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 B2pin2-syn-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 syn-alkenyl boronic ester through energy transfer from the triplet excited state of the copper catalyst. In addition, mechanistic studies shed light into catalyst speciation and the interplay between the two catalytic cycles as critical success factors.

Heterometallic Molecular Complexes Act as Messenger Building Units to Encode Desired Metal-Atom Combinations to Multivariate Metal-Organic Frameworks.

A novel synthetic approach is described for the targeted preparation of multivariate metal-organic frameworks (MTV-MOFs) with specific combinations of metal elements. This methodology is based on the use of molecular complexes that already comprise desired metal-atom combinations, as building units for the MTV-MOF synthesis. These units are transformed into the MOF structural constituents through a ligand/linker exchange process that involves structural modifications while preserving their originally encoded atomic combination. Thus, through the use of heterometallic ring-shaped molecules combining gallium and nickel or cobalt, we have obtained MOFs with identical combinations of the metal elements, now incorporated in the rod-shaped secondary building unit, as confirmed with a combination of X-ray and electron diffraction, electron microscopy, and X-ray absorption spectroscopy techniques.

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. In particular, conjugated porous polymers (CPPs) exhibit an inherent porosity and three-dimensional structure, offering greater surface area, and higher photochemical and mechanical stability than their linear relatives (conjugated polymers, CPs). However, CPP synthesis generally provides large particle powders unsuitable for thin film preparation, limiting its application in optoelectronic devices. Here, a synthetic strategy is presented to prepare nanostructures of a CPP suitable to be used as photoelectrode in a photoelectrochemical (PEC) cell. In this way, electronic and photoelectrochemical properties are measured and, attending to the optoelectronic properties, two hybrid photoelectrodes (photoanode and photocathode) are designed and built to assemble a tandem PEC cell. The final device exhibits photocurrents of 0.5 mA cm-2 at a 0.7 V in the two electrode configuration and the hydrogen evolution reaction is observed and quantified by gas chromatography, achieving 581 µmol of H2 in a one-hour reaction.

Fundamental Insights into Photoelectrocatalytic Hydrogen Production with a Hole-Transport Bismuth Metal-Organic Framework.

Solar fuels production is a cornerstone in the development of emerging sustainable energy conversion and storage technologies. Light-induced H2 production from water represents one of the most crucial challenges to produce renewable fuel. Metal-organic frameworks (MOFs) are being investigated in this process, due to the ability to assemble new structures with the use of suitable photoactive building blocks. However, the identification of the reaction intermediates remains elusive, having negative impacts in the design of more efficient materials. Here, we report the synthesis and characterization of a new MOF prepared with the use of bismuth and dithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxylic acid (DTTDC), an electron-rich linker with hole transport ability. By combining theoretical studies and time-resolved spectroscopies, such as core hole clock and laser flash photolysis measurements, we have completed a comprehensive study at different time scales (fs to ms) to determine the effect of competitive reactions on the overall H2 production. We detect the formation of an intermediate radical anion upon reaction of photogenerated holes with an electron donor, which plays a key role in the photoelectrocatalytic processes. These results shed new light on the use of MOFs for solar fuel production.

Hybrid materials based on conjugated polymers and inorganic semiconductors as photocatalysts: from environmental to energy applications.

Photocatalysts provide a sustainable way to remove pollutants or store energy in the form of solar fuels by processes such as water splitting and CO2 photoreduction (artificial photosynthesis). Research in this topic is an expansive field evidenced by the large number of contributions published in the past few years. Hybrid photocatalysts based on inorganic semiconductors (ISs) and conjugated polymers (CPs) have emerged as novel promising photoactive materials. In addition to the well-known behaviour of ISs in photocatalytic processes, CPs have emerged as an interesting alternative to improve the photocatalytic efficiency due to the possibility of controlling their optoelectronic, textural and morphological properties at the molecular level. Thus, the synergy between ISs and CPs leads to more efficient photocatalysts with enhanced light absorption in the overall solar spectrum, improved photocharge generation and transport, higher stability to photo-corrosion and higher surface areas. Here, we present an overview of the advances in the development of hybrid IS-CP photocatalysts for pollutant degradation and energy conversion through water splitting, CO2 reduction and/or N2 fixation using photo- and photo(electro)catalytic processes.

Combined Photoredox and Iron Catalysis for the Cyclotrimerization of Alkynes.

Successful combinations of visible-light photocatalysis with metal catalysis have recently enabled the development of hitherto unknown chemical reactions. Dual mechanisms from merging metal-free photocatalysts and earth-abundant metal catalysts are still in their infancy. We report a photo-organo-iron-catalyzed cyclotrimerization of alkynes by photoredox activation of a ligand-free Fe catalyst. The reaction operates under very mild conditions (visible light, 20 °C, 1 h) with 1-2 mol % loading of the three catalysts (dye, amine, FeCl2 ).

Hydroxamate Titanium-Organic Frameworks and the Effect of Siderophore-Type Linkers over Their Photocatalytic Activity.

The chemistry of metal-organic frameworks (MOFs) relies on the controlled linking of organic molecules and inorganic secondary building units to assemble an unlimited number of reticular frameworks. However, the design of porous solids with chemical stability still remains limited to carboxylate or azolate groups. There is a timely opportunity to develop new synthetic platforms that make use of unexplored metal binding groups to produce metal-linker joints with hydrolytic stability. Living organisms use siderophores (iron carriers in Greek) to effectively assimilate iron in soluble form. These compounds make use of hard oxo donors as hydroxamate or catecholate groups to coordinate metal Lewis acids such as iron, aluminum, or titanium to form metal complexes very stable in water. Inspired by the chemistry of these microorganisms, we report the first hydroxamate MOF prepared by direct synthesis. MUV-11 (MUV = materials of Universidad de Valencia) is a crystalline, porous material (close to 800 m2·g-1) that combines photoactivity with good chemical stability in acid conditions. By using a high-throughput approach, we also demonstrate that this new chemistry is compatible with the formation of single-crystalline phases for multiple titanium salts, thus expanding the scope of accessible precursors. Titanium frameworks are regarded as promising materials for photocatalytic applications. Our photoelectrochemical and catalytic tests suggest important differences for MUV-11. Compared to other Ti-MOFs, changes in the photoelectrochemical and photocatalytic activity have been rationalized with computational modeling, revealing how the chemistry of siderophores can introduce changes to the electronic structure of the frontier orbitals, relevant to the photocatalytic activity of these solids.

New Concepts for Production of Scalable Single Layer Oxidized Regions by Local Anodic Oxidation of Graphene.

A deep comprehension of the local anodic oxidation process in 2D materials is achieved thanks to an extensive experimental and theoretical study of this phenomenon in graphene. This requires to arrange a novel instrumental device capable to generate separated regions of monolayer graphene oxide (GO) over graphene, with any desired size, from micrometers to unprecedented mm2 , in minutes, a milestone in GO monolayer production. GO regions are manufactured by overlapping lots of individual oxide spots of thousands µm2 area. The high reproducibility and circular size of the spots allows not only an exhaustive experimental characterization inside, but also establishing an original model for oxide expansion which, from classical first principles, overcomes the traditional paradigm of the water bridge, and is applicable to any 2D-material. This tool predicts the oxidation behavior with voltage and exposure time, as well as the expected electrical current along the process. The hitherto unreported transient current is measured during oxidation, gaining insight on its components, electrochemical and transport. Just combining electrical measurements and optical imaging estimating carrier mobility and degree of oxidation is possible. X-ray photoelectron spectroscopy reveals a graphene oxidation about 30%, somewhat lower to that obtained by Hummers' method.

Dichromatic Photocatalytic Substitutions of Aryl Halides with a Small Organic Dye.

Photocatalytic bond activations are generally limited by the photon energy and the efficiency of energy and electron transfer processes. Direct two-photon processes provide sufficient energy but the ultra-short lifetimes of the excited states prohibit chemical reactions. The commercial dye 9,10-dicyanoanthracene enabled photocatalytic aromatic substitutions of non-activated aryl halides. This reaction operates under VIS-irradiation via sequential photonic, electronic, and photonic activation of the simple organic dye. The resultant highly reducing excited photocatalyst anion readily effected C-H, C-C, C-P, C-S, and C-B bond formations. Detailed synthetic, spectroscopic, and theoretical studies support a biphotonic catalytic mechanism.

A Facile Synthesis of Blue Luminescent [7]Helicenocarbazoles Based on Gold-Catalyzed Rearrangement-Iodonium Migration and Suzuki-Miyaura Benzannulation Reactions.

New azahelicenes having interesting photophysical properties have been prepared in a four-step sequence. These [7]helicenocarbazoles are efficient blue luminophores, demonstrating the utility of gold catalysis in the preparation of advanced materials.

Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity for hydrodeoxygenation MoP/SBA-15 appears as a very promising catalyst for the production of advanced biofuels.

Localization and impact of Pb-non-bonded electronic pair on the crystal and electronic structure of Pb2YSbO6.

The synthesis and crystal structure evolution of the double perovskite Pb2YSbO6 is reported for the first time. The structure has been analyzed in the temperature range between 100 and 500 K by using a combination of synchrotron and neutron powder diffraction. This compound shows two consecutive first order phase transformations as previously observed for a subgroup of Pb2RSbO6 perovkites (R = rare earths). The thermodynamic parameters associated with the phase transitions were calculated using differential scanning calorimetry (DSC), and the role of the diverse cations of the structure was studied from DFT calculations for the room temperature polymorph. The crystal structure evolves from a C2/c monoclinic structure (a(-)b(-)b(-) tilting system in Glazer's notation) to another monoclinic P2(1)/n (a(-)a(-)b(+)) phase with an incommensurate modulation and finally to a cubic Fm3m perovskite (a(0)a(0)a(0)). The highly distorted nature of the room temperature crystal structure seems to be driven by the polarization of the Pb lone pair which shows a marked local effect in the atomic spatial arrangements. Moreover, the lone pairs have been localized from DFT calculations and show an antiferroelectric ordering along the b monoclinic axis.

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.].

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. Thus, the reaction of 2, 6-AQDS with Bi(iii) or a combination of Bi(iii) and Fe(iii) resulted in two new MOFs, BiPF-10 and BiFePF-15, respectively. They display similar structural features, where the metal elements are disposed in inorganic-layer building units, which are pillared by the organic linkers by coordination bonds through the sulfonic acid groups. We show that the introduction of iron in the structure plays a crucial role for the practical use of the MOFs as a robust photoelectrode in a photoelectrochemical cell, producing as much as 1.23 mmol H2 cm-2 with the use of BiFePF-15 as photoanode. By means of time-resolved and electrochemical impedance spectroscopic studies we have been able to unravel the charge transfer mechanism, which involves the formation of a radical intermediate species, exhibiting a longer-lived lifetime by the presence of the iron-oxo clusters in BiFePF-15 to reduce the charge transfer resistance.

Tuning mono-divalent cation water composition by the capacitive ion-exchange mechanism.

Soil salinization poses a significant challenge to agricultural activities. To address this, the agricultural industry seeks an irrigation water solution that reduces both ionic conductivity and sodium adsorption rate (SAR), thereby diminishing the risks of soil sodification and fostering sustainable crop production. Capacitive deionization (CDI) is an attractive electrochemical technology to advance this search. Recently, a one-dimensional transient CDI model unveiled a capacitive ion-exchange mechanism presenting the potential to adjust the treated water composition by modifying monovalent and divalent cation concentrations, thereby influencing the SAR index. This behavior would be achieved by using electrodes rich in surface functional groups able to efficiently capture divalent cations during conditioning and releasing them during charging while capturing monovalent ions. Beyond the theoretical modelling, the current experimental research demonstrates, for the first time, the effectiveness of the capacitive ion-exchange mechanism in a CDI pilot plant using real water samples spiked with solutions containing specific mono and divalent ions. Electrosorption experiments and computational modeling, specifically Density-Functional Theory (DFT), were used along with the analysis of the surface functional groups present in the electrodes to describe the capacitive ion-exchange phenomenon and validate the steps involved on it, highlighting the conditioning as a critical step. Various operational and flow modes confirm the versatility of CDI technology, achieving separation factors (RMg/Na) of 5-6 in batch, raising production from 0.5 to 0.8 L m-2 h-1 (batch) to 8.0-8.1 L m-2 h-1 when using single pass although reducing RMg/Na to 2. The reliability of the CDI technology in reducing SAR was also successfully tested with different influent compositions, including magnesium and calcium. Finally, the robustness of the capacitive ion-exchange mechanism was validated by a second CDI laboratory 9-cell stack cycled over 350 cycles. Our results confirm the reported theoretical model and expands the conclusions through the experiments in a pilot plant showing direct implications for employing CDI in agricultural applications.

Dynamic restructuring of nickel sulfides for electrocatalytic hydrogen evolution reaction.

Transition metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen evolution reaction in alkaline media. However, the identification of active sites and the underlying catalytic mechanism remain elusive. In this work, we employ operando X-ray absorption spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy to elucidate that NiS undergoes an in-situ phase transition to an intimately mixed phase of Ni3S2 and NiO, generating highly active synergistic dual sites at the Ni3S2/NiO interface. The interfacial Ni is the active site for water dissociation and OH* adsorption while the interfacial S acts as the active site for H* adsorption and H2 evolution. Accordingly, the in-situ formation of Ni3S2/NiO interfaces enables NiS electrocatalysts to achieve an overpotential of only 95 ± 8 mV at a current density of 10 mA cm-2. Our work highlighted that the chemistry of transition metal chalcogenides is highly dynamic, and a careful control of the working conditions may lead to the in-situ formation of catalytic species that boost their catalytic performance.

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 TiO2 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. To correlate the photoelectrochemical performance with the atomic and chemical structures of the hydrogen-reduced materials, we have modeled the process with in situ scanning tunneling microscopy measurements, which allow us to determine the initial stages of oxygen desorption and the desorption/diffusion of Ti atoms from the surface. This multiscale study opens a door toward improved materials for diverse applications such as more efficient rutile TiO2-based photoelectrocatalysts, green photothermal absorbers for solar energy applications, or NIR-sensing materials.

Triple Play of Band Gap, Interband, and Plasmonic Excitations for Enhanced Catalytic Activity in Pd/HxMoO3 Nanoparticles in the Visible Region.

Plasmonic photocatalysis has been limited by the high cost and scalability of plasmonic materials, such as Ag and Au. By focusing on earth-abundant photocatalyst/plasmonic materials (HxMoO3) and Pd as a catalyst, we addressed these challenges by developing a solventless mechanochemical synthesis of Pd/HxMoO3 and optimizing photocatalytic activities in the visible range. We investigated the effect of HxMoO3 band gap excitation (at 427 nm), Pd interband transitions (at 427 nm), and HxMoO3 localized surface plasmon resonance (LSPR) excitation (at 640 nm) over photocatalytic activities toward the hydrogen evolution and phenylacetylene hydrogenation as model reactions. Although both excitation wavelengths led to comparable photoenhancements, a 110% increase was achieved under dual excitation conditions (427 + 640 nm). This was assigned to a synergistic effect of optical excitations that optimized the generation of energetic electrons at the catalytic sites. These results are important for the development of visible-light photocatalysts based on earth-abundant components.