Labile Coordination Interphase for Regulating Lean Ion Dynamics in Reversible Zn Batteries.

Rechargeability in zinc (Zn) batteries is limited by anode irreversibility. The practical lean electrolytes exacerbate the issue, compromising the cost benefits of zinc batteries for large-scale energy storage. In this study, a zinc-coordinated interphase is developed to avoid chemical corrosion and stabilize zinc anodes. The interphase promotes Zn2+ ions to selectively bind with histidine and carboxylate ligands, creating a coordination environment with high affinity and fast diffusion due to thermodynamic stability and kinetic lability. Experiments and simulations indicate that interphase regulates dendrite-free electrodeposition and reduces side reactions. Implementing such labile coordination interphase results in increased cycling at 20 mA cm-2 and high reversibility of dendrite-free zinc plating/stripping for over 200 hours. A Zn||LiMn2 O4 cell with 74.7 mWh g-1 energy density and 99.7% Coulombic efficiency after 500 cycles realized enhanced reversibility using the labile coordination interphase. A lean-electrolyte full cell using only 10 µL mAh-1 electrolyte is also demonstrated with an elongated lifespan of 100 cycles, five times longer than bare Zn anodes. The cell offers a higher energy density than most existing aqueous batteries. This study presents a proof-of-concept design for low-electrolyte, high-energy-density batteries by modulating coordination interphases on Zn anodes.

Complexation-based selectivity of organic phosphonates adsorption from high-salinity water by neodymium-doped nanocomposite.

Organic phosphonates have been widely used in various industries and are ubiquitous in wastewaters, and efficient removal of phosphonates is still a challenge for the conventional processes because of the severe interferences from the complex water constitutions. Herein, an Nd-based nanocomposite (HNdO@PsAX) was fabricated by immobilizing hydrated neodymium oxide (HNdO) nanoparticles inside a polystyrene anion exchanger (PsAX) to remove phosphonates from high-salinity aqueous media. Batch experiments demonstrated that HNdO@PsAX had an excellent adsorption capacity (∼90.5 mg P/g-Nd) towards a typical phosphonate (1-hydrox-yethylidene-1,1-diphosphonic acid, HEDP) from the background of 8 g/L NaCl, whereas negligible HEDP adsorption was achieved by PsAX. Attractively, various coexisting substances (humic acid, phosphate, citrate, EDTA, metal ligands, and anions) exerted negligible effects on the HEDP adsorption by HNdO@PsAX under high salinity. FT-IR and XPS analyses revealed that the inner-sphere complexation between HEDP and the immobilized HNdO nanoparticles is responsible for HEDP adsorption. Fixed-bed experiments further verified that HNdO@PsAX was capable of successively treating more than 4500 bed volumes (BV) of a synthetic high-salinity wastewater (1.0 mg P/L of HEDP), whereas only ∼2 BV of effective treatment capacity was received by PsAX. The exhausted HNdO@PsAX was amenable to a complete regeneration by a binary NaOHNaCl solution without significant loss in capacity. The capability in removing other organic phosphonates and treating a real electroplating wastewater by HNdO@PsAX was further validated. Generally, HNdO@PsAX exhibited a great potential in efficiently removing phosphonates from high-salinity wastewater.

Enhanced phosphate removal from water by hydrated neodymium oxide-based nanocomposite: Performance, mechanism, and validation.

Phosphorus (P) control has been recognized as an imperative task to mitigate water eutrophication and settle the imminent shortage of P resources. Despite intensive effort put into this matter, it is still generally challenging for the current methods to remove and even potentially recover phosphorus (as phosphate) from complicated water matrices. To this end, we proposed a novel nanocomposite via coupling polystyrene anion exchanger (PsAX) with hydrated neodymium oxide (HNdO) nanoparticle for selective removal of phosphate. The developed nanocomposite, i.e., HNdO-PsAX, exhibited quite stable and efficient phosphate adsorption over a wide pH range of 3.0-10.0 with the maximum adsorption capacity as 85.4 mg P/g. It also showed satisfied anti-interference against various competing substances; notably, HNdO-PsAX obviously outperformed Phoslock, a commercial lanthanum-based adsorbent exclusively for phosphate sequestration, particularly under the interference of bicarbonate and humic acid, which were admitted as the paralyzing factors for Phoslock. The superior affinity of HNdO-PsAX towards phosphate, driven by the specific Nd-P inner-sphere complexation as evidenced by XPS, FT-IR, and the lattice evolution of HNdO nanoparticle, renders the nanocomposite eminently suitable for sequestrating trace phosphate. Fixed-bed treatment validated that HNdO-PsAX was capable of treating ∼11,800 bed volume of a simulated wastewater (from 2.0 to below 0.5 mg P/L), approximately 12 times higher than that of the previously reported Fe-based nanocomposite (HFO-PsAX, ∼ 900 BV); also, a satisfactory outcome in treating authentic municipal wastewater by HNdO-PsAX and the feasibility of regenerating the exhausted one by a binary NaOH-NaCl solution were recognized. This work provides a new potion of enhanced phosphorous control for surface water and wastewater.

Using stable isotopes to identify nitrogen transformations and estimate denitrification in a semi-constructed wetland.

Constructed wetlands are effective at removing nitrate, one of the major pollutants in aquatic ecosystems. In this study, nitrogen and oxygen isotopes (δ15N and δ18O) were used to determine the sources and transformations of nitrate (NO3-), evaluate isotopic fractionation, and estimate nitrogen (N) removal in the Xixi Wetland, a large semi-constructed wetland in East China. The values of δ15N and δ18O in the Xixi Wetland ranged from +3.7‰ to +19.0‰ and from +1.1‰ to +13.7‰, respectively. The main NO3- sources included sewage/manure, chemical fertiliser and soil nitrogen. Anthropogenic sources became more significant in the Xixi Westland, especially in autumn, as the increased number of tourists resulted in increased sewage/manure input. The results indicated that nitrification and denitrification were the key processes governing N transformations. The monthly variations in the NO3- concentrations and δ15N values indicated that denitrification was strong from spring to autumn in the Xixi Wetland. Based on measurements of the natural abundance of δ15N, it was determined that the enrichment factors (ε) of the Xixi Wetland ranged from -0.7‰ to -1.0‰, and were smaller than those in a laboratory denitrification experiment (-1.6‰). In this study, denitrification, nitrification, and assimilation in plants/microbes were responsible for the low enrichment factors. Additionally, the amount of N removal via denitrification varied widely, from 22 kg N·ha-1 yr-1 to 798 kg N·ha-1 yr-1; thus, significant potential for N removal was found in the Xixi Wetland.