Hydrated cation-π interactions of π-electrons with hydrated Mg2+ and Ca2+ cations.

Hydrated cation-π interactions at liquid-solid interfaces between hydrated cations and aromatic ring structures of carbon-based materials are pivotal in many material, biological, and chemical processes, and water serves as a crucial mediator in these interactions. However, a full understanding of the hydrated cation-π interactions between hydrated alkaline earth cations and aromatic ring structures, such as graphene remains elusive. Here, we present a molecular picture of hydrated cation-π interactions for Mg2+ and Ca2+ by using the density functional theory methods. Theoretical results show that the graphene sheet can distort the hydration shell of the hydrated Ca2+ to interact with Ca2+ directly, which is water-cation-π interactions. In contrast, the hydration shell of the hydrated Mg2+ is quite stable and the graphene sheet interacts with Mg2+ indirectly, mediated by water molecules, which is the cation-water-π interactions. These results lead to the anomalous order of adsorption energies for these alkaline earth cations, with hydrated Mg2+-π < hydrated Ca2+-π when the number of water molecules is large (n ≥ 6), contrary to the order observed for cation-π interactions in the absence of water molecules (n = 0). The behavior of hydrated alkaline earth cations adsorbed on a graphene surface is mainly attributed to the competition between the cation-π interactions and hydration effects. These findings provide valuable details of the structures and the adsorption energy of hydrated alkaline earth cations adsorbed onto the graphene surface.

Platinum-Loaded Cerium Oxide Capable of Repairing Neuronal Homeostasis for Cerebral Ischemia-Reperfusion Injury Therapy.

Effective neuroprotective agents are required to prevent neurological damage caused by reactive oxygen species (ROS) generated by cerebral ischemia-reperfusion injury (CIRI) following an acute ischemic stroke. Herein, it is aimed to develop the neuroprotective agents of cerium oxide loaded with platinum clusters engineered modifications (Ptn-CeO2). The density functional theory calculations show that Ptn-CeO2 could effectively scavenge ROS, including hydroxyl radicals (·OH) and superoxide anions (·O2 -). In addition, Ptn-CeO2 exhibits the superoxide dismutase- and catalase-like enzyme activities, which is capable of scavenging hydrogen peroxide (H2O2). The in vitro studies show that Ptn-CeO2 could adjust the restoration of the mitochondrial metabolism to ROS homeostasis, rebalance cytokines, and feature high biocompatibility. The studies in mice CIRI demonstrate that Ptn-CeO2 could also restore cytokine levels, reduce cysteine aspartate-specific protease (cleaved Caspase 3) levels, and induce the polarization of microglia to M2-type macrophages, thus inhibiting the inflammatory responses. As a result, Ptn-CeO2 inhibits the reperfusion-induced neuronal apoptosis, relieves the infarct volume, reduces the neurological severity score, and improves cognitive function. Overall, these findings suggest that the prominent neuroprotective effect of the engineered Ptn-CeO2 has a significant neuroprotective effect and provides a potential therapeutic alternative for CIRI.

Thermally Reduced Graphene Oxide Membranes Revealed Selective Adsorption of Gold Ions from Mixed Ionic Solutions.

The recovery of gold from water is an important research area. Recent reports have highlighted the ultrahigh capacity and selective extraction of gold from electronic waste using reduced graphene oxide (rGO). Here, we made a further attempt with the thermal rGO membranes and found that the thermal rGO membranes also had a similarly high adsorption efficiency (1.79 g gold per gram of rGO membranes at 1000 ppm). Furthermore, we paid special attention to the detailed selectivity between Au3+ and other ions by rGO membranes. The maximum adsorption capacity for Au3+ ions was about 16 times that of Cu2+ ions and 10 times that of Fe3+ ions in a mixture solution with equal proportions of Au3+/Cu2+ and Au3+/Fe3+. In a mixed-ion solution containing Au3+:Cu2+:Na+:Fe3+:Mg2+ of printed circuit board (PCB), the mass of Au3+:Cu2+:Na+:Fe3+:Mg2+ in rGO membranes is four orders of magnitude higher than the initial mass ratio. A theoretical analysis indicates that this selectivity may be attributed to the difference in the adsorption energy between the metal ions and the rGO membrane. The results are conducive to the usage of rGO membranes as adsorbents for Au capture from secondary metal resources in the industrial sector.

Turning Electrocatalytic Activity Sites for the Oxygen Evolution Reaction on Brownmillerite to Oxyhydroxide.

One of the major challenges that hinder the practical application of water electrolysis lies in the design of advanced electrocatalysts toward the anodic oxygen evolution reaction (OER). In this work, a pure Co-based precatalyst of CoOOH/brownmillerite derived from the surface activation of brownmillerite by a surface acid etching method exhibits high activity and stable electrical properties toward the OER. Different from oxyhydroxide derived from in situ surface reconstruction during the electrochemical process, the growth of highly crystalline CoOOH from the brownmillerite surface enables rational control over the surface/bulk structure as well as the concentration of active sites, and this structure can be well maintained and serve as highly active sites. The catalyst shows a low overpotential of 320 mV to obtain 10 mA cm-2 and high stability in an alkaline electrolyte for the OER, which is comparable to the majority of Co-based electrocatalysts. Moreover, the appropriate interfacial interaction of the composite catalysts greatly contributes to the hydroxide insertion to improve water oxidation ability. This work proposes an effective strategy to develop high-performance metal oxide-based materials for the OER.

Novel 2D CaCl crystals with metallicity, room-temperature ferromagnetism, heterojunction, piezoelectricity-like property and monovalent calcium ions.

Under ambient conditions, the only known valence state of calcium ions is +2, and the corresponding crystals with calcium ions are insulating and nonferromagnetic. Here, using cryo-electron microscopy, we report direct observation of two-dimensional (2D) CaCl crystals on reduced graphene oxide (rGO) membranes, in which the calcium ions are only monovalent (i.e. +1). Remarkably, metallic rather than insulating properties are displayed by those CaCl crystals. More interestingly, room-temperature ferromagnetism, graphene-CaCl heterojunction, coexistence of piezoelectricity-like property and metallicity, as well as the distinct hydrogen storage and release capability of the CaCl crystals in rGO membranes are experimentally demonstrated. We note that such CaCl crystals are obtained by simply incubating rGO membranes in salt solutions below the saturated concentration, under ambient conditions. Theoretical studies suggest that the formation of those abnormal crystals is attributed to the strong cation-π interactions of the Ca cations with the aromatic rings in the graphene surfaces. The findings highlight the realistic potential applications of such abnormal CaCl material with unusual electronic properties in designing novel transistors and magnetic devices, hydrogen storage, catalyzers, high-performance conducting electrodes and sensors, with a size down to atomic scale.

Hydrated cation-π interactions of π-electrons with hydrated Li+, Na+, and K+ cations.

Cation-π interactions are essential for many chemical, biological, and material processes, and these processes usually involve an aqueous salt solution. However, there is still a lack of a full understanding of the hydrated cation-π interactions between the hydrated cations and the aromatic ring structures on the molecular level. Here, we report a molecular picture of hydrated cation-π interactions, by using the calculations of density functional theory (DFT). Specifically, the graphene sheet can distort the hydration shell of the hydrated K+ to interact with K+ directly, which is hereafter called water-cation-π interactions. In contrast, the hydration shell of the hydrated Li+ is quite stable and the graphene sheet interacts with Li+ indirectly, mediated by water molecules, which we hereafter call the cation-water-π interactions. The behavior of hydrated cations adsorbed on a graphene surface is mainly attributed to the competition between the cation-π interactions and hydration effects. These findings provide valuable details of the structures and the adsorption energy of hydrated cations adsorbed onto the graphene surface.

Tuning the Interlayer Spacings in Dry Graphene Oxide Membranes via Ions.

We show the experimental achievement of dry GO membranes with interlayer spacings in the range from 7.09 Što 8.72 Å, tuned and fixed by salts. We found that the interlayer spacings were dominated by the anions or the groups with negative charges in between the GO membranes. Density functional theory (DFT) calculations reveal that the highly efficient tuning of the interlayer spacing in dry GO membranes is due to ion-π interactions on the graphene sheets, together with the steric effects of anions in between the GO sheets. The findings are helpful for extending their potential applications including chemical sensors, nanomaterial devices preparation, chemical catalysis and synthesis, and gas separation.

Effects of cationic concentration on controlling the interlayer spacings for highly effective ion rejection via graphene oxide membranes.

The effect of cationic concentration on controlling the interlayer spacings of graphene oxide (GO) membranes is systemically studied. It was found that a higher concentration leads to narrower interlayer spacings, and thus, ions in salt solutions were effectively rejected. This provides a new avenue for ion separation using graphene-based membranes.

Precise control of the interlayer spacing between graphene sheets by hydrated cations.

Recently, we have demonstrated that highly efficient ion rejection by graphene oxide membranes can be facilely achieved using hydrated cations to control the interlayer spacing in GO membranes. By using density functional theory calculations, we have shown that different hydrated cations can also precisely control the interlayer spacings between graphene sheets, which are smaller than graphene oxide sheets; this indicates ion sieving. The interlayer distances are 9.35, 8.96 and 8.82 Å for hydrated Li+, Na+ and K+, respectively. Since the radii of the hydrated Na+ and Li+ ions are larger than that of hydrated K+, graphene membranes controlled by the hydrated K+ ion can exclude K+ and the other two cations with larger hydrated volumes. Further analysis of charge transfer and orbit analysis showed that this type of control by the hydrated cations is attributed to the strong hydrated cation-π interactions; moreover, when soaked in a salt solution, graphene membranes adsorb hydrated Na+ and Li+ and form intercalation compounds. However, it is hard to find K-doped intercalation compounds in the inner part of graphene.