Global energy consumption is projected to increase, even in the face of substantial declines in energy intensity, at least 2-fold by midcentury relative to the present because of population and economic growth. This demand could be met, in principle, from fossil energy resources, particularly coal. However, the cumulative nature of CO2 emissions in the atmosphere demands that holding atmospheric CO2 levels to even twice their preanthropogenic values by midcentury will require 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 energy resources, solar energy is by far the largest exploitable resource, providing more energy in 1 hour to the earth than all of the energy consumed by humans in an entire year. In view of the intermittency of insolation, if solar energy is to be a major primary energy source, it must be stored and dispatched on demand to the end user. An especially attractive approach is to store solar-converted energy in the form of chemical bonds, i.e., in a photosynthetic process at a year-round average efficiency significantly higher than current plants or algae, to reduce land-area requirements. Scientific challenges involved with this process include schemes to capture and convert solar energy and then store the energy in the form of chemical bonds, producing oxygen from water and a reduced fuel such as hydrogen, methane, methanol, or other hydrocarbon species.

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Powering the planet: Chemical challenges in solar energy utilization

BACKGROUND With a rising global population, increasing energy demands, and impending climate change, major concerns have been raised over the security of our energy future. Developing sustainable, fossil-free pathways to produce fuels and chemicals of global importance could play a major role in reducing carbon dioxide emissions while providing the feedstocks needed to make the products we use on a daily basis. One prospective goal is to develop electrochemical conversion processes that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable energy. Electrocatalysts play a key role in these energy conversion technologies because they increase the rate, efficiency, and selectivity of the chemical transformations involved. Today’s electrocatalysts, however, are inadequate. The grand challenge is to develop advanced electrocatalysts with the enhanced performance needed to enable widespread penetration of clean energy technologies. ADVANCES Over the past decade, substantial progress has been made in understanding several key electrochemical transformations, particularly those that involve water, hydrogen, and oxygen. The combination of theoretical and experimental studies working in concert has proven to be a successful strategy in this respect, yielding a framework to understand catalytic trends that can ultimately provide rational guidance toward the development of improved catalysts. Catalyst design strategies that aim to increase the number of active sites and/or increase the intrinsic activity of each active site have been successfully developed. The field of hydrogen evolution, for example, has seen important breakthroughs over the years in the development of highly active non–precious metal catalysts in acid. Notable advancements have also been made in the design of oxygen reduction and evolution catalysts, although there remains substantial room for improvement. The combination of theory and experiment elucidates the remaining challenges in developing further improved catalysts, often involving scaling relations among reactive intermediates. This understanding serves as an initial platform to design strategies to circumvent technical obstacles, opening up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions. OUTLOOK A systematic framework of combining theory and experiment in electrocatalysis helps to uncover broader governing principles that can be used to understand a wide variety of electrochemical transformations. These principles can be applied to other emerging and promising clean energy reactions, including hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, among others. Although current paradigms for catalyst development have been helpful to date, a number of challenges need to be successfully addressed in order to achieve major breakthroughs. One important frontier, for example, is the development of both experimental and computational methods that can rapidly elucidate reaction mechanisms on broad classes of materials and in a wide range of operating conditions (e.g., pH, solvent, electrolyte). Such efforts would build on current frameworks for understanding catalysis to provide the deeper insights needed to fine-tune catalyst properties in an optimal manner. The long-term goal is to continue improving the activity and selectivity of these catalysts in order to realize the prospects of using renewable energy to provide the fuels and chemicals that we need for a sustainable energy future.

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Combining theory and experiment in electrocatalysis: Insights into materials design

Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

Noble metal-free hydrogen evolution catalysts for water splitting

We present a new local density functional, called M06-L, for main-group and transition element thermochemistry, thermochemical kinetics, and noncovalent interactions. The functional is designed to capture the main dependence of the exchange-correlation energy on local spin density, spin density gradient, and spin kinetic energy density, and it is parametrized to satisfy the uniform-electron-gas limit and to have good performance for both main-group chemistry and transition metal chemistry. The M06-L functional and 14 other functionals have been comparatively assessed against 22 energetic databases. Among the tested functionals, which include the popular B3LYP, BLYP, and BP86 functionals as well as our previous M05 functional, the M06-L functional gives the best overall performance for a combination of main-group thermochemistry, thermochemical kinetics, and organometallic, inorganometallic, biological, and noncovalent interactions. It also does very well for predicting geometries and vibrational frequencies. Because of the computational advantages of local functionals, the present functional should be very useful for many applications in chemistry, especially for simulations on moderate-sized and large systems and when long time scales must be addressed. © 2006 American Institute of Physics. DOI: 10.1063/1.2370993

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A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions.

There is still an ongoing effort to search for sustainable, clean and highly efficient energy generation to satisfy the energy needs of modern society. Among various advanced technologies, electrocatalysis for the oxygen evolution reaction (OER) plays a key role and numerous new electrocatalysts have been developed to improve the efficiency of gas evolution. Along the way, enormous effort has been devoted to finding high-performance electrocatalysts, which has also stimulated the invention of new techniques to investigate the properties of materials or the fundamental mechanism of the OER. This accumulated knowledge not only establishes the foundation of the mechanism of the OER, but also points out the important criteria for a good electrocatalyst based on a variety of studies. Even though it may be difficult to include all cases, the aim of this review is to inspect the current progress and offer a comprehensive insight toward the OER. This review begins with examining the theoretical principles of electrode kinetics and some measurement criteria for achieving a fair evaluation among the catalysts. The second part of this review acquaints some materials for performing OER activity, in which the metal oxide materials build the basis of OER mechanism while non-oxide materials exhibit greatly promising performance toward overall water-splitting. Attention of this review is also paid to in situ approaches to electrocatalytic behavior during OER, and this information is crucial and can provide efficient strategies to design perfect electrocatalysts for OER. Finally, the OER mechanism from the perspective of both recent experimental and theoretical investigations is discussed, as well as probable strategies for improving OER performance with regards to future developments.

Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives

Dimolybdenum–μ-cyanide complexes supported by N - tert -butylanilide ligation: in pursuit of cyanide reductive cleavage

Heterobimetallic NiZn complexes featuring metal centers in distinct coordination environments have been synthesized using diimine–dioxime ligands as binucleating scaffolds. A tetramethylfuran-containing ligand derivative enables a stable one-electron-reduced S = 1/2 species to be accessed using Cp2Co as a chemical reductant. The resulting pseudo-square planar complex exhibits spectroscopic and crystallographic characteristics of a ligand-centered radical bound to a Ni(II) center. Upon coordination of a π-acidic ligand such as PPh3, however, a five-coordinate Ni(I) metalloradical is formed. The electronic structures of these reduced species provide insight into the subtle effects of ligand structure on the potential and reversibility of the NiII/I couple for complexes of redox-active tetraazamacrocycles.

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Access to formally Ni(I) states in a heterobimetallic NiZn system

Nitrogenase enzymes mediate the six-electron reductive cleavage of cyanide to CH_4 and NH_3. Herein we demonstrate for the first time the liberation of CH_4 and NH_3 from a well-defined iron cyanide coordination complex, [SiP^(iPr)_3]Fe(CN) (where [SiP^(iPr)_3] represents a tris(phosphine)silyl ligand), on exposure to proton and electron equivalents. [SiP^(iPr)_3]Fe(CN) additionally serves as a useful entry point to rare examples of terminally-bound Fe(CNH) and Fe(CNH_2) species that, in accord with preliminary mechanistic studies, are plausible intermediates of the cyanide reductive protonation to generate CH_4 and NH_3. Comparative studies with a related [SiP^(iPr)_3]Fe(CNMe_2) complex suggests the possibility of multiple, competing mechanisms for cyanide activation and reduction.

Proton‐Coupled Reduction of an Iron Cyanide Complex to Methane and Ammonia

Terminal NiIII hydrides are proposed intermediates in proton reduction catalyzed by both molecular electrocatalysts and metalloenzymes, but well-defined examples of paramagnetic nickel hydride comp...

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H2 Evolution from a Thiolate-Bound Ni(III) Hydride.

The activity of nitrogenase enzymes, which catalyze the conversion of atmospheric dinitrogen to bioavailable ammonia, is most commonly assayed by the reduction of acetylene gas to ethylene. Despite the practical importance of acetylene as a substrate, little is known concerning its binding or activation in the iron-rich active site. "Fischer-Tropsch" type coupling of non-native C1 substrates to higher-order C≥2 products is also known for nitrogenase, though potential metal-carbon multiply bonded intermediates remain underexplored. Here we report the activation of acetylene gas at a mononuclear tris(phosphino)silyl-iron center, (SiP3)Fe, to give Fe(I) and Fe(II) side-on adducts, including S = 1/2 FeI(η2-HCCH); the latter is characterized by pulse EPR spectroscopy and DFT calculations. Reductive protonation reactions with these compounds converge at stable examples of unusual, formally iron(IV) and iron(V) carbyne complexes, as in diamagnetic (SiP3)Fe≡CCH3 and the paramagnetic cation S = 1/2 [(SiP3)Fe≡CCH3]+. Both alkylcarbyne compounds possess short Fe-C triple bonds (approximately 1.7 A) trans to the anchoring silane. Pulse EPR experiments, X-band ENDOR and HYSCORE, reveal delocalization of the iron-based spin onto the α-carbyne nucleus in carbon p-orbitals. Furthermore, isotropic coupling of the distal β-CH3 protons with iron indicates hyperconjugation with the spin/hole character on the Fe≡CCH3 unit. The electronic structures of (SiP3)Fe≡CCH3 and [(SiP3)Fe≡CCH3]+ are discussed in comparison to previously characterized, but heterosubstituted, iron carbynes, as well as a hypothetical nitride species, (SiP3)Fe≡N. Such comparisons are germane to the consideration of formally high-valent, multiply bonded Fe≡C and/or Fe≡N intermediates in synthetic or biological catalysis by iron.

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Jonas C. Peters

Papers

Dimolybdenum–μ-cyanide complexes supported by N - tert -butylanilide ligation: in pursuit of cyanide reductive cleavage

Access to formally Ni(I) states in a heterobimetallic NiZn system

Proton‐Coupled Reduction of an Iron Cyanide Complex to Methane and Ammonia

H2 Evolution from a Thiolate-Bound Ni(III) Hydride.

Mononuclear Fe(I) and Fe(II) Acetylene Adducts and their Reductive Protonation to Terminal Fe(IV) and Fe(V) Carbynes