CuO nanostructures: Synthesis, characterization, growth mechanisms, fundamental properties, and applications

and Perspectives Sophie Carenco,†,‡,§,∥,⊥ David Portehault,*,†,‡,§ Ced́ric Boissier̀e,†,‡,§ Nicolas Meźailles, and Cleḿent Sanchez*,†,‡,§ †Chimie de la Matier̀e Condenseé de Paris, UPMC Univ Paris 06, UMR 7574, Colleg̀e de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France ‡Chimie de la Matier̀e Condenseé de Paris, CNRS, UMR 77574, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Chimie de la Matier̀e Condenseé de Paris, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Laboratory Heteroelements and Coordination, Chemistry Department, Ecole Polytechnique, CNRS-UMR 7653, Palaiseau, France

Nanoscaled metal borides and phosphides: recent developments and perspectives

This article reviews the progress made in the past 5 years in the field of direct and non-enzymatic electrochemical sensing of glucose. Following a brief discussion of the merits and limitations of enzymatic glucose sensors, we discuss the history of unraveling the mechanism of direct oxidation of glucose and theories of non-enzymatic electrocatalysis. We then review non-enzymatic glucose electrodes based on the use of the metals platinum, gold, nickel, copper, of alloys and bimetals, of carbon materials (including graphene and graphene-based composites), and of metal-metal oxides and layered double hydroxides. This review contains more than 200 refs.

Non-enzymatic electrochemical sensing of glucose

Low-cost and resourceful transition metal phosphides (TMPs) have gradually received wide acceptance in the energy industry through exhibiting comparable catalytic activity and long-term stability to traditional catalysts (e.g., Pt/C, LiCoO2, LiFePO4, etc.). With the emergence of the research hotspot of TMPs, probing their mechanism of catalytic energy conversion and storage inspired by the superb structure of metal-phosphorus chelate is of great significance. To this end, recent developments in TMPs with various crystal structures and morphologies have attracted much attention. The design of TMPs ranging from the choice of different transition metals to phosphorus sources has been intensively explored. This research has indicated that multidimensional morphologies of TMPs prominently enrich the patterns of charge storage and electron transportation, and ultra-nanoscaled TMPs obtained by multiple tools and techniques might challenge the threshold of electrocatalytic reactions. Here, recent developments in synthetic strategies of TMPs from different precursors are classified. The underlying mechanism between the structural and crystallographic characteristics and the tuned properties of TMPs in energy applications is also presented. Additionally, the key trends in structure and morphology characterization of TMPs are highlighted. Future perspectives on the challenges and opportunities facing TMPs catalysts are thereby proposed.

Earth-Rich Transition Metal Phosphide for Energy Conversion and Storage

The coordination chemistry of white phosphorus is nowadays a mature discipline, which during the last four decades has reached a deep understanding of the mechanisms governing the metal-mediated activation of this unique and highly reactive molecule. The birth certificate of this story dates back to 1970 when the synthesis of [RhCl(PPh3)2(η-P4)] together with other rhodium and iridium species was reported by Ginsberg and Lindsell as a short communication in Transactions of the New York Academy of Sciences.1,2 Immediately, this seminal discovery motivated intense research activity worldwide. Worth mentioning among the pioneers in this area are the groups led by Markó in Veszprem, Hungary; Dahl in Madison, Wisconsin, U.S.A.; and Sacconi in Florence, Italy. While the first two demonstrated that fragments deriving from P4 degradation could be stabilized as ligands in the coordination sphere of cobalt carbonyl3 and cyclopentadienyl derivatives,4 Sacconi first succeeded in coordinating the intact tetrahedral P4 molecule to a metal,5 obtaining the Ni(0) complex [(κ-P,P,P-NP3)Ni(ηP4)], and in fully characterizing a vast family of cyclo-P3 late transition metal derivatives spanning from iron to osmium.6 In the following decade, the development of the isolobal concept7 and its application to organometallic and main group chemistry paved the way to the synthesis of an incredible variety of polyphosphorus architectures where CH, CH2, and CH3 fragments in acyclic and cyclic hydrocarbons could be formally replaced by naked P atoms and substituted PH and PH2 units, respectively. Spectacular examples of organometallic phosphorus topologies ruled by the isolobal relationship can be found in the systematic work done in Kaiserslautern by Scherer and his co-workers who applied the isolobal P T C-H relation to the synthesis of a myriad of polycyclic phosphorus species mimicking benzene and other arenes. Landmarks in this area were the discovery of the cyclo-P6 ligand stabilized as internal layer in the triple-decker dimolybdenum complex [{Cp*Mo}2(μ,η-P6)] and the pentaphosphaferrocene derivative [{Cp*Fe}(η-P5)]. These species, within the loose boundaries of the isolobal concept, may be considered as the all-phosphorus analogues of benzene and cyclopentadienyl anion, respectively. The intriguing analogy between hydrocarbon species and organophosphorus compounds has been reviewed in the successful book “Phosphorus: The Carbon Copy” published by Wiley in 1998.10 In the last two decades, several reviews have also appeared covering different aspects of transition metalmediated white phosphorus activation. These include specific surveys addressing the formation of P-H11 and P-C species12 as well as some general reviews targeting the synthesis and the characterization of transition metal complexes incorporating naked phosphorus atoms and units as ligands.13-17 The importance of studying the coordination chemistry of elemental phosphorus by late (and early) transition metal complexes also stems from the need to replace the current technology for the production of organophosphorus derivatives. This reaction, which is of great industrial relevance, is still based on the chlorination of white phosphorus followed by the reaction of PCl3, PCl5, or POCl3 with the † This contribution is dedicated to our colleague and friend Prof. Piero Stoppioni on occasion of his 65th birthday and in recognition of his outstanding achievements in the field of white phosphorus activation. ‡ Note: In figures showing X-ray crystal structures, H atoms are generally omitted for clarity unless specified. * To whom correspondence should be addressed. E-mail: mperuzzini@ iccom.cnr.it. Chem. Rev. 2010, 110, 4178–4235 4178

P4 Activation by Late-Transition Metal Complexes†‡

Porous cuprous oxide microcubes for non-enzymatic amperometric hydrogen peroxide and glucose sensing

Preparation, conversion, and comparison of the photocatalytic property of Cd(OH)2, CdO, CdS and CdSe

Urchin-like CuO microspheres: Synthesis, characterization, and properties

Hydrothermal synthesis of Ni12P5 hollow microspheres, characterization and photocatalytic degradation property

In this paper we report an in situ template route for the synthesis of porous Ni12P5 superstructures through an improved hydrothermal synthesis strategy in the presence of a high concentration of Co2+ ions. The phase and morphology of the as-prepared product were characterized by means of powder X-ray diffraction (XRD), energy dispersive spectrometry (EDS), selected area electron diffraction (SAED), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Research showed that Co2+ ions in the system could significantly tune the shape and size of Ni12P5 and had a profound effect on the yield of Ni12P5. A possible growth mechanism was proposed based on the experimental results. Furthermore, the as-prepared porous Ni12P5 superstructures showed good adsorption capacities for Pb2+ and Cd2+ ions in water, and could strongly degrade some organic dyes such as pyronine B under irradiation of 254 nm UV light, indicating that the as-prepared product has potential applications in environmental treatments.

Jun Li

Papers

Porous cuprous oxide microcubes for non-enzymatic amperometric hydrogen peroxide and glucose sensing

Preparation, conversion, and comparison of the photocatalytic property of Cd(OH)2, CdO, CdS and CdSe

Urchin-like CuO microspheres: Synthesis, characterization, and properties

Hydrothermal synthesis of Ni12P5 hollow microspheres, characterization and photocatalytic degradation property

In situ template route for synthesis of porous Ni12P5 superstructures and their applications in environmental treatments