Efficient photochemical water oxidation by a dinuclear molecular ruthenium complex

Mild-condition ammonia synthesis from N2 and H2 is a long-sought-after scientific goal and a practical need, especially for the intensively pursued “Green Ammonia” production using renewable H2. Under this context, there have been growing interests in the development of new catalysts for effectively catalyzing N2+H2 to NH3. Particular attention has been given to Ru-based catalysts because they are well known to be more active at lower temperatures and pressures than non-noble-metal based catalysts. Here, we demonstrate that a series of Ru complex hydrides An[RuHm], where A is alkali or alkaline earth metal, n= 2, 3 or 4 and m = 6 or 7, exhibit universal and high catalytic activities that far exceed the benchmark Ru metal catalysts under mild conditions. Detailed investigations on the ternary Ru complex hydride catalytic system disclose that the kinetic behaviors depend strongly on the identity of alkali or alkaline earth metal cations. In clear contrast to the closed packed Ru metal catalyst, the unique configuration and synergized scenario of the Ru complex hydride center prefer a non-dissociative mechanism for N2 activation and hydrogenation, which provides a new platform for the design and development of efficient NH3 synthesis catalysts.

Download Full-text

A New Dinuclear Ruthenium Complex as an Efficient Water Oxidation Catalyst

Inorganic Chemistry ◽

10.1021/ic802052u ◽

2009 ◽

Vol 48 (7) ◽

pp. 2717-2719 ◽

Cited By ~ 121

Author(s):

Yunhua Xu ◽

Torbjörn Åkermark ◽

Viktor Gyollai ◽

Dapeng Zou ◽

Lars Eriksson ◽

...

Keyword(s):

Water Oxidation ◽

Ruthenium Complex ◽

Oxidation Catalyst ◽

Dinuclear Ruthenium

Download Full-text

Oxygen Kinetic Isotope Effects upon Catalytic Water Oxidation by a Monomeric Ruthenium Complex

Inorganic Chemistry ◽

10.1021/ic202745n ◽

2012 ◽

Vol 51 (8) ◽

pp. 4722-4729 ◽

Cited By ~ 21

Author(s):

Alfredo M. Angeles-Boza ◽

Justine P. Roth

Keyword(s):

Water Oxidation ◽

Ruthenium Complex ◽

Isotope Effects ◽

Kinetic Isotope Effects ◽

Kinetic Isotope

Download Full-text

Ruthenium Complex Hydride Catalysts as a Platform for Ammonia Synthesis

10.26434/chemrxiv.14213711.v1 ◽

2021 ◽

Author(s):

Qianru Wang ◽

Jianping Guo ◽

Ping Chen

Keyword(s):

Alkaline Earth ◽

Ammonia Synthesis ◽

Ruthenium Complex ◽

Earth Metal ◽

Metal Catalyst ◽

Alkaline Earth Metal ◽

Dissociative Mechanism ◽

Complex Hydride ◽

Ru Complex ◽

Scientific Goal

Mild-condition ammonia synthesis from N2 and H2 is a long-sought-after scientific goal and a practical need, especially for the intensively pursued “Green Ammonia” production using renewable H2. Under this context, there have been growing interests in the development of new catalysts for effectively catalyzing N2+H2 to NH3. Particular attention has been given to Ru-based catalysts because they are well known to be more active at lower temperatures and pressures than non-noble-metal based catalysts. Here, we demonstrate that a series of Ru complex hydrides An[RuHm], where A is alkali or alkaline earth metal, n= 2, 3 or 4 and m = 6 or 7, exhibit universal and high catalytic activities that far exceed the benchmark Ru metal catalysts under mild conditions. Detailed investigations on the ternary Ru complex hydride catalytic system disclose that the kinetic behaviors depend strongly on the identity of alkali or alkaline earth metal cations. In clear contrast to the closed packed Ru metal catalyst, the unique configuration and synergized scenario of the Ru complex hydride center prefer a non-dissociative mechanism for N2 activation and hydrogenation, which provides a new platform for the design and development of efficient NH3 synthesis catalysts.

Download Full-text

Activity analysis of electrocatalytic water oxidation by trinuclear ruthenium complex on an Au particle matrix

Electrochimica Acta ◽

10.1016/s0013-4686(98)00379-x ◽

1999 ◽

Vol 44 (14) ◽

pp. 2493-2497 ◽

Cited By ~ 4

Author(s):

Masayuki Yagi ◽

Eriko Takano ◽

Masao Kaneko

Keyword(s):

Water Oxidation ◽

Ruthenium Complex ◽

Activity Analysis

Download Full-text

Basic Research of Water Photolysis Using Pyrochlore Oxides

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.388.297 ◽

2008 ◽

Vol 388 ◽

pp. 297-300 ◽

Cited By ~ 1

Author(s):

Naohisa Mori ◽

Yutori Tagoku ◽

Hidenobu Shiroishi ◽

Yoshinobu Saito ◽

Morihiro Saito ◽

...

Keyword(s):

Water Oxidation ◽

Ruthenium Complex ◽

Basic Research ◽

Catalyst System ◽

Oxidation Catalyst ◽

Complex Catalyst ◽

Proton Reduction ◽

Water Photolysis ◽

Pyrochlore Type ◽

Reduction Catalysts

Photocatalytic proton reduction and water oxidation have been studied in a tris(2,2’-bipyridyl)ruthenium complex-catalyst system. Pyrochlore-type oxides have been used as proton reduction catalysts with a sacrificial electron donor (Na2EDTA) at pH 7 and as water oxidation catalysts with a sacrificial electron acceptor (K2S2O8) at pH 3. Rate constants for the proton reduction were estimated on the basis of photochemical processes. Yb2Ru2O7-δ was found to be the most active catalyst for proton reduction and water oxidation catalyst in this system.

Download Full-text

The Effect of UV-Irradiation (under Short-Circuit Condition) on Dye-Sensitized Solar Cells Sensitized with a Ru-Complex Dye Functionalized with a (diphenylamino)Styryl-Thiophen Group

International Journal of Photoenergy ◽

10.1155/2009/471828 ◽

2009 ◽

Vol 2009 ◽

pp. 1-9 ◽

Cited By ~ 3

Author(s):

Kazuteru Nonomura ◽

Yunhua Xu ◽

Tannia Marinado ◽

Daniel P. Hagberg ◽

Rong Zhang ◽

...

Keyword(s):

Solar Cells ◽

Uv Irradiation ◽

Ruthenium Complex ◽

Short Circuit ◽

Dye Sensitized Solar Cells ◽

Dye Sensitized ◽

Ru Complex ◽

Redox Electrolyte ◽

Sensitized Solar Cells ◽

Short Circuit Condition

A new ruthenium complex, cis-di(thiocyanato)(2,2′-bipyridine-4,4′-dicarboxylic acid)(4,4′-bis(2-(5-(2-(4-diphenylaminophenyl)ethenyl)-thiophen-2-yl)ethenyl)-2,2′-bipyridine)ruthenium(II) (named E322) has been synthesized for use in dye-sensitized solar cells (DSCs). Higher extinction coefficient and a broader absorption compared to the standard Ru-dye, N719, were aimed. DSCs were fabricated with E322, and the efficiency was 0.12% initially. (4.06% for N719, as reference). The efficiency was enhanced to 1.83% by exposing the cell under simulated sunlight containing UV-irradiation at short-circuit condition. The reasons of this enhancement are (1) enhanceing electron injection from sensitizer toTiO2following a shift toward positive potentials of the conduction band ofTiO2by the adsorption of protons or cations from the sensitizer, or from the redox electrolyte and (2) improving the regeneration reaction of the oxidized dye by the redox electrolyte by the dissolution of aggregated dye from the surface ofTiO2following the treatment.

Download Full-text