Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation.

Stable metal nitrides (MN) are promising materials to fit the future "green" ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation.

Metamaterials are a new class of artificial materials that can achieve electromagnetic properties that do not occur naturally, and as such they can also be a new class of photocatalytic structures. We show that metal-based catalysts can achieve electromagnetic field amplification and broadband absorption by decoupling optical properties from the material composition as exemplified with a ZnO/Cu metamaterial surface comprising periodically arranged nanocubes. Through refractive index engineering close to the index of air, the metamaterial exhibits near-perfect 98% absorption. The combination of plasmonics and broadband absorption elevates the weak electric field intensities across the nonplasmonic absorption range. This feedback between optical excitation and plasmonic excitation dramatically enhances light-to-dark catalytic rates by up to a factor of 181 times, compared to a 3 times photoenhancement of ZnO/Cu nanoparticles or films, and with angular invariance. These results show that metamaterial catalysts can act as a singular light harvesting device that substantially enhances photocatalysis of important reactions.

Solar Urea: Towards a Sustainable Fertilizer Industry.

Urea, an agricultural fertilizer, nourishes humanity. The century-old Bosch-Meiser process provides the world's urea. It is multi-step, consumes enormous amounts of non-renewable energy, and has a large CO2 footprint. Thus, developing an eco-friendly synthesis for urea is a priority. Herein we report a single-step Pd/LTA-3A catalyzed synthesis of urea from CO2 and NH3 under ambient conditions powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH3 and providing the photothermal driving force for urea formation, while the absorption capacity of LTA-3A removes by-product H2 O to shift the equilibrium towards urea production. The solar urea conversion rate from NH3 and CO2 is 87 µmol g-1 h-1 . This advance represents a first step towards the use of solar energy in urea production. It provides insights into green fertilizer production, and inspires the vision of sustainable, modular plants for distributed production of urea on farms.

Linear End-On Coordination Modes of CO2.

The second case of linear end-on and evidence for an unprecedented bridging end-on coordination mode of CO2 have been discovered for vanadium aryloxide complexes of the tetradentate ligand system (ONNO)2- (ONNO=2,4-Me2 -2-(OH) C6 H2 CH2 ]2 N(CH2 )2 NMe2 ). The reaction of divalent (ONNO)VII (TMEDA) with CO2 and under the appropriate reaction conditions affords the trivalent (ONNO)VIII (OH)(η1 -CO2 ) resulting from an intermediate CO2 deoxygenation pathway followed by H-atom abstraction from the aromatic solvent, and CO2 fixation. In contrast, the reduction of trivalent (ONNO)VIII Cl(THF) with K, followed by exposure to CO2 in ethereal solvent, afforded the dinuclear [(ONNO)VII ]2 (µ, η1 -CO2 ).

Reaction of CO2 with a Vanadium(II) Aryl Oxide: Synergistic Activation of CO2 /Oxo Groups towards H-Atom Radical Abstraction.

Treatment of divalent (ONNO)V(TMEDA) (1; ONNO=[2,4-Me2 -2-(OH)C6 H2 CH2 ]2 N(CH2 )2 NMe2 ) with CO2 afforded [(ONNO)V]2 (µ-OH)(µ-formate) (2). Whereas the bridging hydroxo and formate groups both originated from CO2 , the H atoms present on the two residues were obtained through H-atom radical abstraction from the solvent. DFT calculations revealed an initially linear CO2 bonding mode, followed by deoxygenation, and highlighted a synergistic effect between the so-formed oxo group and an additional bridging CO2 residue in promoting radical behavior.

Radical Behavior of CO2 versus its Deoxygenation Promoted by Vanadium Aryloxide Complexes: How the Geometry of Intermediate CO2 -Adducts Determines the Reactivity.

The reactivity of carbon dioxide with vanadium(III) aryloxo complexes has been investigated. The formation of either carbon monoxide or incorporation into the ligand system with the ultimate formation of organic ester was observed depending on the overall electron donor ability of the ligand field. DFT calculations were carried out to investigate the proposed mechanism for carbon dioxide coordination and reduction.

Revisiting the behaviour of BiVO4 as a carbon dioxide reduction photo-catalyst.

Bismuth vanadate is a widely known photocatalyst for the hydro-reduction of CO2. In spite of the great appeal of such a catalytic system, problems arise due to deactivation of the catalyst with consequent low reaction yield. We have investigated the catalyst behavior during methanol production and have found that the catalyst irreversibly loses vanadium from the structure whilst depositing bismuth oxides on the surface of the catalyst. While catalyst activity can be restored upon heating, leaching of vanadium, leading in long term to catalyst decomposition, is unavoidable and irreversible.