Dynamic dissolution of Cm3+ ions incorporated at the calcite-water interface: an ab initio molecular dynamics simulation study.

The stability of actinide-mineral solid solution in a water environment is critical for assessing the safety of nuclear-waste geological repositories and studying actinide migration in natural systems. However, the dissolution behavior of actinide ions incorporated at the mineral-water interface is still unclear at the atomic level. Herein, we present metadynamics simulations of the reaction pathways, thermodynamics and kinetics of trivalent curium ions (Cm3+) dissolving from calcite surfaces. Cm3+ ions incorporated in different calcite surfaces (i.e., terrace and stepped surfaces) with distinct coordination environments have different reaction pathways, free energy barriers and free energy changes. We found that Cm dissolution from a stepped surface is more favorable than that from a terrace surface, both thermodynamically and kinetically. In addition, water molecules seem to promote the detachment of curium ions from the surface by exerting a pulling force via water coordination with Cm3+ and a pushing force via proton migration to the surface layer and water diffusion in the vacant Cm site. Thus, the findings from this work prove to be a milestone in revealing the dynamic dissolution mechanism of trivalent actinides from minerals and would also help predict the dissolution behaviors of other metal ions at the solid-water interface in chemical and environmental sciences.

Theoretical insights into the coordination structures, stabilities and electronic spectra of Cm3+ species at the gibbsite-water interface: A computational study combing ab initio molecular dynamics and wave function theory.

The information of structure and stability of actinide species is key to understand the sorption mechanism of actinides at mineral-water interface. Such information is approximately derived from experimental spectroscopic measurements and needs to be accurately obtained by a direct atomic-scale modelling. Herein, systematic first-principles calculations and ab initio molecular dynamics (AIMD) simulations are carried out to study the coordination structures and absorption energies of Cm(III) surface complexes at gibbsite-water interface. Eleven representative complexing sites are investigated. The most stable Cm3+ sorption species are predicted to be a tridentate surface complex in weakly acidic/neutral solution condition and a bidentate one in the alkaline solution condition. Moreover, luminescence spectra of the Cm3+ aqua ion and the two surface complexes are predicted based on the high-accuracy ab initio wave function theory (WFT). The results give a gradually decreasing emission energy in good agreement with experimental observation of a red shift of peak maximum with pH increasing from 5 to 11. This work is a comprehensive computational study involving AIMD and ab initio WFT methods to gain the coordination structures, stabilities, and electronic spectra of actinide sorption species at the mineral-water interface, thus providing important theoretical support for geological disposal of actinide waste.

Two-dimensional Zr/Hf-hydroxamate metal-organic frameworks.

Novel two-dimensional kagome metal-organic frameworks with mononuclear Zr4+/Hf4+ nodes chelated by benzene-1,4-dihydroxamate linkers were synthesized. The MOFs, namely SUM-1, are chemically robust and kinetically favorable, as confirmed by theoretical and experimental studies. SUM-1(Zr) can be readily made into large (∼100 µm) single crystals and nanoplates (∼50 nm), constituting a versatile MOF platform.

Single metal atom anchored on a CN monolayer as an excellent electrocatalyst for the nitrogen reduction reaction.

Based on first-principles calculations, we have studied the behavior of single-atom catalysts formed by a series of single metal atoms (from Ti to Cu) and a CN monolayer in nitrogen reduction reactions (NRRs). It was demonstrated that TM atoms could be anchored on CN and Ti@CN has good electrical conductivity, high stability and good catalytic performance. The onset potential of Ti@CN is as low as -0.38 V through the enzymatic mechanism, which well suppresses the competitive hydrogen evolution reaction. In addition, the determinate step of Ti@CN for the N2 reduction reaction is lower than that of the Ru(0001) stepped surface (-0.98 V). We further examine the effect of coordination on activity and propose a single Ti atom anchored on CN as a promising catalyst with high catalytic capability for N2 reduction to NH3. Our work offers a new opportunity and useful guidance for the NRR in an ambient environment.

Single transition metal anchored C9N4 sheets as an efficient catalyst for CO oxidation: a first-principles study.

Single-atom catalysts (SACs) often exhibit superb catalytic activity due to their high atom utilization. By comparing the adsorption energies of O2 and CO adsorbed on TM@C9N4, we expect that Co and Ni anchored at the cavity of C9N4 exhibit a higher catalytic activity for CO oxidation. For the entire reaction, the Eley-Rideal, New Eley-Rideal, Ter-molecular Eley-Rideal and Langmuir-Hinshelwood mechanisms are all taken into account. Depending on the reaction mechanisms, the catalysts Co@C9N4 and Ni@C9N4 show excellent activity, with a kinetic energy barrier ranging from 0.19 eV to 0.54 eV for the former, while the corresponding energy barrier is 0.26 eV to 0.44 eV for the latter. The superior stability and activity of Co/Ni@C9N4 can efficiently oxidize the large amounts of CO caused by inadequate combustion of coal and natural gas resources.

Chemico-physical synthesis of surfactant- and ligand-free gold nanoparticles and their anti-galvanic reduction property.

Galvanic reduction (GR) is a classic reaction. In simple terms, metals can reduce less reactive (or more noble) metal ions, while the opposite--metals reduce more reactive (or less noble) metal ions--should not occur. However, recently we found that anti-galvanic reduction (AGR) occurred to thiolated gold and silver nanoparticles. However, the essential issue whether the occurrence of AGR requires the assistance of reductive thiolate ligands or not still remained unanswered. In this work, by using a novel protocol (chemical reduction and physical ablation), we synthesized surfactant- and ligand-free gold nanoparticles. We found that these as-prepared nanoparticles can reduce silver ions and copper ions, thus illustrating that AGR is not dependent on reductive ligands. Further experiments demonstrated that AGR is applicable to other metal (such as Pt and Pd) nanoparticles and that the AGR process is size-dependent. Finally, it was found that the Raman scattering signals of Rhodamine 6G are distinctly enhanced on the gold nanoparticles that had been reacted with silver ions, which indicates the use of AGR for tuning the property of nanoparticles.

Nanocontainers made of various materials with tunable shape and size.

Nanocontainers have great potentials in targeted drug delivery and nanospace-confined reactions. However, the previous synthetic approaches exhibited limited control over the morphology, size and materials of the nanocontainers, which are crucial in practical applications. Here, we present a synthetic approach to multi-segment linear-shaped nanopores with pre-designed morphologies inside anodic aluminium oxide (AAO), by tailoring the anodizing duration after a rational increase of the applied anodizing voltage and the number of voltage increase during Al foil anodization. Then, we achieve nanocontainers with designed morphologies, such as nanofunnels, nanobottles, nano-separating-funnels and nanodroppers, with tunable sizes and diverse materials of carbon, silicon, germanium, hafnium oxide, silica and nickel/carbon magnetic composite, by depositing a thin layer of materials on the inner walls of the pre-designed AAO nanopores. The strategy has far-reaching implications in the designing and large-scale fabrication of nanocontainers, opening up new opportunities in nanotechnology applications.

Nanochannel-directed growth of multi-segment nanowire heterojunctions of metallic Au(1-x)Ge(x) and semiconducting Ge.

We report on the synthesis of multi-segment nanowire (NW) junctions of Au(1-x)Ge(x) and Ge inside the nanochannels of porous anodic aluminum oxide template. The one-dimensional heterostructures are grown with a low-temperature chemical vapor deposition process, assisted by electrodeposited Au nanowires (AuNWs). The Au-catalyzed vapor-liquid-solid growth process occurs simultaneously in multiple locations along the nanochannel, which leads to multi-segment Au(1-x)Ge(x)/Ge heterojunctions. The structures of the as-grown hybrid NWs, analyzed by using transmission electron microscopy and energy-dispersive X-ray spectroscopy elemental mapping, show clear compositional modulation with variable modulation period and controllable junction numbers. Remarkably, both GeNW and Au(1-x)Ge(x)NW segments are single crystalline with abrupt interfaces and good crystallographic coherences. The electronic and transport properties of individual NW junctions are measured by using a multi-probe scanning tunneling microscope, which confirms the semiconducting nature of Ge segments and the metallic behavior of Au(1-x)Ge(x) segments, respectively. The high yield of multiple segment NW junctions of a metal-semiconductor can facilitate the applications in nanoelectronics and optoelectronics that harness multiple functionalities of heterointerfaces.

Controlled synthesis of germanium nanowires and nanotubes with variable morphologies and sizes.

We report on the controlled growth of germanium (Ge) nanostructures in the form of both nanowire (NW) and nanotube (NT) with ultrahigh aspect ratios and variable diameters. The nanostructures are grown inside a porous anodic aluminum oxide (AAO) template by low-temperature chemical vapor deposition (CVD) assisted by an electrodeposited metal nanorod catalyst. Depending on the choice of catalytic metals (Au, Ni, Cu, Co) and germane (GeH(4)) concentration during CVD, either Ge NWs or NTs can be synthesized at low growth temperatures (310-370 °C). Furthermore, Ge NWs and NTs with two or more branches can be grown from the same stem while using AAO with branched channels as templates. Transmission electron microscopy studies show that NWs are single crystalline and that branches grow epitaxially from the stem of NWs with a crystalline direction independent of diameter. As-grown NTs are amorphous but can crystallize via postannealing at 400 °C in Ar/H(2) atmosphere, with a wall thickness controllable between 6 and 18 nm in the CVD process. The yield and quality of the NTs are critically dependent on the choice of the catalyst, where Ni appears the best choice for Ge NT growth among Ni, Cu, Co, and Au. The synthesis of structurally uniform and morphologically versatile Ge nanostructures may open up new opportunities for integrated Ge-nanostructure-based nanocircuits, nanodevices, and nanosystems.

FITC-modified PPy nanotubes embedded in nanoporous AAO membrane can detect trace PCB20 via fluorescence ratiometric measurement.

A highly sensitive and selective fluorescence ratiometric sensor membrane for 2,3,3'-trichlorobiphenyl has been achieved, via depositing polypyrrole nanotubes (PPyNTs, the fluorescence indicator) in nano-porous anodic aluminium oxide (NPAAO) template and subsequently immobilizing fluorescein isothiocyanate (as an internal reference) onto the inner walls of the PPyNTs embedded in the NPAAO.

Ag nanosheet-assembled micro-hemispheres as effective SERS substrates.

Large-scale Ag nanosheet-assembled micro-hemispheres, with sufficient hot spots on their surfaces, have been achieved on an indium tin oxide substrate via electrodeposition. Surface-enhanced Raman scattering (SERS) measurements demonstrate that the Ag nanosheet-assembled micro-hemispheres can serve as sensitive and reproducible SERS substrates.

Crystalline silicon nanotubes and their connections with gold nanowires in both linear and branched topologies.

Silicon, being in the same group in the periodic table as carbon, plays a key role in modern semiconductor industry. However, unlike carbon nanotube (NT), progress remains relatively slow in silicon NT (SiNT) and SiNT-based heteroarchitectures, which would be the fundamental building blocks of various nanoscale circuits, devices, and systems. Here, we report the synthesis of linear and branched crystalline SiNTs via porous anodic aluminum oxide (AAO) self-catalyzed growth and postannealing, and the connection of crystalline SiNTs and gold nanowires (AuNWs) via a combinatorial process of electrodepositing AuNWs with predesired length and location in the channels of the AAO template and subsequent AAO self-catalyzed and postannealing growth of SiNTs in the remaining empty channels adjacent to the AuNWs. Using the approach, a large variety of two-segment AuNW/SiNT and three-segment SiNT/AuNW/SiNT heteronanostructures with both linear and branched topologies have been achieved, paving the way for the rational design and fabrication of SiNT-based nanocircuits, nanodevices, and multifunctional nanosystems in the future.