Microbial Mineralization with Lysinibacillus sphaericus for Selective Lithium Nanoparticle Extraction.

Lithium is a critical mineral in a wide range of current technologies, and demand continues to grow with the transition to a green economy. Current lithium mining and extraction practices are often highly ecologically damaging, in part due to the large amount of water and energy they consume. Biomineralization is a natural process that transforms inorganic precursors to minerals. Microbial biomineralization has potential as an ecofriendly alternative to current lithium extraction techniques. This work demonstrates Lysinibacillus sphaericus biomineralization of lithium chloride to lithium hydroxide. Quantitative analysis of biomineralized lithium via the 2-(2-hydroxyphenyl)-benzoxazole fluorescence assay reveals significantly greater recovery with L. sphaericus than without. Furthermore, L. sphaericus biomineralization is specific to lithium over sodium. The nanoparticles produced were further characterized via Fourier transform infrared and transmission electron microscopy analysis as crystalline lithium hydroxide, which is an advanced functional material. Finally, ESI-LC/MS was used to identify several proteins involved in this microbial biomineralization process, including the S-layer protein. Through the isolation of L. sphaericus ghosts, this work shows that the S-layer protein alone plays a critical role in the biomineralization of crystalline lithium hydroxide nanoparticles. Through this study of microbial biomineralization of lithium with L. sphaericus, there is potential to develop innovative and environmentally friendly extraction techniques.

Surfactants Used in Colloidal Synthesis Modulate Ni Nanoparticle Surface Evolution for Selective CO2 Hydrogenation.

Colloidal chemistry holds promise to prepare uniform and size-controllable pre-catalysts; however, it remains a challenge to unveil the atomic-level transition from pre-catalysts to active catalytic surfaces under the reaction conditions to enable the mechanistic design of catalysts. Here, we report an ambient-pressure X-ray photoelectron spectroscopy study, coupled with in situ environmental transmission electron microscopy, infrared spectroscopy, and theoretical calculations, to elucidate the surface catalytic sites of colloidal Ni nanoparticles for CO2 hydrogenation. We show that Ni nanoparticles with phosphine ligands exhibit a distinct surface evolution compared with amine-capped ones, owing to the diffusion of P under oxidative (air) or reductive (CO2 + H2) gaseous environments at elevated temperatures. The resulting NiPx surface leads to a substantially improved selectivity for CO production, in contrast to the metallic Ni, which favors CH4. The further elimination of surface metallic Ni sites by designing multi-step P incorporation achieves unit selectivity of CO in high-rate CO2 hydrogenation.

Surfactant Removal for Colloidal Nanocrystal Catalysts Mediated by N-Heterocyclic Carbenes.

We report the facile removal of surfactants from colloidally synthesized nanocrystals via ligand exchange with N-heterocyclic carbenes (NHCs). Subsequent protonation of the NHC ligands in acid efficiently cleans the nanocrystals' surface while preserving their uniform morphology and structure for catalysis. The broad efficacy of this strategy is validated using monodisperse Pt, Pd, and Au nanocrystals, each prepared with strongly bound phosphine stabilizers. The surface-activated nanocrystals exhibit significantly improved catalytic activities, superior to those obtained with other surface cleaning methods, as demonstrated in two centrally important electrochemical reactions (glycerol oxidation and CO2 reduction). This work highlights a new surface activation strategy for catalysis and other applications that enables the efficient use of well-defined nanocrystal libraries prepared by colloidal chemistry.

Generalized Synthetic Strategy for Transition-Metal-Doped Brookite-Phase TiO2 Nanorods.

We report a generalized wet-chemical methodology for the synthesis of transition-metal (M)-doped brookite-phase TiO2 nanorods (NRs) with unprecedented wide-range tunability in dopant composition (M = V, Cr, Mn, Fe, Co, Ni, Cu, Mo, etc.). These quadrangular NRs can selectively expose {210} surface facets, which is induced by their strong affinity for oleylamine stabilizer. This structure is well preserved with variable dopant compositions and concentrations, leading to a diverse library of TiO2 NRs wherein the dopants in single-atom form are homogeneously distributed in a brookite-phase solid lattice. This synthetic method allows tuning of dopant-dependent properties of TiO2 nanomaterials for new opportunities in catalysis applications.

Phosphate-Functionalized CeO2 Nanosheets for Efficient Catalytic Oxidation of Dichloromethane.

Tuning the nature and profile of acidic and basic sites on the surface of redox-active metal oxide nanostructures is a promising approach to constructing efficient catalysts for the oxidative removal of chlorinated volatile organic compounds (CVOCs). Herein, using dichloromethane (DCM) oxidation as a model reaction, we report that phosphate (PO x) Brønsted acid sites can be incorporated onto a CeO2 nanosheet (NS) surface via an organophosphate-mediated route, which can effectively enhance the CeO2's catalytic performance by promoting the removal of chlorine poisoning species. From the systematic study of the correlation between PO x composition, surface structure (acid and basic sites), and catalytic properties, we find that the incorporated Brønsted acid sites can also function to decrease the amount of medium-strong basic sites (O2-), reducing the formation of chlorinated organic byproduct monochloromethane (MCM) and leading to the desirable product, HCl. At the optimized P/Ce ratio (0.2), the PO x-CeO2 NSs can perform a stable DCM conversion of 65-70% for over 10 h at 250 °C and over 95% conversion at 300 °C, superior to both pristine and other phosphate-modified CeO2 NSs. Our work clearly identifies the critical role of acid and basic sites over functionalized CeO2 for efficient catalytic CVOCs oxidation, guiding future advanced catalyst design for environmental remediation.

Photoluminescence switching in quantum dots connected with fluorinated and hydrogenated photochromic molecules.

We investigate switching of photoluminescence (PL) from PbS quantum dots (QDs) crosslinked with two different types of photochromic diarylethene molecules, 4,4'-(1-cyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] (1H) and 4,4'-(1-perfluorocyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] (2F). Our results show that the QDs crosslinked with the hydrogenated molecule (1H) exhibit a greater amount of switching in photoluminescence intensity compared to QDs crosslinked with the fluorinated molecule (2F). With a combination of differential pulse voltammetry and density functional theory, we attribute the different amount of PL switching to the different energy levels between 1H and 2F molecules which result in different potential barrier heights across adjacent QDs. Our findings provide a deeper understanding of how the energy levels of bridge molecules influence charge tunneling and PL switching performance in QD systems and offer deeper insights for the future design and development of QD based photo-switches.

Surface Ligand Environment Boosts the Electrocatalytic Hydrodechlorination Reaction on Palladium Nanoparticles.

We present an enhanced catalytic efficiency of palladium (Pd) nanoparticles (NPs) for the electrocatalytic hydrodechlorination (EHDC) reaction by incorporating the tetraethylammonium chloride (TEAC) ligand into the surface of NPs. Both experimental and theoretical analyses reveal that the surface-adsorbed TEAC is converted to molecular amine (primarily triethylamine) under reductive potentials, forming a strong ligand-Pd interaction that is beneficial to the EHDC kinetics. Using the EHDC of 2,4-dichlorophenol (2,4-DCP), a dominant persistent pollutant identified by the U.S. Environmental Protection Agency, as an example, the Pd/amine composite delivers a mass activity of 2.32 min-1 gPd-1 and a specific activity of 0.16 min-1 cm-2 at -0.75 V versus Ag/AgCl, outperforming Pd and most of the previously reported catalysts. The mechanistic study reveals that the amine ligand offers three functions: the H+-pumping effect, the electronic effect, and the steric effect, providing a favorable environment for the generation of reactive hydrogen radicals (H*) for hydrogenolysis of the C-Cl bond. It also weakens the adsorption strength of EHDC products, alleviating their poisoning on Pd. Investigation into the intermediate products of EHDC on Pd/amine and the biological safety of the 2,4-DCP-contaminated water after EHDC treatment demonstrates that EHDC on Pd/amine is environmentally benign for halogenated organic pollutant abatement. This work suggests that the tuning of NP catalysis using facile ligand post-treatment may lead to new strategies to improve EHDC for environmental remediation applications.

AgPd nanoparticles for electrocatalytic CO2 reduction: bimetallic composition-dependent ligand and ensemble effects.

Monodisperse AgPd nanoparticles (NPs) were synthesized and studied as an efficient catalyst for electrocatalytic CO2 reduction by modulating bimetallic compositions. The mechanistic studies, based on density functional theory (DFT) calculations and environmental diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) analysis, revealed that the incorporation of Ag in AgPd NPs can effectively weaken CO adsorption on all possible Pd surface sites (the ligand effects), and more importantly, disrupt the strongest multi-centered CO-binding sites (the ensemble effects). With properly tuned CO adsorption, which is ordinarily too strong over pure Pd, Ag15Pd85 NPs were found to be the best composition for the efficient production of CO. They deliver a unity conversion of CO2 to CO with a high mass activity of 15.2 mA mgmetal-1 at -0.8 V vs. the reversible hydrogen electrode (RHE) and high stability with minimal change in the CO faradaic efficiency (FECO) after 12 hours of operation.

Two-Dimensional Metal Organic Framework Nanosheets as Bifunctional Catalyst for Electrochemical and Photoelectrochemical Water Oxidation.

Electrochemical (EC) and photoelectrochemical (PEC) water splitting represent promising strategies for renewable energy conversion and fuel production and require design of efficient catalysts for the oxygen evolution reaction (OER). Herein, we report the synthesis of two-dimensional (2D) Co-based metal organic framework (Co-MOF) nanosheets and their bifunctional catalytic properties for both EC and PEC OER. Benefiting from the large surface area and abundant isolated metal active sites, the Co-MOF nanosheets exhibited excellent OER activity and stability. The efficient electron-hole generation and separation of the nanosheets, owing to dimensional confinement, contributed to an improved visible light response in PEC OER. This study presents a new strategy to design EC/PEC bifunctional catalyst utilizing unique structural and electronic features of 2D MOF.

Mercury and Lead Contamination in Three Fish Species and Sediments from Lake Rukwa and Catchment Areas in Tanzania.

BACKGROUND: Mining activity in the catchment area of Tanzania's Lake Rukwa is suspected of adding to the lake and connected rivers' heavy metal load. There has been no study done, however, on the levels of mercury (Hg) and lead (Pb) in lake sediment and fish muscle, and what the results could mean for human health. OBJECTIVES: This study investigated the concentration of Hg and Pb in lake sediment and in the muscles of African sharptooth catfish (Clarias gariepinus), Lake Rukwa tilapia (Oreochromis rukwaensis) and Singida tilapia (Oreochromis esculentus) from Tanzania's Lake Rukwa and connected rivers. METHODS: Concentrations of Hg and Pb in fish muscle and lake sediment were measured using inductively coupled plasma atomic emission spectroscopy (ICP-AES) and mercury analyzers, respectively. RESULTS: Levels of Pb and Hg from C. gariepinus ranged between 0.01 to 1.9 µg/g and 0.03 to 0.33 µg/g, respectively. Pb and Hg in O. esculentus varied between 0.02 to 1.4 µg/g and <0.01 to 0.29 µg/g, respectively. Pb and Hg levels in O. rukwaensis ranged from 0.12 to 0.88 µg/g and 0.12 to 0.88 µg/g, respectively. On the other hand, concentrations of Pb and Hg in the sediment samples ranged between 0.02 to 16.23 µg/g and from 0.01 to 1.43 µg/g, respectively. Concentrations of Hg in the muscles of C. gariepinus and O. esculentus were above World Health Organization (WHO) permissible limits, indicating that they are not safe for human consumption. Concentrations of Pb in fish muscle samples were below WHO permissible limits and United States Environmental Protection Agency (USAEPA) provisional tolerable weekly intake (PTWI) standards. Furthermore, Hg and Pb in sediment were below the threshold value of Environment Canada and Florida's 'No effect level'. CONCLUSIONS: Although levels of Pb in fish samples and Hg and Pb levels in sediment were below international standards, it is important to consider that fish forms an important source of animal protein for local inhabitants, who are likely to consume more fish than considered by these standards. The study recommends further research on the levels of mercury and lead in humans, especially children and pregnant women.