Towards the Use of Renewable Syngas for the Decarbonization of Industry.

In this article we analyze how syngas produced in a renewable way can replace fossil-fuel based syngas production and thereby play an essential role in the decarbonization of industry. We show that in essentially all industrial applications renewable H2 and/or CO can replace syngas from fossil fuel feedstocks, and quantify the flows of these chemical building blocks required for the transformation of industry towards a net-zero emitting sector. We also undertake a techno-economic analysis, in which we demonstrate that under specific assumptions for the learning rates of some of the key process components, renewable syngas can become cost-competitive with that produced from fossil fuels. Cost competitiveness, however, only materializes for four of the five routes when natural gas prices are at least around 3 €/GJ and carbon taxes increase from 90 €/tCO2 today to 300 €/tCO2 in 2050.

Increased solar-driven chemical transformations through surface-induced benzoperylene aggregation in dye-sensitized photoanodes.

The impact of benzo[ghi]perylenetriimide (BPTI) dye aggregation on the performance of photoelectrochemical devices was explored, through imide-substitution with either alkyl (BPTI-A, 2-ethylpropyl) or bulky aryl (BPTI-B, 2,6-diisopropylphenyl) moieties, to, respectively, enable or suppress aggregation. While both dyes demonstrated similar monomeric optoelectronic properties in solution, adsorption onto mesoporous SnO2 revealed different behavior, with BPTI-A forming aggregates via π-stacking and BPTI-B demonstrating reduced aggregation in the solid state. BPTI photoanodes were tested in dye-sensitized solar cells (DSSCs) before application to dye-sensitized photoelectrochemical cells (DSPECs) for Br2 production (a strong oxidant) coupled to H2 generation (a solar fuel). BPTI-A demonstrated a twofold higher dye loading of the SnO2 surface than BPTI-B, resulting in a fivefold enhancement to both photocurrent and Br2 production. The enhanced output of the photoelectrochemical systems (with respect to dye loading) was attributed to both J- and H- aggregation phenomena in BPTI-A photoanodes that lead to improved light harvesting. Our investigation provides a strategy to exploit self-assembly via aggregation to improve molecular light-harvesting and charge separation properties that can be directly applied to dye-sensitized photoelectrochemical devices.

Aqueous Biphasic Dye-Sensitized Photosynthesis Cells for TEMPO-Based Oxidation of Glycerol.

This work reports an aqueous dye-sensitized photoelectrochemical cell (DSPEC) capable of oxidizing glycerol (an archetypical biobased compound) coupled with H2 production. We employed a mesoporous TiO2 photoanode sensitized with the high potential thienopyrroledione-based dye AP11, encased in an acetonitrile-based redox-gel that protects the photoanode from degradation by aqueous electrolytes. The use of the gel creates a biphasic system with an interface at the organic (gel) electrode and aqueous anolyte. Embedded in the acetonitrile gel is 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), acting as both a redox-mediator and a catalyst for oxidative transformations. Upon oxidation of TEMPO by the photoexcited dye, the in situ generated TEMPO+ shuttles through the gel to the acetonitrile-aqueous interface, where it acts as an oxidant for the selective conversion of glycerol to glyceraldehyde. The introduction of the redox-gel layer affords a 10-fold increase in the conversion of glycerol compared to the purely aqueous system. Our redox-gel protected photoanode yielded a stable photocurrent over 48 hours of continuous operation, demonstrating that this DSPEC is compatible with alkaline aqueous reactions.

Nickel is a Different Pickle: Trends in Water Oxidation Catalysis for Molecular Nickel Complexes.

The development of novel water oxidation catalysts is important in the context of renewable fuels production. Ligand design is one of the key tools to improve the activity and stability of molecular catalysts. The establishment of ligand design rules can facilitate the development of improved molecular catalysts. In this paper it is shown that chemical oxidants can be used to probe oxygen evolution activity for nickel-based systems, and trends are reported that can improve future ligand design. Interestingly, different ligand effects were observed in comparison to other first-row transition metal complexes. For example, nickel complexes with secondary amine donors were more active than with tertiary amine donors, which is the opposite for iron complexes. The incorporation of imine donor groups in a cyclam ligand resulted in the fastest and most durable nickel catalyst of our series, achieving oxygen evolution turnover numbers up to 380 and turnover frequencies up to 68 min-1 in a pH 5.0 acetate buffer using Oxone as oxidant. Initial kinetic experiments with this catalyst revealed a first order in chemical oxidant and a half order in catalyst. This implies a rate-determining oxidation step from a dimeric species that needs to break up to generate the active catalyst. These findings lay the foundation for the rational design of molecular nickel catalysts for water oxidation and highlight that catalyst design rules are not generally applicable for different metals.

Potential- and Buffer-Dependent Catalyst Decomposition during Nickel-Based Water Oxidation Catalysis.

The production of hydrogen by water electrolysis benefits from the development of water oxidation catalysts. This development process can be aided by the postulation of design rules for catalytic systems. The analysis of the reactivity of molecular complexes can be complicated by their decomposition under catalytic conditions into nanoparticles that may also be active. Such a misinterpretation can lead to incorrect design rules. In this study, the nickel-based water oxidation catalyst [NiII (meso-L)](ClO4 )2 , which was previously thought to operate as a molecular catalyst, is found to decompose to form a NiOx layer in a pH 7.0 phosphate buffer under prolonged catalytic conditions, as indicated by controlled potential electrolysis, electrochemical quartz crystal microbalance, and X-ray photoelectron spectroscopy measurements. Interestingly, the formed NiOx layer desorbs from the surface of the electrode under less anodic potentials. Therefore, no nickel species can be detected on the electrode after electrolysis. Catalyst decomposition is strongly dependent on the pH and buffer, as there is no indication of NiOx layer formation at pH 6.5 in phosphate buffer nor in a pH 7.0 acetate buffer. Under these conditions, the activity stems from a molecular species, but currents are much lower. This study demonstrates the importance of in situ characterization methods for catalyst decomposition and metal oxide layer formation, and previously proposed design elements for nickel-based catalysts need to be revised.

A Functional Hydrogenase Mimic Chemisorbed onto Fluorine-Doped Tin Oxide Electrodes: A Strategy towards Water Splitting Devices.

A diiron benzenedithiolate hydrogen-evolving catalyst immobilized onto fluorine-doped tin oxide (FTO) electrodes is prepared, characterized, and studied in the context of the development of water splitting devices based on molecular components. FTO was chosen as the preferred electrode material owing to its conductive properties and electrochemical stability. An FTO nanocrystalline layer is also used to greatly improve the surface area of commercially available FTO while preserving the properties of the material. Electrodes bearing a covalently anchored diiron catalyst are shown to be competent for electrocatalytic hydrogen evolution from acidic aqueous media at relatively low overpotential (500 mV) with a faradaic efficiency close to unity. Compared with bulk solution catalysts, the catalyst immobilized onto the electrode surface operates at roughly 160 mV lower overpotentials, yet with similar rates.

Rational Design Rules for Molecular Water Oxidation Catalysts based on Scaling Relationships.

Lowering the overpotential required for water oxidation is of paramount importance for the efficient production of carbon-neutral fuels. This article highlights the intrinsic influence of the water oxidation mechanism used by molecular catalysts on the theoretically achievable minimal overpotential, based on scaling relationships typically used for heterogeneous catalysts. Due to such scaling relationships, catalysts that operate through the water nucleophilic attack mechanism have a fundamental minimal overpotential of about 0.3 V, whereas those that follow the dinuclear radical oxo coupling mechanism should in principle be able to operate with a lower overpotential. Therefore, it is recommended to design catalysts operating through the latter mechanism to achieve very efficient water oxidation systems.

Rational Optimization of Supramolecular Catalysts for the Rhodium-Catalyzed Asymmetric Hydrogenation Reaction.

Rational design of catalysts for asymmetric transformations is a longstanding challenge in the field of catalysis. In the current contribution we report a catalyst in which a hydrogen bond between the substrate and the catalyst plays a crucial role in determining the selectivity and the rate of the catalytic hydrogenation reaction, as is evident from a combination of experiments and DFT calculations. Detailed insight allowed in silico mutation of the catalyst such that only this hydrogen bond interaction is stronger, predicting that the new catalyst is faster. Indeed, we experimentally confirmed that optimization of the catalyst can be realized by increasing the hydrogen bond strength of this interaction by going from a urea to phosphine oxide H-bond acceptor on the ligand.

Anode Preparation Strategies for the Electrocatalytic Oxidation of Water Based on Strong Interactions between Multiwalled Carbon Nanotubes and Cationic Acetylammonium Pyrene Moieties in Aqueous Solutions.

A strategy is reported for the immobilization of iridium-based water oxidation catalyst 3 onto fluorine-doped tin oxide (FTO) anodes evaluated for the electrocatalytic oxidation of H2 O. The strategy is based on noncovalent π-π interactions between multiwalled carbon nanotubes (MWCNTs) and the cationic acetylammonium pyrene moiety (Pyr+ ) covalently attached to a NHC IrCp*Cl2 catalytically active center (NHC=N-heterocyclic carbene, Cp*=C5 Me5 ). The dispersive properties of the Pyr+ moiety in compound 3 leads to the formation of stable MWCNT dispersions in aqueous solutions. In addition, the MWCNT/3 assembly shows activity in the Ce4+ -driven oxidation of H2 O. FTO/MWCNT/3 anodes show increased current densities when used as a working electrode for the electrocatalytic oxidation of H2 O. At higher anodic polarizations initially high current densities were achieved; however, these currents prove to be non-sustained due to delamination and degradation of the catalytically active surface. The immobilization strategy is limited to applications below 1.4 V vs normal hydrogen electrode (NHE) as oxidation of the pyrene backbone is evident at higher potentials.

Towards a Bioinspired-Systems Approach for Solar Fuel Devices.

What lies ahead? In the development of solar fuel devices Nature provides the blueprint for artificial photosynthesis and water oxidation/reduction catalysts. Researchers have come a long way, but many challenges lie ahead.

A Fluorescence-Based Screening Protocol for the Identification of Water Oxidation Catalysts.

Efficient catalysts are crucial for the sustainable generation of fuel by splitting water. A versatile screening protocol would simplify the identification of novel and better catalysts by using high throughput experimentation. Herein, such a screening approach for the identification of molecular catalysts for chemical oxidation of water is reported, which is based on oxygen-sensitive fluorescence quenching using an OxoDish. More than 200 reactions were performed revealing several catalysts, for example, a dinuclear Fe complex that produced oxygen under the used reaction conditions. Clark electrode measurements confirmed a similar rate in oxygen evolution, making the developed parallel screening approach a robust and versatile tool to screen for molecular water oxidation catalysts using chemical oxidants under acidic and neutral conditions.

Organic-Inorganic Hybrid Solution-Processed H2-Evolving Photocathodes.

Here we report for the first time an H2-evolving photocathode fabricated by a solution-processed organic-inorganic hybrid composed of CdSe and P3HT. The CdSe:P3HT (10:1 (w/w)) hybrid bulk heterojunction treated with 1,2-ethanedithiol (EDT) showed efficient water reduction and hydrogen generation. A photocurrent of -1.24 mA/cm(2) at 0 V versus reversible hydrogen electrode (V(RHE)), EQE of 15%, and an unprecedented Voc of 0.85 V(RHE) under illumination of AM1.5G (100 mW/cm(2)) in mild electrolyte were observed. Time-resolved photoluminescence (TRPL), internal quantum efficiency (IQE), and transient photocurrent measurements were carried out to clarify the carrier dynamics of the hybrids. The exciton lifetime of CdSe was reduced by one order of magnitude in the hybrid blend, which is a sign of the fast charge separation upon illumination. By comparing the current magnitude of the solid-state devices and water-splitting devices made with identical active layers, we found that the interfaces of the water-splitting devices limit the device performance. The electron/hole transport properties investigated by comparing IQE spectra upon front- and back-side illumination evidenced balanced electron/hole transport. The Faradaic efficiency is 80-100% for the hybrid photocathodes with Pt catalysts and ∼70% for the one without Pt catalysts.

Enantioselective synthesis of tunable chiral Clickphine P,N-ligands and their application in Ir-catalyzed asymmetric hydrogenation.

A small library of highly tunable chiral Clickphine P,N-ligands has been prepared in an enantioselective fashion by Cu(I)-catalyzed asymmetric propargylic amination using a single chiral complex and a subsequent in situ cycloaddition click reaction. The scope of the propargylic amination to yield optically active triazolyl amines is described. The amines are transformed in a one-pot procedure to the corresponding Ir-Clickphine complexes, which serve as catalysts for the asymmetric hydrogenation of di-, tri-, and tetrasubstituted unfunctionalized alkenes. Enantioselectivities of up to 90% ee were obtained in these hydrogenations, which are among the best reported in the case of the tetrasubstituted substrate 2-(4'-methoxyphenyl)-3-methylbut-2-ene (9) (87% ee). This is a demonstration of the effective use of the chiral pool, as from one chiral catalyst a library of chiral Ir complexes has been synthesized that can hydrogenate various alkenes with high selectivity.

Beyond classical reactivity patterns: hydroformylation of vinyl and allyl arenes to valuable ß- and γ-aldehyde intermediates using supramolecular catalysis.

In this study, we report on properties of a series of rhodium complexes of bisphosphine and bisphosphite L1-L7 ligands, which are equipped with an integral anion binding site (the DIM pocket), and their application in the regioselective hydroformylation of vinyl and allyl arenes bearing an anionic group. In principle, the binding site of the ligand is used to preorganize a substrate molecule through noncovalent interactions with its anionic group to promote otherwise unfavorable reaction pathways. We demonstrate that this strategy allows for unprecedented reversal of selectivity to form otherwise disfavored ß-aldehyde products in the hydroformylation of vinyl 2- and 3-carboxyarenes, with chemo- and regioselectivity up to 100%. The catalyst has a wide substrate scope, including the most challenging substrates with internal double bonds. Coordination studies of the catalysts under catalytically relevant conditions reveal the formation of the hydridobiscarbonyl rhodium complexes [Rh(Ln)(CO)2H]. The titration studies confirm that the rhodium complexes can bind anionic species in the DIM binding site of the ligand. Furthermore, kinetic studies and in situ spectroscopic investigations for the most active catalyst give insight into the operational mode of the system, and reveal that the catalytically active species are involved in complex equilibria with unusual dormant (reversibly inactivated) species. In principle, this involves the competitive inhibition of the recognition center by product binding, as well as the inhibition of the metal center via reversible coordination of either a substrate or a product molecule. Despite the inhibition effects, the substrate preorganization gives rise to very high activities and efficiencies (TON > 18,000 and TOF > 6000 mol mol(-1) h(-1)), which are adequate for commercial applications.

Precise supramolecular control of selectivity in the Rh-catalyzed hydroformylation of terminal and internal alkenes.

In this study, we report a series of DIMPhos ligands L1-L3, bidentate phosphorus ligands equipped with an integral anion binding site (the DIM pocket). Coordination studies show that these ligands bind to a rhodium center in a bidentate fashion. Experiments under hydroformylation conditions confirm the formation of the mononuclear hydridobiscarbonyl rhodium complexes that are generally assumed to be active in hydroformylation. The metal complexes formed still strongly bind the anionic species in the binding site of the ligand, without affecting the metal coordination sphere. These bifunctional properties of DIMPhos are further demonstrated by the crystal structure of the rhodium complex with acetate anion bound in the binding site of the ligand. The catalytic studies demonstrate that substrate preorganization by binding in the DIM pocket of the ligand results in unprecedented selectivities in hydroformylation of terminal and internal alkenes functionalized with an anionic group. Remarkably, the selectivity controlling anionic group can be even 10 bonds away from the reactive double bond, demonstrating the potential of this supramolecular approach. Control experiments confirm the crucial role of the anion binding for the selectivity. DFT studies on the decisive intermediates reveal that the anion binding in the DIM pocket restricts the rotational freedom of the reactive double bound. As a consequence, the pathway to the undesired product is strongly hindered, whereas that for the desired product is lowered in energy. Detailed kinetic studies, together with the in situ spectroscopic measurements and isotope-labeling studies, support this mode of operation and reveal that these supramolecular systems follow enzymatic-type Michaelis-Menten kinetics, with competitive product inhibition.

Enantioselective copper-catalysed propargylic substitution: synthetic scope study and application in formal total syntheses of (+)-anisomycin and (-)-cytoxazone.

A copper catalyst with a chiral pyridine-2,6-bisoxazoline (pybox) ligand was used to convert a variety of propargylic esters with different side chains (R=Ar, Bn, alkyl) into their amine counterparts in very high yields and with good enantioselectivities (up to 90% enantiomeric excess (ee)). Different amine nucleophiles were applied in the reactions and the highest enantioselectivities were obtained for aniline and its analogues. Interestingly, some carbon nucleophiles could also be used and with indoles excellent ee values were obtained (up to 98% ee). The versatility of the propargylic amines obtained was demonstrated by their further elaboration to formal total syntheses of the antibiotic (+)-anisomycin and the cytokine modulator (-)-cytoxazone.

Rhodium-P,O-bidentate coordinated ureaphosphine ligands for asymmetric hydrogenation reactions.

We present new ureaphosphine ligands that coordinate in a P,O-bidentate fashion to rhodium(i). The ureaphosphine-Rh(i)-complexes were effectively used in the asymmetric hydrogenation of cyclic enamides giving high conversions and enantioselectivity.

"Clickphine": a novel and highly versatile P,N ligand class via click chemistry.

[Structure: see text] A novel P,N-type ligand family (ClickPhine) is disclosed that is easily accessible using the Cu(I)-catalyzed azide-alkyne "click" cycloaddition. A diverse set of ligands was made in just three steps from readily available starting materials to give several homogeneous and a heterogeneous catalyst. Preliminary experiments show the efficacy of these ligands in the Pd-catalyzed allylic alkylation reaction.