Light-driven nitrogen fixation routes for green ammonia production.

The global goal for decarbonization of the energy sector and the chemical industry could become a reality by a massive increase in renewable-based technologies. For this clean energy transition, the versatile green ammonia may play a key role in the future as a fossil-free fertilizer, long-term energy storage medium, chemical feedstock, and clean burning fuel for transportation and decentralized power generation. The high energy-intensive industrial ammonia production has triggered researchers to look for a step change in new synthetic approaches powered by renewable energies.

A Multimetal Approach for the Reticulation of Iridium into Metal-Organic Framework Building Units.

Noble metal elements are ubiquitous in our everyday life, from medical applications to electronic devices and synthetic chemistry. Iridium is one of the least abundant elements, and despite its scarcity, it remains essential for efficient and active catalytic processes. Consequently, the development of heterogeneous catalysts with the presence of active iridium sites is of enormous interest as it leads to the improvement of their recyclability and reusability.

Tuning (Photo)Electronic Properties of an Electron Deficient Porous Polymer via n-Doping with Tetrathiafulvalene.

Charge-transfer complex formation within the pores of porous polymers is an efficient way to tune their electronical properties. Introduction of electron accepting guests to the electron donating hosts to conduct their p-doping is intensively studied in this context. However, the vice versa scenario, n-doping by treating the electron deficient (i.

Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation.

Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption.

Regioselectivity in Pyrene-Templated Polymerization Using MOFs as 1D Porous Scaffolds.

Physicochemical properties of polymers strongly depend on the arrangement and distribution of attached monomers. Templated polymerization using porous crystalline materials appears as a promising route to gain control on the process. Thus, we demonstrate here the potential of metal-organic frameworks as scaffolds with a versatile and very regular porosity, well adapted for the regioselective oxidative polymerization of pyrene.

An anthraquinone-based bismuth-iron metal-organic framework as an efficient photoanode in photoelectrochemical cells.

Metal-organic frameworks (MOFs) are appealing candidate materials to design new photoelectrodes for use in solar energy conversion because of their modular nature and chemical versatility. However, to date there are few examples of MOFs that can be directly used as photoelectrodes, for which they must be able to afford charge separation upon light absorption, and promote the catalytic dissociation of water molecules, while maintaining structural integrity. Here, we have explored the use of the organic linker anthraquinone-2, 6-disulfonate (2, 6-AQDS) for the preparation of MOFs to be used as photoanodes.

Hydrogen-Induced Reduction Improves the Photoelectrocatalytic Performance of Titania.

One of the main challenges to expand the use of titanium dioxide (titania) as a photocatalyst is related to its large band gap energy and the lack of an atomic scale description of the reduction mechanisms that may tailor the photocatalytic properties. We show that rutile TiO single crystals annealed in the presence of atomic hydrogen experience a strong reduction and structural rearrangement, yielding a material that exhibits enhanced light absorption, which extends from the ultraviolet to the near-infrared (NIR) spectral range, and improved photoelectrocatalytic performance. We demonstrate that both magnitudes behave oppositely: heavy/mild plasma reduction treatments lead to large/negligible spectral absorption changes and poor/enhanced (×10) photoelectrocatalytic performance, as judged from the higher photocurrent.

Correction to "Iterative Dual-Metal and Energy Transfer Catalysis Enables Stereodivergence in Alkyne Difunctionalization: Carboboration as Case Study".

[This corrects the article DOI: 10.1021/acscatal.3c03570.

Iterative Dual-Metal and Energy Transfer Catalysis Enables Stereodivergence in Alkyne Difunctionalization: Carboboration as Case Study.

Stereochemically defined tetrasubstituted olefins are widespread structural elements of organic molecules and key intermediates in organic synthesis. However, flexible methods enabling stereodivergent access to and isomers of fully substituted alkenes from a common precursor represent a significant challenge and are actively sought after in catalysis, especially those amenable to complex multifunctional molecules. Herein, we demonstrate that iterative dual-metal and energy transfer catalysis constitutes a unique platform for achieving stereodivergence in the difunctionalization of internal alkynes.

Light-Driven Nitrogen Fixation to Ammonia over Aqueous-Dispersed Mo-Doped TiO Colloidal Nanocrystals.

Photocatalytic nitrogen fixation to ammonia and nitrates holds great promise as a sustainable route powered by solar energy and fed with renewable energy resources (N and HO). This technology is currently under deep investigation to overcome the limited efficiency of the process. The rational design of efficient and robust photocatalysts is crucial to boost the photocatalytic performance.

Impact of NiCoO/SrTiO p-n Heterojunctions on the Interface of Photoelectrochemical Water Oxidation.

Forming semiconductor heterojunctions is a promising strategy to boost the efficiency of solar-driven photoelectrochemical (PEC) water splitting by accelerating the separation and transport of photogenerated charge carriers via an interfacial electric field. However, there is limited research considering the influence of electrolytes on the band alignment of the heterojunction under PEC conditions. In this work, we use a single crystal NiCoO/SrTiO (NCO/STO) heterojunction with atomic-precision controlled thickness as a model photoelectrode to study the band structure modulations upon getting in contact with the electrolyte and the correlation with the PEC activity.

Synergistic binding sites in a metal-organic framework for the optical sensing of nitrogen dioxide.

Luminescent metal-organic frameworks are an emerging class of optical sensors, able to capture and detect toxic gases. Herein, we report the incorporation of synergistic binding sites in MOF-808 through post-synthetic modification with copper for optical sensing of NO at remarkably low concentrations. Computational modelling and advanced synchrotron characterization tools are applied to elucidate the atomic structure of the copper sites.

Highly Active and Stable Ni/La-Doped Ceria Material for Catalytic CO Reduction by Reverse Water-Gas Shift Reaction.

The design of an active, effective, and economically viable catalyst for CO conversion into value-added products is crucial in the fight against global warming and energy demand. We have developed very efficient catalysts for reverse water-gas shift (rWGS) reaction. Specific conditions of the synthesis by combustion allow the obtention of macroporous materials based on nanosized Ni particles supported on a mixed oxide of high purity and crystallinity.

Advanced Nanostructured Conjugated Microporous Polymer Application in a Tandem Photoelectrochemical Cell for Hydrogen Evolution Reaction.

Solar energy conversion through photoelectrochemical cells by organic semiconductors is a hot topic that continues to grow due to the promising optoelectronic properties of this class of materials. In this sense, conjugated polymers have raised the interest of researchers due to their interesting light-harvesting properties. Besides, their extended π-conjugation provides them with an excellent charge conduction along the whole structure.

Influence of the Synthesis and Crystallization Processes on the Cation Distribution in a Series of Multivariate Rare-Earth Metal-Organic Frameworks and Their Magnetic Characterization.

The incorporation of multiple metal atoms in multivariate metal-organic frameworks is typically carried out through a one-pot synthesis procedure that involves the simultaneous reaction of the selected elements with the organic linkers. In order to attain control over the distribution of the elements and to be able to produce materials with controllable metal combinations, it is required to understand the synthetic and crystallization processes. In this work, we have completed a study with the RPF-4 MOF family, which is made of various rare-earth elements, to investigate and determine how the different initial combinations of metal cations result in different atomic distributions in the obtained materials.

A Graphene Acid - TiO Nanohybrid as Multifunctional Heterogeneous Photocatalyst for the Synthesis of 1,3,4-Oxadiazoles.

The immobilization of TiO nanoparticles on graphene acid (GA), a conductive graphene derivative densely functionalized with COOH groups, is presented. The interaction between the carboxyl groups of the surface and the titanium precursor leads to a controlled TiO heterogenization on the nanosheet according to microscopic and spectroscopic characterizations. Electronic communication shared among graphene and semiconductor nanoparticles shifts the hybrid material optical features toward less energetic radiation but maintaining the conductivity.

Laser-Reduced BiVO for Enhanced Photoelectrochemical Water Splitting.

The present study proposes a laser irradiation method to superficially reduce BiVO photoelectrodes and boost their water oxidation reaction performance. The origin of this enhanced performance toward oxygen evolution reaction (OER) was studied using a combination of a suite of structural, chemical, and mechanistic advanced characterization techniques including X-ray photoelectron (XPS), X-ray absorption spectroscopy (XAS), electrochemical impedance spectroscopy (EIS), and transient absorption spectroscopy (TAS), among others. We found that the reduction of the material is localized at the surface of the sample and that this effect creates effective n-type doping and a shift to more favorable energy band positions toward water oxidation.

One-Metal/Two-Ligand for Dual Activation Tandem Catalysis: Photoinduced Cu-Catalyzed Anti-hydroboration of Alkynes.

A dual catalyst system based on ligand exchange of two diphosphine ligands possessing different properties in a copper complex has been devised to merge metal- and photocatalytic activation modes. This strategy has been applied to the formal anti-hydroboration of activated internal alkynes via a tandem sequence in which Cu/Xantphos catalyzes the Bpin--hydroboration of the alkyne whereas Cu/BINAP serves as a photocatalyst for visible light-mediated isomerization of the resulting alkenyl boronic ester. Photochemical studies by means of UV-vis absorption, steady-state and time-resolved fluorescence, and transient absorption spectroscopy have allowed characterizing the photoactive Cu/BINAP species in the isomerization reaction and its interaction with the intermediate -alkenyl boronic ester through energy transfer from the triplet excited state of the copper catalyst.

New Insight into Sorption Cycling Stability of Three Al-Based MOF Materials in Water Vapour.

Three porous aluminium benzene-1,3,5-tricarboxylates MIL-96(Al), MIL-100(Al) and MIL-110(Al) materials were studied for their hydrothermal stability. The 40-cycles water vapour sorption experiments for the three samples were performed by varying the temperature between 40 and 140 °C at 75% relative humidity to simulate working conditions for materials used in water sorption-based low-T heat storage and reallocation applications. The materials were characterized by powder X-ray diffraction, N physisorption, and Nuclear Magnetic Resonance and Infrared spectroscopies before and after the cycling tests.

Degradation of Benzotriazole UV-stabilizers in the presence of organic photosensitizers and visible light: A time-resolved mechanistic study.

Benzotriazole UV-stabilizers (BUVSs) are commonly used in industry as solar filters, due to their strong UV light absorption. Because of their extended usage, environmental contamination of waters due to BUVSs constitutes a growing concern. Direct photodegradation of BUVSs is not efficient due to their intrinsic thermal pathways to release the absorbed light.

Improved Methane Production by Photocatalytic CO Conversion over Ag/InO/TiO Heterojunctions.

In this work, the role of InO in a heterojunction with TiO is studied as a way of increasing the photocatalytic activity for gas-phase CO reduction using water as the electron donor and UV irradiation. Depending on the nature of the employed InO, different behaviors appear. Thus, with the high crystallite sizes of commercial InO, the activity is improved with respect to TiO, with modest improvements in the selectivity to methane.