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Lanthanide/actinide separation is a worldwide challenge for atomic energy and nuclear waste treatment. Separation of americium (Am), a critical actinide element in the nuclear fuel cycle, from lanthanides (Ln) is highly desirable for minimizing the long-term radiotoxicity of nuclear waste, yet it is extremely challenging given the chemical similarity between trivalent Am(III) and Ln(III). Selective oxidation of Am(III) to a higher oxidation state (OS) could facilitate this separation, but so far, it is far from satisfactory for practical application as a result of the unstable nature of Am in a high OS. Herein, we find a novel strategy to generate stable pentavalent Am (Am(V)) through coordination of Am(III) with a diglycolamide ligand and oxidation with Bi(V) species in the presence of an organic solvent. This strategy leads to efficient stabilization of Am(V) and an extraordinarily high separation factor (10

Selective cleavage of C-C linkages is the key and a challenge for lignin degradation to harvest value-added aromatic compounds. To this end, electrocatalytic oxidation presents a promising technique by virtue of mild reaction conditions and strong sustainability. However, the existing electrocatalysts (traditional bulk metal and metal oxides) for C-C bond oxidative cleavage suffer from poor selectivity and low product yields. We show for the first time that atomically dispersed Pt-N3C1 sites planted on nitrogen-doped carbon nanotubes (Pt1/N-CNTs), constructed via a stepwise polymerization-carbonization-electrostatic adsorption strategy, are highly active and selective toward Cα-Cβ bond cleavage in β-O-4 model compounds under ambient conditions. Pt1/N-CNTs exhibits 99% substrate conversion with 81% yield of benzaldehyde, which is exceptional and unprecedented compared with previously reported electrocatalysts. Moreover, Pt1/N-CNTs using only 0.41 wt % Pt achieved a much higher benzaldehyde yield than those of the state-of-the-art bulk Pt electrode (100 wt % Pt) and commercial Pt/C catalyst (20 wt % Pt). Systematic experimental investigation together with density functional theory (DFT) calculation suggests that the superior performance of Pt1/N-CNTs arises from the atomically dispersed Pt-N3C1 sites facilitating the formation of a key Cβ radical intermediate, further inducing a radical/radical cross-coupling path to break the Cα-Cβ bond. This work opens up opportunities in lignin valorization via a green and sustainable electrochemical route with ultralow noble metal usage.

While reduction reactions are ubiquitous in chemistry, it is very challenging to further reduce electron-rich compounds, especially the anionic ones. In this work, the reduction of 1,3-butadienyl dianion, the anionic conjugated olefin, has been realized by divalent rare-earth metal compounds (SmI2), resulting in the formation of novel 2-butene tetraanion bridged disamarium(III) complexes. Density functional theory (DFT) analyses reveal two features: (i) the single electron transfer (SET) from 4f atomic orbitals (AOs) of each Sm center to the antibonding π*-orbitals of 1,3-butadienyl dianion is feasible and the new HOMO formed by the bonding interaction between Sm 5d orbitals (AOs) and the π*-orbitals of 1,3-butadienyl dianion can accept favorably 2e- from 4f AOs of Sm(II); (ii) the 2-butene tetraanionic ligand serves as a unique 10e- donating system, in which 4e- act as two σ-donation bonding interactions while the rest 6e- as three π-donation bonding interactions. The disamarium(III) complexes represent a unique class of the bridged bis-alkylidene rare-earth organometallic complexes. The ligand-based reductive reactivity of 2-butene tetraanion bridged disamarium(III) complexes demonstrates that 2-butene tetraanionic ligand serves as a 3e- reductant toward cyclooctatetraene (COT) to provide doubly COT-supported disamarabutadiene complexes. The reaction of the disamarium(III) complexes with Cp*Li produces the doubly Cp*-coordinated Sm(III) complexes via salt metathesis. In addition, the reaction with Mo(CO)6 affords the oxycyclopentadienyl dinuclear complex via CO insertion.

We report a series of Si(μ-X)AnF3 (An = Th, U; X = H, F) complexes with silicon-actinide(IV) single bonds and unexpected multiradical features that form rare triplet silylenes. These bridged molecules have been prepared in microscopic scale through reactions of laser-ablated uranium and thorium atoms with silicon fluorides and identified from infrared spectra in argon and neon matrixes and relativistic quantum chemical calculations. Similar neon matrix experiments for the reactions of uranium with CF4 and CHF3 were carried out for comparison. Our density functional theory calculations show that the Si-U single-bonded species Si(μ-X)UF3 (X = H, F) with U(IV) oxidation state and the quasi-agostic bridge ligand of H or F are most stable among all the isomers, whereas the naively anticipated triple-bonded species XSi≡UF3 with U(VI) oxidation state and the double-bonded species XSi(•)═(•)UF3 with U(V) oxidation state lie markedly higher in energy. Similar thorium products from reactions with XSiF3 are also found to prefer the Si(μ-X)ThF3 structures with Si-Th single bonds and bridged H or F ligands. High level ab initio wave function theory calculations with the CCSD(T) and CASPT2 methods confirm that the ground states are quintet for Si(μ-X)UF3 and triplet for Si(μ-X)ThF3 with two unpaired electrons on the silylene group. These silicon-bearing molecules as the lowest-energy isomer of XSiAnF3 represent the first silicon-actinide systems with unusual "triplet" silylenes and Si-An single bonds with multiradical character. They are in dramatic contrast to the uranium-carbon analogs, XC≡UF3, which form triple-bonded singlet ground states with C3v symmetry. The calculated vibrational frequencies of the Si(μ-X)AnF3 complexes agree well with experimental observations. These results accentuate the critical difference of chemical bonding of 3p- and 2p-row main-group elements with actinides. The Lewis electron-pair model and the octet rule break down for these silicon compounds.

Ultrathin nanostructures exhibit many interesting properties which are absent or less-pronounced in traditional nanomaterials of larger sizes. In this work, we report the synthesis of ultrathin nanowires and nanoribbons of rare earth hydroxides and demonstrate some new phenomena caused by their atomic-level lateral size (1 nm), including ligand-induced gelation, self-assembly framework, and conformational diversity. These features are typically, although not exclusively, found in polymer solutions. The properties of the inorganic backbone and the emerging polymeric characteristics combined prove to be very promising in the design of new hybrid materials.

The finding of the periodic law is a milestone in chemical science. The periodicity of light elements in the Periodic Table is fully accounted for by quantum mechanics. Here we report that relativistic effects change the bond multiplicity of the group 6 diatomic molecules M2 (M = Cr, Mo, W, Sg) from hextuple bonds for Cr2, Mo2, W2 to quadruple bonds for Sg2, thus breaking the periodicity in the nonrelativistic domain. The same trend is also found for other superheavy-element diatomics Rf2, Db2, Bh2, and Hs2.

Elemental boron is electron-deficient and cannot form graphene-like structures. Instead, triangular boron lattices with hexagonal vacancies have been predicted to be stable. A recent experimental and computational study showed that the B36 cluster has a planar C6v structure with a central hexagonal hole, providing the first experimental evidence for the viability of atom-thin boron sheets with hexagonal vacancies, dubbed borophene. Here we report a boron cluster with a double-hexagonal vacancy as a new and more flexible structural motif for borophene. Photoelectron spectrum of B35(-) displays a simple pattern with certain similarity to that of B36(-). Global minimum searches find that both B35(-) and B35 possess planar hexagonal structures, similar to that of B36, except a missing interior B atom that creates a double-hexagonal vacancy. The closed-shell B35(-) is found to exhibit triple π aromaticity with 11 delocalized π bonds, analogous to benzo(g,h,i)perylene (C22H12). The B35 cluster can be used to build atom-thin boron sheets with various hexagonal hole densities, providing further experimental evidence for the viability of borophene.

In this work, we successfully fabricated near-monodisperse colloids of a new type of inorganic fullerene-like structure (IF) of nickel hydroxychloride as the first example of the application of colloidal synthetic routes to the synthesis of IFs. The formation mechanism and interesting magnetic properties are briefly discussed.

Uniform MoO3 single-walled nanotubes (SWNTs) have been successfully synthesized for the first time through a simple thiol-assisted hydrothermal method. TEM, HRTEM, EELS and XPS characterization showed that the as-obtained sample was composed of high purity SWNTs. We hope our endeavor could blaze a new path in the field of NT research, especially in the barely explored noncarbon SWNT areas.