Urea, an agricultural fertilizer, nourishes humanity. The century-old Bosch-Meiser process provides the worlds urea. It is multi-step, consumes enormous amounts of nonrenewable energy, and has a large CO 2 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 CO 2 and NH 3 under ambient conditions powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH 3 and providing the photothermal driving force for urea formation, while the absorption capacity of LTA-3A removes by-product H 2 O to shift the equilibrium towards urea production. The solar urea conversion rate from NH 3 and CO 2 is 87 mmol g À1 h À1 . 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.Humans and animals excrete excess nitrogen in the form of urea. Historically, urea was the first naturally occurring organic compound to be synthesized by Friedrich Wçhler in 1828. Surprisingly at the time, he made all-organic urea by a thermally induced reconstruction of an all-inorganic compound, ammonium cyanate, connecting the fields of organic and inorganic chemistry.

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 H2O 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.

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.

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

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 nearperfect 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.