode surface has been discussed on the basis of microstructural analysis. The present findings provide a promising route to fabricate nanostructured Pd electrocatalysts with ultrahigh EASAs

Three-Dimensional Cu Foam-Supported Single Crystalline Mesoporous Cu₂O Nanothorn Arrays for Ultra-Highly Sensitive and Efficient Nonenzymatic Detection of Glucose

Highly sensitive and efficient biosensors play a crucial role in clinical, environmental, industrial, and agricultural applications, and tremendous efforts have been dedicated to advanced electrode materials with superior electrochemical activities and low cost. Here, we report a three-dimensional binder-free Cu foam-supported Cu₂O nanothorn array electrode developed via facile electrochemistry. The nanothorns growing in situ along the specific direction of <011> have single crystalline features and a mesoporous surface. When being used as a potential biosensor for nonenzyme glucose detection, the hybrid electrode exhibits multistage linear detection ranges with ultrahigh sensitivities (maximum of 97.9 mA mM^–1 cm^–2) and an ultralow detection limit of 5 nM. Furthermore, the electrode presents outstanding selectivity and stability toward glucose detection. The distinguished performances endow this novel electrode with powerful reliability for analyzing human serum samples. These unprecedented sensing characteristics could be ascribed to the synergistic action of superior electrochemical catalytic activity of nanothorn arrays with dramatically enhanced surface area and intimate contact between the active material (Cu₂O) and current collector (Cu foam), concurrently supplying good conductivity for electron/ion transport during glucose biosensing. Significantly, our findings could guide the fabrication of new metal oxide nanostructures with well-organized morphologies and unique properties as well as low materials cost

Recovery of Rare Earth Elements from Geothermal Fluids through Bacterial Cell Surface Adsorption

The increasing demand for rare earth elements (REEs) in the modern economy motivates the development of novel strategies for cost-effective REE recovery from nontraditional feedstocks. We previously engineered E. coli to express lanthanide binding tags on the cell surface, which increased the REE biosorption capacity and selectivity. Here we examined how REE adsorption by the engineered E. coli is affected by various geochemical factors relevant to geothermal fluids, including total dissolved solids (TDS), temperature, pH, and the presence of specific competing metals. REE biosorption is robust to TDS, with high REE recovery efficiency and selectivity observed with TDS as high as 165,000 ppm. Among several metals tested, U, Al, and Pb were found to be the most competitive, causing >25% reduction in REE biosorption when present at concentrations ∼3- to 11-fold higher than the REEs. Optimal REE biosorption occurred between pH 5–6, and sorption capacity was reduced by ∼65% at pH 2. REE recovery efficiency and selectivity increased as a function of temperature up to ∼70 °C due to the thermodynamic properties of metal complexation on the bacterial surface. Together, these data define the optimal and boundary conditions for biosorption and demonstrate its potential utility for selective REE recovery from geofluids

Amorphous CeO₂–Cu Heterostructure Enhances CO₂ Electroreduction to Multicarbon Alcohols

Electrochemical conversion of carbon dioxide (CO2) gas to value-added chemicals such as multicarbon (C2+) alcohols is a promising and attractive decarbonization strategy. However, there are tremendous challenges in tuning the intrinsic activity and selectivity of the catalysts to produce C2+ alcohols. In this work, we prepared a CeO2–Cu composite catalyst via a combination of metallurgy and dealloying method. The interfacial sites of amorphous CeO2–Cu heterostructure improve the adsorption of key reaction intermediates *CO and promote the C–C coupling. Significantly, they also stabilize *CH2CHO at the bifurcation step, steering the reaction pathway toward the formation of C2+ alcohols over ethylene. The CeO2–Cu catalyst achieves a remarkable faradaic efficiency of 32.9% ± 2.6% for C2+ alcohols at −0.6 V vs RHE. This work demonstrates an effective strategy of improving the intrinsic activity and selectivity of the Cu-based catalysts for the generation of C2+ alcohols