Surface-Reconstructed Ru-Doped Nickel/Iron Oxyhydroxide Arrays for Efficient Oxygen Evolution.

The generation of an active phase through dynamic surface reconstruction is a promising strategy for improving the activity of electrocatalysts. However, studies investigating the reconstruction process and its impact on the intrinsic properties of the catalysts are scarce. Herein, the surface reconstruction of NiFe2 O4 interfaced with NiMoO4 (Ru-NFO/NMO) facilitated by Ru doping is reported. The electrochemical and material characterizations demonstrate that Ru doping can regulate the electronic structure of NFO/NMO and induce the high-valence state of Ni3.6+ δ , facilitating the surface reconstruction to highly active Ru-doped NiFeOOH/NiOOH (SR-Ru-NFO/NMO). The optimized SR-Ru-NFO/NMO exhibits promising performance in the oxygen evolution reaction, displaying a low overpotential of 229 mV at 10 mA cm-2 and good stability at varying current densities for 80 h. Density functional theory calculations indicate that Ru doping can increase the electron density and optimize intermediate adsorption by shifting the d-band center downward. This work provides valuable insights into the tuning of electrocatalysts by surface reconstruction and offers a rational design strategy for the development of highly active oxygen evolution reaction electrocatalysts.

Recycling Spent Lithium-Ion Batteries Using Waste Benzene-Containing Plastics: Synergetic Thermal Reduction and Benzene Decomposition.

Spent lithium-ion batteries (LIBs) and benzene-containing polymers (BCPs) are two major pollutants that cause serious environmental burdens. Herein, spent LIBs and BCPs are copyrolyzed in a sealed reactor to generate Li2CO3, metals, and/or metal oxides without emitting toxic benzene-based gases. The use of a closed reactor allows the sufficient reduction reaction between the BCP-derived polycyclic aromatic hydrocarbon (PAH) gases and lithium transition metal oxides, achieving the Li recovery efficiencies of 98.3, 99.9, and 97.5% for LiCoO2, LiMn2O4, and LiNi0.6Co0.2Mn0.2O2, respectively. More importantly, the thermal decomposition of PAHs (e.g., phenol and benzene) is further catalyzed by the in situ generated Co, Ni, and MnO2 particles, which forms metal/carbon composites and thus prevent the emissions of toxic gases. Overall, the copyrolysis in a closed system paves a green way to synergistically recycle spent LIBs and handle waste BCPs.

Tuning the Site-to-Site Interaction in Ru-M (M = Co, Fe, Ni) Diatomic Electrocatalysts to Climb up the Volcano Plot of Oxygen Electroreduction.

The modulating of the geometric and electronic structures of metal-N-C atomic catalysts for improving their performance in catalyzing oxygen reduction reactions (ORRs) is highly desirable yet challenging. We herein report a delicate "encapsulation-substitution" strategy for the synthesis of paired metal sites in N-doped carbon. With the regulation of the d-orbital energy level, a significant increment in oxygen electroreduction activity was demonstrated in Ru-Co diatomic catalyst (DAC) compared with other diatomic (Ru-Fe and Ru-Ni) and single-atomic counterparts. The Ru-Co DAC efficiently reduces oxygen with a halfwave potential of 0.895 V vs RHE and a turnover frequency of 2.424 s-1 at 0.7 V, establishing optimal thermodynamic and kinetic behaviors in the triple-phase reaction under practical conditions. Moreover, the Ru-Co DAC electrode displays bifunctional activity in a gas diffusion Zn-air battery with a small voltage gap of 0.603 V, outperforming the commercial Pt/C|RuO2 catalyst. Our findings provide a clear understanding of site-to-site interaction on ORR and a benchmark evaluation of atomic catalysts with correlations of diatomic structure, energy level, and overall catalytic performance at the subnanometer level.

Tuning the Morphology and Chiroptical Properties of Discrete Gold Nanorods with Amino Acids.

The synthesis of discrete nanostructures with a strong, persistent, stable plasmonic circular dichroism (PCD) signal is challenging. We report a seed-mediated growth approach to obtain discrete Au nanorods with high and stable chiroptical responses (c-Au NRs) in the visible to near-IR region. The morphology of the c-Au NRs was governed by the concentration of l- or d-cysteine used. The amino acids encapsulated within the discrete gold nanostructure enhance their PCD signal, attributed to coupling of dipoles of chiral molecules with the near-field induced optical activity at the hot spots inside the c-Au NRs. The stability of the PCD signal and biocompatibility of c-Au NRs was improved by coating with silica or protein corona. Discrete c-Au NR@SiO2 with Janus or core-shell configurations retained their PCD signal even in organic solvents. A side-by-side assembly of c-Au NRs induced by l-glutathione led to further PCD signal enhancement, with anisotropic g factors as high as 0.048.

Tailored transition metal-doped nickel phosphide nanoparticles for the electrochemical oxygen evolution reaction (OER).

Foreign transition metals are doped into the hexagonal nickel phosphide structure through a simple and facile bottom-up wet-chemical synthesis process via stabilization with oleylamine, trioctylphosphine (TOP), and trioctylphosphine oxide (TOPO): the as-prepared transition metal-doped nickel phosphide nanoparticles show a high level of doping but create no significant distortion of the crystal structure and morphology against pristine nickel phosphide nanoparticles, which exhibit excellent activity in the electrochemical oxygen evolution reaction (OER), having overpotential as small as 330 mV at 20 mA cm-2 with a low Tafel slope value of 39 mV dec-1.

Ruthenium terpyridine complexes containing a pyrrole-tagged 2,2'-dipyridylamine ligand-synthesis, crystal structure, and electrochemistry.

Ruthenium(II) terpyridine complexes containing the pyrrole-tagged 2,2'-dipyridylamine ligand PPP (where PPP stands for N-(3-bis(2-pyridyl)aminopropyl)pyrrole with the general formula [Ru(tpy)(PPP)X](n+) (1, X = Cl(-); 2, X = H(2)O; 3, X = CH(3)CN; tpy = 2,2':6',2"-terpyridine) have been synthesized and characterized by (1)H NMR, IR, UV-vis, mass spectrometry, and elemental analysis. 1 and 2 have been structurally characterized by X-ray crystallography. Both 1 and 2 were successfully immobilized onto glassy carbon electrode via anodic oxidation of the pyrrole moiety on the PPP ligand to give stable and highly electroactive polymer films. Cyclic voltammetric studies of 1 in acetonitrile revealed a Ru(III)/Ru(II) couple at 0.4 V vs Cp(2)Fe(+/0) initially, but another redox couple resulting from chloride substitution by acetonitrile developed at E(1/2) = 0.82 V upon repetitive potential scan. This ligand substitution was induced by the acidic local environment caused by the release of protons during pyrrole polymerization. The electropolymerization of 2 in aqueous medium allowed the observation of the formation of Ru(IV)═O species in polypyrrole film. As the film grew thicker, the size of the Ru(III)/(/)Ru(II) couple (E(1/2) = 0.8 V vs SCE at pH 1) of poly[Ru(tpy)(PPP)(OH(2))](n+) increased accordingly, whereas the growth of the Ru(IV)/Ru(III) couple (E(1/2) = 0.89 V vs SCE at pH 1) leveled off after the film had reached a certain thickness. The Pourbaix diagram of the E(1/2) of the Ru(III) /Ru(II) and Ru(IV)/Ru(III) couples vs pH of the electrolyte medium has been obtained. The resulting poly[Ru(tpy)(PPP)(OH(2))](n+) film is electrocatalytically active toward the oxidation of benzyl alcohol.