Recent Advances and Challenges of Electrocatalytic N2 Reduction to Ammonia.

Global ammonia production reached 175 million metric tons in 2016, 90% of which is produced from high purity N2 and H2 gases at high temperatures and pressures via the Haber-Bosch process. Reliance on natural gas for H2 production results in large energy consumption and CO2 emissions. Concerns of human-induced climate change are spurring an international scientific effort to explore new approaches to ammonia production and reduce its carbon footprint. Electrocatalytic N2 reduction to ammonia is an attractive alternative that can potentially enable ammonia synthesis under milder conditions in small-scale, distributed, and on-site electrolysis cells powered by renewable electricity generated from solar or wind sources. This review provides a comprehensive account of theoretical and experimental studies on electrochemical nitrogen fixation with a focus on the low selectivity for reduction of N2 to ammonia versus protons to H2. A detailed introduction to ammonia detection methods and the execution of control experiments is given as they are crucial to the accurate reporting of experimental findings. The main part of this review focuses on theoretical and experimental progress that has been achieved under a range of conditions. Finally, comments on current challenges and potential opportunities in this field are provided.

Shape-Controlled Synthesis of Luminescent Hemoglobin Capped Hollow Porous Platinum Nanoclusters and their Application to Catalytic Oxygen Reduction and Cancer Imaging.

Engineering hollow and porous platinum nanostructures using biomolecular templates is currently a significant focus for the enhancement of their facet-dependent optical, electronic, and electrocatalytic properties. However, remains a formidable challenge due to lack of appropriate biomolecules to have a structure-function relationship with nanocrystal facet development. Herein, human hemoglobin found to have facet-binding abilities that can control the morphology and optical properties of the platinum nanoclusters (Pt NCs) by regulation of the growth kinetics in alkaline media. Observations revealed the growth of unusual polyhedra by shape-directed nanocluster attachment along a certain orientation accompanied by Ostwald ripening and, in turn, yield well-dispersed hollow single-crystal nanotetrahedrons, which can easily self-aggregated and crystallized into porous and polycrystalline microspheres. The spontaneous, biobased organization of Pt NCs allow the intrinsic aggregation-induced emission (AIE) features in terms of the platinophilic interactions between Pt(II)-Hb complexes on the Pt(0) cores, thereby controlling the degree of aggregation and the luminescent intensity of Pt(0)@Pt(II)-Hb core-shell NCs. The Hb-Pt NCs exhibited high-performance electrocatalytic oxygen reduction providing a fundamental basis for outstanding catalytic enhancement of Hb-Pt catalysts based on morphology dependent and active site concentration for the four-electron reduction of oxygen. The as-prepared Hb-Pt NCs also exhibited high potential to use in cellular labeling and imaging thanks to the excellent photostability, chemical stability, and low cytotoxicity.

Cyclometalated heteronuclear Pt/Ag and Pt/Tl complexes: a structural and photophysical study.

To investigate the factors influencing the luminescent properties of polymetallic cycloplatinated complexes a detailed study of the photophysical and structural properties of the heteronuclear complexes [Pt2Me2(bhq)2(µ-dppy)2Ag2(µ-acetone)](BF4)2, 2, [PtMe(bhq)(dppy)Tl]PF6, 3, and [Pt2Me2(bhq)2(dppy)2Tl]PF6, 4, [bhq = benzo[h]quinoline, dppy = 2-(diphenylphosphino)pyridine] was conducted. Complexes 3 and 4 synthesized by the reaction of [PtMe(bhq)(dppy)], 1, with TlPF6 (1 or 1/2 equiv.) and stabilized by unsupported Pt-Tl bonds as revealed by multinuclear NMR spectroscopy and confirmed by X-ray crystallography for 3. DFT calculations for the previously reported butterfly Pt2Ag2 cluster 2 reveal that in the optimized geometry the bridging acetone molecule is removed and the metal core displays a planar-shaped geometry in which according to a QTAIM calculation and natural bond orbital (NBO) analysis the Ag···Ag metallophilic interaction is strengthened. In contrast to the precursor 1, which is only emissive in glassy solutions ((3)MLCT 485 nm), all 2-4 heteropolynuclear complexes display intense emissions in the solid state and in glassy solutions. Time-dependent density functional theory (TD-DFT) is used to elucidate the origin of the electronic transitions in the heteronuclear complexes 2 and 3. The low energy absorption and intense orange emission for cluster 2 (solid 77 K and glass) are attributed to metal-metal to ligand charge transfer (MM'LCT) with a minor L'LCT contribution. For 3 and 4 two different bands are developed: the high energy band (602-630 nm) observed for 4 at 77 K (solid, glass) and in diluted glasses for 3 is ascribed to emission from discrete Pt2Tl units of mixed (3)L'LCT/(3)LM'CT origin. However, the low energy band (670-690 nm) observed at room temperature (solid) for both complexes and also in concentrated glasses for 3 is assigned to (3)ππ excited states arising from intermolecular interactions.