Zuofeng Chen

Metal Nanowire Networks: The Next Generation of Transparent Conductors

There is an ongoing drive to replace the most common transparent conductor, indium tin oxide (ITO), with a material that gives comparable performance, but can be coated from solution at speeds orders of magnitude faster than the sputtering processes used to deposit ITO. Metal nanowires are currently the only alternative to ITO that meets these requirements. This Progress Report summarizes recent advances toward understanding the relationship between the structure of metal nanowires, the electrical and optical properties of metal nanowires, and the properties of a network of metal nanowires. Using the structure-property relationship of metal nanowire networks as a roadmap, this Progress Report describes different synthetic strategies to produce metal nanowires with the desired properties. Practical aspects of processing metal nanowires into high-performance transparent conducting films are discussed, as well as the use of nanowire films in a variety of applications.

Catalytic Water Oxidation by Single-Site Ruthenium Catalysts

A series of monomeric ruthenium polypyridyl complexes have been synthesized and characterized, and their performance as water oxidation catalysts has been evaluated. The diversity of ligand environments and how they influence rates and reaction thermodynamics create a platform for catalyst design with controllable reactivity based on ligand variations.

Concerted O atom–proton transfer in the O—O bond forming step in water oxidation

As the terminal step in photosystem II, and a potential half-reaction for artificial photosynthesis, water oxidation (2H2O → O2 + 4e- + 4H+) is key, but it imposes a significant mechanistic challenge with requirements for both 4e-/4H+ loss and O—O bond formation. Significant progress in water oxidation catalysis has been achieved recently by use of single-site Ru metal complex catalysts such as [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2′-bipyridine]. When oxidized from to RuV = O3+, these complexes undergo O—O bond formation by O-atom attack on a H2O molecule, which is often the rate-limiting step. Microscopic details of O—O bond formation have been explored by quantum mechanical/molecular mechanical (QM/MM) simulations the results of which provide detailed insight into mechanism and a strategy for enhancing catalytic rates. It utilizes added bases as proton acceptors and concerted atom–proton transfer (APT) with O-atom transfer to the O atom of a water molecule in concert with proton transfer to the base (B). Base catalyzed APT reactivity in water oxidation is observed both in solution and on the surfaces of oxide electrodes derivatized by attached phosphonated metal complex catalysts. These results have important implications for catalytic, electrocatalytic, and photoelectrocatalytic water oxidation.

Copper(II) Catalysis of Water Oxidation

Copper leads to a breakup: simple Cu(II) salts are shown to be highly reactive as water oxidation electrocatalysts in neutral to weakly basic aqueous buffer solutions of CO(2)/HCO(3)(-)/CO(3)(2-) or HPO(4)(2-)/PO(4)(3-). Coordination to the buffer anions under these conditions prevents the precipitation of Cu(OH)(2), CuCO(3), or Cu(3)(PO(4))(2) and appears to stabilize higher oxidation states of copper.

Selective Electrocatalytic Reduction of CO2 to Formate by Water-Stable Iridium Dihydride Pincer Complexes

Iridium dihydride complexes supported by PCP-type pincer ligands rapidly insert CO(2) to yield κ(2)-formate monohydride products in THF. In acetonitrile/water mixtures, these complexes become efficient and selective catalysts for electrocatalytic reduction of CO(2) to formate. Electrochemical and NMR spectroscopic studies have provided mechanistic details and structures of key intermediates.

Copper as a Robust and Transparent Electrocatalyst for Water Oxidation

Copper metal is in theory a viable oxidative electrocatalyst based on surface oxidation to Cu(III) and/or Cu(IV) , but its use in water oxidation has been impeded by anodic corrosion. The in situ formation of an efficient interfacial oxygen-evolving Cu catalyst from Cu(II) in concentrated carbonate solutions is presented. The catalyst necessitates use of dissolved Cu(II) and accesses the higher oxidation states prior to decompostion to form an active surface film, which is limited by solution conditions. This observation and restriction led to the exploration of ways to use surface-protected Cu metal as a robust electrocatalyst for water oxidation. Formation of a compact film of CuO on Cu surface prevents anodic corrosion and results in sustained catalytic water oxidation. The Cu/CuO surface stabilization was also applied to Cu nanowire films, which are transparent and flexible electrocatalysts for water oxidation and are an attractive alternative to ITO-supported catalysts for photoelectrochemical applications.

Making solar fuels by artificial photosynthesis

In order for solar energy to serve as a primary energy source, it must be paired with energy storage on a massive scale. At this scale, solar fuels and energy storage in chemical bonds is the only practical approach. Solar fuels are produced in massive amounts by photosynthesis with the reduction of CO2 by water to give carbohydrates but efficiencies are low. In photosystem II (PSII), the oxygen-producing site for photosynthesis, light absorption and sensitization trigger a cascade of coupled electron-proton transfer events with time scales ranging from picoseconds to microseconds. Oxidative equivalents are built up at the oxygen evolving complex (OEC) for water oxidation by the Kok cycle. A systematic approach to artificial photo-synthesis is available based on a “modular approach” in which the separate functions of a final device are studied separately, maximized for rates and stability, and used as modules in constructing integrated devices based on molecular assemblies, nanoscale arrays, self-assembled monolayers, etc. Considerable simplification is available by adopting a “dye-sensitized photoelectrosynthesis cell” (DSPEC) approach inspired by dye-sensitized solar cells (DSSCs). Water oxidation catalysis is a key feature, and significant progress has been made in developing a single-site solution and surface catalysts based on polypyridyl complexes of Ru. In this series, ligand variations can be used to tune redox potentials and reactivity over a wide range. Water oxidation electrocatalysis has been extended to chromophore-catalyst assemblies for both water oxidation and DSPEC applications.

The role of proton coupled electron transfer in water oxidation

Water oxidation is a key half reaction in energy conversion schemes based on solar fuels and targets such as light driven water splitting or carbon dioxide reduction into CO, other oxygenates, or hydrocarbons. Carrying out these reactions at rates that exceed the rate of solar insolation for the extended periods of time required for useful applications presents a major challenge. Water oxidation is the key “other” half reaction in these schemes and it is dominated by PCET given its multi-electron, multi-proton character, 2H2O → O2 + 4e− + 4H+. Identification of PCET was an offshoot of experiments designed to investigate energy conversion by electron transfer quenching of molecular excited states. The concepts “redox potential leveling” and concerted electron–proton transfer came from measurements on stepwise oxidation of cis-RuII(bpy)2(py)(OH2)2+ to RuIV(bpy)2(py)(O)2+. The Ru “blue dimer”, cis,cis-(bpy)2(H2O)RuORu(OH2)(bpy)24+, was the first designed catalyst for water oxidation. It undergoes oxidative activation by PCET to give the transient (bpy)2(O)RuVORuV(O)(bpy)24+, O-atom attack on water to give a peroxidic intermediate, and further oxidation and O2 release. More recently, a class of single site water oxidation catalysts has been identified, e.g., Ru(tpy)(bpm)(OH2)2+ (tpy is 2,2′:6′,2′′-terpyridine; bpm is 2,2′-bipyrimidine). They undergo stepwise PCET oxidation to RuIV=O2+ or RuV(O)3+ followed by O-atom transfer with formation of peroxidic intermediates which undergo further oxidation and O2 release. PCET plays a key role in the three zones of water oxidation reactivity: oxidative activation, O⋯O bond formation, oxidation and O2 release from peroxidic intermediates. Similar schemes have been identified for electrocatalytic water oxidation on oxide electrode surfaces based on phosphonated derivatives such as [Ru(Mebimpy)(4,4′-(PO3H2CH2)2bpy)(OH2)]2+. A PCET barrier to RuIII–OH2+ → RuIV=O2+ oxidation arises from the large difference in pKa values between RuIII–OH2+ and RuIV(OH)3+. On oxide surfaces this oxidation occurs by multiple pathways. Kinetic, mechanistic, and DFT results on single site catalysts reveal a new pathway for the O⋯O bond forming step (Atom-Proton Transfer, APT), significant rate enhancements by added proton acceptor bases, and accelerated water oxidation in propylene carbonate as solvent with water added as a stoichiometric reagent. Lessons learned about water oxidation and the role of PCET and concerted pathways appear to have direct relevance for water oxidation in Photosystem II (PSII) with PSII a spectacular example of PCET in action. This includes a key role for Multiple Site-Electron Proton Transfer in oxidative activation of the Oxygen Evolving Complex (OEC) in the S0 → S1 transition in the Kok cycle.

Single-Site Copper(II) Water Oxidation Electrocatalysis: Rate Enhancements with HPO42− as a Proton Acceptor at pH 8†

The complex Cu(II)(Py3P) (1) is an electrocatalyst for water oxidation to dioxygen in H2PO4(-)/HPO4(2-) buffered aqueous solutions. Controlled potential electrolysis experiments with 1 at pH 8.0 at an applied potential of 1.40 V versus the normal hydrogen electrode resulted in the formation of dioxygen (84% Faradaic yield) through multiple catalyst turnovers with minimal catalyst deactivation. The results of an electrochemical kinetics study point to a single-site mechanism for water oxidation catalysis with involvement of phosphate buffer anions either through atom-proton transfer in a rate-limiting O-O bond-forming step with HPO4(2-) as the acceptor base or by concerted electron-proton transfer with electron transfer to the electrode and proton transfer to the HPO4(2-) base.

Application of High Surface Area Tin-Doped Indium Oxide Nanoparticle Films as Transparent Conducting Electrodes

Metal complex derivatized, optically transparent nanoparticle films of Sn(IV)-doped In(2)O(3) (nanoITO) undergo facile interfacial electron transfer allowing for rapid, potential controlled color changes, direct spectral (rather than current) monitoring of voltammograms, and multilayer catalysis of water oxidation.