Phong D. Tran

From Hydrogenases to Noble Metal–Free Catalytic Nanomaterials for H2 Production and Uptake

Electrolysis at Nickel One drawback of solar and wind power is the need for an efficient storage system to release accumulated energy when neither source is readily available (during still nights, for example). Hydrogen derived from electrolysis of water is potentially a useful medium for this purpose, but catalyzing the interconversion efficiently at large scale would currently require a substantial amount of the scarce precious metal platinum. An alternative approach would be to mimic natural enzymatic reactions, which accomplish the interconversion using hydrogenases that incorporate the more abundant metals iron and nickel. In this vein, Le Goff et al. (p. 1384; see the Perspective by Hambourger and Moore) have lightly modified a hydrogenase-inspired nickel complex in order to append it to a conductive carbon nanotube support. The resulting hybrid material shows promising catalytic efficiency for reversible aqueous electrolysis in a standard apparatus. A nickel electrocatalyst supported on carbon nanotubes shows promising activity for proton-hydrogen interconversion in water. Interconversion of water and hydrogen in unitized regenerative fuel cells is a promising energy storage framework for smoothing out the temporal fluctuations of solar and wind power. However, replacement of presently available platinum catalysts by lower-cost and more abundant materials is a requisite for this technology to become economically viable. Here, we show that the covalent attachment of a nickel bisdiphosphine–based mimic of the active site of hydrogenase enzymes onto multiwalled carbon nanotubes results in a high–surface area cathode material with high catalytic activity under the strongly acidic conditions required in proton exchange membrane technology. Hydrogen evolves from aqueous sulfuric acid solution with very low overvoltages (20 millivolts), and the catalyst exhibits exceptional stability (more than 100,000 turnovers). The same catalyst is also very efficient for hydrogen oxidation in this environment, exhibiting current densities similar to those observed for hydrogenase-based materials.

Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H 2 evolution under fully aqueous conditions

The viability of a hydrogen economy depends on the design of efficient catalytic systems based on earth-abundant elements. Innovative breakthroughs for hydrogen evolution based on molecular tetraimine cobalt compounds have appeared in the past decade. Here we show that such a diimine-dioxime cobalt catalyst can be grafted to the surface of a carbon nanotube electrode. The resulting electrocatalytic cathode material mediates H(2) generation (55,000 turnovers in seven hours) from fully aqueous solutions at low-to-medium overpotentials. This material is remarkably stable, which allows extensive cycling with preservation of the grafted molecular complex, as shown by electrochemical studies, X-ray photoelectron spectroscopy and scanning electron microscopy. This clearly indicates that grafting provides an increased stability to these cobalt catalysts, and suggests the possible application of these materials in the development of technological devices.

A cuprous oxide–reduced graphene oxide (Cu2O–rGO) composite photocatalyst for hydrogen generation : employing rGO as an electron acceptor to enhance the photocatalytic activity and stability of Cu2O

Photocorrosion, that causes rapid deactivation of Cu(2)O photocatalysts, was addressed by incorporating this oxide in a composite with reduced graphene oxide which acts as an electron acceptor to extract photogenerated electrons from Cu(2)O. Cu(2)O-rGO composite engineering also allows enhancing significantly photocatalytic activities of Cu(2)O for H(2) generation.

Noncovalent Modification of Carbon Nanotubes with Pyrene‐Functionalized Nickel Complexes: Carbon Monoxide Tolerant Catalysts for Hydrogen Evolution and Uptake

Hydrogen production through the reduction of water appears to be a very attractive solution for the long-term storage of renewable energy. However, economically viable processes require platinum-free catalysts, since this expensive and scarce metal is not a sustainable resource. We recently showed that the combination of a bioinspired molecular approach with nanochemical tools, through the covalent attachment of mimics 3] of the active site of hydrogenase enzymes onto carbon nanotubes (CNTs), results in a noblemetal-free electrocatalytic nanomaterial with low overpotential and exceptional stability for H2 evolution or uptake. [4,5] In this initial study, we used the electroreduction of a diazonium salt to decorate multiwalled carbon nanotubes (MWCNTs) deposited on the electrode support with a polyphenylene layer bearing amino groups. These amino groups were then used to attach an activated ester derivative [Ni(P2N Ar 2)2] 2+

Copper molybdenum sulfide: a new efficient electrocatalyst for hydrogen production from water

A new inorganic solid state electrocatalyst for the hydrogen evolution reaction (HER) is reported. Highly crystalline layered ternary sulfide copper-molybdenum-sulfide (Cu2MoS4) was prepared by a simple precipitation method from CuI and [MoS4]2− precursors. In aqueous solution and over a wide pH range (pH 0 to 7), this Cu2MoS4 showed very good catalytic activity for HER with an overvoltage requirement of only ca. 135 mV and an apparent exchange current density of 0.040 mA cm−2 (Tafel slope of ca. 95 mV per decade was found irrespective of the pH value). This Cu2MoS4 catalyst was found to be stable during electrocatalytic hydrogen generation. Therefore, it represents an attractive alternative to platinum.

Water electrolysis and photoelectrolysis on electrodes engineered using biological and bio-inspired molecular systems

Photoelectrocatalytic cells for water splitting should combine one or two photosensitive units with a water oxidation catalyst at the anode and a hydrogen evolution catalyst at the cathode. In this perspective article, we first show how a chemist can take the naturally occurring multi-electron catalysts for these two electro- and photochemical reactions, photosystem II and hydrogenases, as a source of inspiration for the design of original, efficient and robust molecular catalysts. The focus of this article is given to the immobilisation of these natural or bio-inspired catalysts onto conducting surfaces and the design of electrode and photoelectrode materials for hydrogen evolution/uptake and water oxidation.

From natural to artificial photosynthesis

Demand for energy is projected to increase at least twofold by mid-century relative to the present global consumption because of predicted population and economic growth. This demand could be met, in principle, from fossil energy resources, particularly coal. However, the cumulative nature of carbon dioxide (CO2) emissions demands that stabilizing the atmospheric CO2 levels to just twice their pre-anthropogenic values by mid-century will be extremely challenging, requiring invention, development and deployment of schemes for carbon-neutral energy production on a scale commensurate with, or larger than, the entire present-day energy supply from all sources combined. Among renewable and exploitable energy resources, nuclear fusion energy or solar energy are by far the largest. However, in both cases, technological breakthroughs are required with nuclear fusion being very difficult, if not impossible on the scale required. On the other hand, 1 h of sunlight falling on our planet is equivalent to all the energy consumed by humans in an entire year. If solar energy is to be a major primary energy source, then it must be stored and despatched on demand to the end user. An especially attractive approach is to store solar energy in the form of chemical bonds as occurs in natural photosynthesis. However, a technology is needed which has a year-round average conversion efficiency significantly higher than currently available by natural photosynthesis so as to reduce land-area requirements and to be independent of food production. Therefore, the scientific challenge is to construct an ‘artificial leaf’ able to efficiently capture and convert solar energy and then store it in the form of chemical bonds of a high-energy density fuel such as hydrogen while at the same time producing oxygen from water. Realistically, the efficiency target for such a technology must be 10 per cent or better. Here, we review the molecular details of the energy capturing reactions of natural photosynthesis, particularly the water-splitting reaction of photosystem II and the hydrogen-generating reaction of hydrogenases. We then follow on to describe how these two reactions are being mimicked in physico-chemical-based catalytic or electrocatalytic systems with the challenge of creating a large-scale robust and efficient artificial leaf technology.

A novel strategy for surface treatment on hematite photoanode for efficient water oxidation

In this paper, we report a novel strategy for surface treatment of hematite nanorods for efficient photo-driven water oxidation. This is the first report describing the growth of Sn treated hematite from α-FeOOH nanorod arrays in one step without substantially altering morphologies. With this treatment the photocurrent density increased from 1.24 for pristine hematite nanorods to 2.25 mA cm−2 at 1.23 V vs. RHE (i.e. 81% improvement). The increase in photocurrent density was also accompanied by improved incident-photon-to-current efficiencies and oxygen evolution. The photocurrent improvement is mainly attributed to a reduced electron–hole recombination at the hematite–electrolyte interface through the formation of FexSn1−xO4 layer at the hematite nanorod surface as shown by XPS, HRTEM, EDAX line scan analyses and PEC measurements.

In situ photo-assisted deposition of MoS2 electrocatalyst onto zinc cadmium sulphide nanoparticle surfaces to construct an efficient photocatalyst for hydrogen generation

We reported herein a facile and scalable preparation process for MoS(2)-decorated Zn(x)Cd(1-x)S hybrid photocatalysts for hydrogen generation. Zn(x)Cd(1-x)S nanopowder was first prepared from commercially available precursors employing a solution based process. MoS(2) hydrogen evolution reaction catalyst was then loaded onto the Zn(x)Cd(1-x)S nanopowder via a photo-assisted deposition process which employed mild conditions (room temperature, atmospheric pressure and visible light illumination). Thus, this process represents an important advantage in the large scale production of semiconductor/MoS(2) hybrid photocatalysts in comparison to the conventional method relying on thermal decomposition of (NH(4))(2)[MoS(4)] precursor at high temperature and under H(2)S pressure. The best Zn(0.2)Cd(0.8)S/MoS(2) 3% showed two hundred-and-ten times (210 times) faster hydrogen generation rate on visible light illumination compared with that obtained for un-treated Zn(0.2)Cd(0.8)S. That was the most impressive catalytic enhancement ever recorded for a semiconductor photocatalyst decorated with a noble metal free electrocatalyst.

Novel cobalt/nickel–tungsten-sulfide catalysts for electrocatalytic hydrogen generation from water

The potential of water (photo)electrolysis technology to provide hydrogen as a fuel on a large scale depends on how viable electrocatalysts for the water oxidation reaction (WOR) and the hydrogen evolution reaction (HER) are and whether they can be constructed from elements which are abundant in the Earths crust. Here we show that ternary sulfides of cobalt–tungsten and nickel–tungsten (MWSx where M is Co or Ni) are efficient and robust electrocatalysts for the HER in water over a wide pH range. These novel ternary sulfides were readily grown on a conducting electrode surface by employing a scalable electrodeposition process from aqueous solutions of [M(WS4)2]2−. In terms of HER activity, the MWSx catalysts represent attractive alternatives to platinum. Moreover, we show that the HER activity is governed by the nature of the metal M within M–S–W heterobimetallic sulfide centres, located in the WS2-like layered structure of MWSx. Our work provides structural and mechanistic keys to understand how HER activity is promoted in previously described nickel and cobalt-doped molybdenum and tungsten sulfide materials.