Zr-based metalloporphyrin MOF probe for electrochemical detection of parathion-methyl.

An electrochemical (EC) sensor based on metalloporphyrin metal-organic framework (MOF) for the detection of parathion-methyl (PM) has been developed. The prepared MOF-525(Fe) exhibits great signal enhancement toward the electrochemical detection of PM owing to its unique structural properties and electrochemical activities. Under optimal experimental conditions, the as-prepared MOF-525(Fe) based EC sensor exhibited excellent PM sensing performance with a wide linear detection range (0.1 µM-100 µM) and low limit of detection (LOD, 1.4 nM). Compared to its corresponding Fe metalloporphyrin (linker), MOF-525(Fe) exhibited a superior sensitivity (28.31 µA cm-2·µM-1), which is 3.7 times higher than the sensitivity of FeTCPP linker (7.56 µA cm-2·µM-1) towards PM. The improved performance is associated with the high specific surface area and the large pore channels of MOF-525(Fe) facilitating a better interaction between PM and the Fe metalloporphyrin active sites, especially in the lower concentration range. Moreover, a possible affinity of the PM molecules toward Zr6 clusters may also contribute to the selective enrichment of PM on MOF-525(Fe). This EC sensor further demonstrated high selectivity in the presence of interfering molecules. The recovery results further confirm accurate PM sensing in actual samples, which suggests promising applications for the rapid detection of environmental organophosphates by metalloporphyrin MOFs.

Decoupled Solar Energy Storage and Dark Photocatalysis in a 3D Metal-Organic Framework.

Materials enabling solar energy conversion and long-term storage for readily available electrical and chemical energy are key for off-grid energy distribution. Herein, the specific confinement of a rhenium coordination complex in a metal-organic framework (MOF) unlocks a unique electron accumulating property under visible-light irradiation. About 15 C gMOF -1 of electric charges can be concentrated and stored for over four weeks without loss. Decoupled, on-demand discharge for electrochemical reactions and H2 evolution catalysis is shown and light-driven recharging can be conducted for >10 cycles with ≈90% of the initial charging capacity retained. Experimental investigations and theoretical calculations link electron trapping to MOF-induced geometry constraints as well as the coordination environment of the Re-center, highlighting the key role of MOF confinement on molecular guests. This study serves as the seminal report on 3D porous colloids achieving photoaccumulation of long-lived electrons, unlocking dark photocatalysis, and a path toward solar capacitor and solar battery systems.

Photocatalytic CO2 -to-Syngas Evolution with Molecular Catalyst Metal-Organic Framework Nanozymes.

Syngas, a mixture of CO and H2 , is a high-priority intermediate for producing several commodity chemicals, e.g., ammonia, methanol, and synthetic hydrocarbon fuels. Accordingly, parallel sunlight-driven catalytic conversion of CO2 and protons to syngas is a key step toward a sustainable energy cycle. State-of-the-art catalytic systems and materials often fall short as application-oriented concurrent CO and H2 evolution requires challenging reaction conditions which can hamper stability, selectivity, and efficiency. Here a light-harvesting metal-organic framework hosting two molecular catalysts is engineered to yield colloidal, water-stable, versatile nanoreactors for photocatalytic syngas generation with highly controllable product ratios. In-depth fluorescence, X-ray, and microscopic studies paired with kinetic analysis show that the host delivers energy efficiently to active sites, conceptually yielding nanozymes. This unlocked sustained CO2 reduction and H2 evolution with benchmark turnover numbers and record incident photon conversions up to 36%, showcasing a highly active and durable all-in-one material toward application in solar energy-driven syngas generation.

Topology- and wavelength-governed CO2 reduction photocatalysis in molecular catalyst-metal-organic framework assemblies.

Optimising catalyst materials for visible light-driven fuel production requires understanding complex and intertwined processes including light absorption and catalyst stability, as well as mass, charge, and energy transport. These phenomena can be uniquely combined (and ideally controlled) in porous host-guest systems. Towards this goal we designed model systems consisting of molecular complexes as catalysts and porphyrin metal-organic frameworks (MOFs) as light-harvesting and hosting porous matrices. Two MOF-rhenium molecule hybrids with identical building units but differing topologies (PCN-222 and PCN-224) were prepared including photosensitiser-catalyst dyad-like systems integrated via self-assembled molecular recognition. This allowed us to investigate the impact of MOF topology on solar fuel production, with PCN-222 assemblies yielding a 9-fold turnover number enhancement for solar CO2-to-CO reduction over PCN-224 hybrids as well as a 10-fold increase compared to the homogeneous catalyst-porphyrin dyad. Catalytic, spectroscopic and computational investigations identified larger pores and efficient exciton hopping as performance boosters, and further unveiled a MOF-specific, wavelength-dependent catalytic behaviour. Accordingly, CO2 reduction product selectivity is governed by selective activation of two independent, circumscribed or delocalised, energy/electron transfer channels from the porphyrin excited state to either formate-producing MOF nodes or the CO-producing molecular catalysts.

Dual In Situ Laser Techniques Underpin the Role of Cations in Impacting Electrocatalysts.

Understanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. Here, we demonstrate that the nature of alkali metal cations can profoundly impact the oxygen evolution activity of surface-mounted metal-organic framework (SURMOF) derived electrocatalysts, which are based on NiFe(OOH). In situ Raman spectroscopy results show that Raman shifts of the Ni-O bending vibration are inversely proportional to the mass activities from Cs+ to Li+ . Particularly, a laser-induced current transient technique was introduced to study the cation-dependent electric double layer properties and their effects on the activity. The catalytic trend appeared to be closely related to the potential of maximum entropy of the system, suggesting a strong cation impact on the interfacial water layer structure. Our results highlight how the electrolyte composition can be used to maximize the performance of SURMOF derivatives toward electrochemical water splitting.

Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry.

Benzene-1,3,5-tri(dithiocarboxylate) (BTDTC3-), the sulfur-donor analogue of trimesate (BTC3-, benzene-1,3,5-tricarboxylate), is introduced, and its potential as a multidentate, electronically bridging ligand in coordination chemistry is evaluated. For this, the sodium salt Na3BTDTC has been synthesized, characterized, and compared with the sodium salt of the related ditopic benzene-1,4-di(dithiocarboxylate) (Na2BDDTC). Single-crystal X-ray diffraction of the respective tetrahydrofuran (THF) solvates reveals that such multitopic aromatic dithiocarboxylate linkers can form both discrete metal complexes (Na3BTDTC·9THF) and (two-dimensional) coordination polymers (Na2BDDTC·4THF). Additionally, the versatile coordination behavior of the novel BTDTC3- ligand is demonstrated by successful synthesis and characterization of trinuclear Cu(I) and hexanuclear Mo(II)2 paddlewheel complexes. The electronic structure and molecular orbitals of both dithiocarboxylate ligands as well as their carboxylate counterparts are investigated by density functional theory computational methods. Electrochemical investigations suggest that BTDTC3- enables electronic communication between the coordinated metal ions, rendering it a promising tritopic linker for functional coordination polymers.

Understanding entrapped molecular photosystem and metal-organic framework synergy for improved solar fuel production.

Artificial photosystems assembled from molecular complexes, such as the photocatalyst fac-ReBr(CO)3(4,4'-dcbpy) (dcbpy = dicarboxy-2,2'-bipyridine) and the photosensitiser Ru(bpy)2(5,5'-dcbpy)Cl2 (bpy = 2,2'-bipyridine), are a wide-spread approach for solar fuel production. Recently metal-organic framework (MOF) entrapping of such complexes was demonstrated as a promising concept for catalyst stabilisation and reaction environment optimisation in colloidal-based CO2 reduction. Building on this strategy, here we examined the influence of MIL-101-NH2(Al) MOF particle size, the electron donor source, and the presence of an organic base on the photocatalytic CO2-to-CO reduction performance, and the differences to homogeneous systems. A linear relation between smaller scaffold particle size and higher photocatalytic activity, longer system lifetimes for benign electron donors, and increased turnover numbers (TONs) with certain additive organic bases, were determined. This enabled understanding of key molecular catalysis phenomena and synergies in the nanoreactor-like host-guest assembly, and yielded TONs of ∼4300 over 96 h of photocatalysis under optimised conditions, surpassing homogeneous TON values and lifetimes.

Host-Guest Interactions in a Metal-Organic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction.

A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3 (4,4'-dcbpy)] and a photosensitizer [Ru(bpy)2 (5,5'-dcbpy)]Cl2 using the isoreticular series of metal-organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location-either at the outer MOF particle surface or inside the MOF cavities-affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.

Synthetic Organic Design for Solar Fuel Systems.

From the understanding of biological processes and metalloenzymes to the development of inorganic catalysts, electro- and photocatalytic systems for fuel generation have evolved considerably during the last decades. Recently, organic and hybrid organic systems have emerged to challenge the classical inorganic structures through their enormous chemical diversity and modularity that led earlier to their success in organic (opto)electronics. This Minireview describes recent advances in the design of synthetic organic architectures and promising strategies toward (solar) fuel synthesis, highlighting progress on materials from organic ligands and chromophores to conjugated polymers and covalent organic frameworks.

A Precious-Metal-Free Hybrid Electrolyzer for Alcohol Oxidation Coupled to CO2 -to-Syngas Conversion.

Electrolyzers combining CO2 reduction (CO2 R) with organic substrate oxidation can produce fuel and chemical feedstocks with a relatively low energy requirement when compared to systems that source electrons from water oxidation. Here, we report an anodic hybrid assembly based on a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) electrocatalyst modified with a silatrane-anchor (STEMPO), which is covalently immobilized on a mesoporous indium tin oxide (mesoITO) scaffold for efficient alcohol oxidation (AlcOx). This molecular anode was subsequently combined with a cathode consisting of a polymeric cobalt phthalocyanine on carbon nanotubes to construct a hybrid, precious-metal-free coupled AlcOx-CO2 R electrolyzer. After three-hour electrolysis, glycerol is selectively oxidized to glyceraldehyde with a turnover number (TON) of ≈1000 and Faradaic efficiency (FE) of 83 %. The cathode generated a stoichiometric amount of syngas with a CO:H2 ratio of 1.25±0.25 and an overall cobalt-based TON of 894 with a FE of 82 %. This prototype device inspires the design and implementation of nonconventional strategies for coupling CO2 R to less energy demanding, and value-added, oxidative chemistry.

A diketopyrrolopyrrole dye-based dyad on a porous TiO2 photoanode for solar-driven water oxidation.

Dye-sensitised photoanodes modified with a water oxidation catalyst allow for solar-driven O2 evolution in photoelectrochemical cells. However, organic chromophores are generally considered unsuitable to drive the thermodynamically demanding water oxidation reaction, mainly due to their lack of stability upon photoexcitation. Here, the synthesis of a dyad photocatalyst (DPP-Ru) consisting of a diketopyrrolopyrrole chromophore (DPPdye) and ruthenium-based water oxidation catalyst (RuWOC) is described. The DPP-Ru dyad features a cyanoacrylic acid anchoring group for immobilisation on metal oxides, strong absorption in the visible region of the electromagnetic spectrum, and photoinduced hole transfer from the dye to the catalyst unit. Immobilisation of the dyad on a mesoporous TiO2 scaffold was optimised, including the use of a TiCl4 pretreatment method as well as employing chenodeoxycholic acid as a co-adsorbent, and the assembled dyad-sensitised photoanode achieved O2 evolution using visible light (100 mW cm-2, AM 1.5G, λ > 420 nm). An initial photocurrent of 140 µA cm-2 was generated in aqueous electrolyte solution (pH 5.6) under an applied potential of +0.2 V vs. NHE. The production of O2 has been confirmed by controlled potential electrolysis with a faradaic efficiency of 44%. This study demonstrates that metal-free dyes are suitable light absorbers in dyadic systems for the assembly of water oxidising photoanodes.

Charge accumulation kinetics in multi-redox molecular catalysts immobilised on TiO2.

Multi-redox catalysis requires the accumulation of more than one charge carrier and is crucial for solar energy conversion into fuels and valuable chemicals. In photo(electro)chemical systems, however, the necessary accumulation of multiple, long-lived charges is challenged by recombination with their counterparts. Herein, we investigate charge accumulation in two model multi-redox molecular catalysts for proton and CO2 reduction attached onto mesoporous TiO2 electrodes. Transient absorption spectroscopy and spectroelectrochemical techniques have been employed to study the kinetics of photoinduced electron transfer from the TiO2 to the molecular catalysts in acetonitrile, with triethanolamine as the hole scavenger. At high light intensities, we detect charge accumulation in the millisecond timescale in the form of multi-reduced species. The redox potentials of the catalysts and the capacity of TiO2 to accumulate electrons play an essential role in the charge accumulation process at the molecular catalyst. Recombination of reduced species with valence band holes in TiO2 is observed to be faster than microseconds, while electron transfer from multi-reduced species to the conduction band or the electrolyte occurs in the millisecond timescale. Finally, under light irradiation, we show how charge accumulation on the catalyst is regulated as a function of the applied bias and the excitation light intensity.

Rational Design of Polymers for Selective CO2 Reduction Catalysis.

A series of copolymers comprising a terpyridine ligand and various functional groups were synthesized toward integrating a Co-based molecular CO2 reduction catalyst. Using porous metal oxide electrodes designed to host macromolecules, the Co-coordinated polymers were readily immobilized via phosphonate anchoring groups. Within the polymeric matrix, the outer coordination sphere of the Co terpyridine catalyst was engineered using hydrophobic functional moieties to improve CO2 reduction selectivity in the presence of water. Electrochemical and photoelectrochemical CO2 reduction were demonstrated with the polymer-immobilized hybrid cathodes, with a CO:H2 product ratio of up to 6:1 compared to 2:1 for a corresponding "monomeric" Co terpyridine catalyst. This versatile platform of polymer design demonstrates promise in controlling the outer-sphere environment of synthetic molecular catalysts, analogous to CO2 reductases.

Solar electricity and fuel production with perylene monoimide dye-sensitised TiO2 in water.

Dye-sensitisation of TiO2 and other metal oxides is an established strategy to couple solar light harvesting with efficient charge separation for the production of electricity in dye-sensitised solar cells (DSCs) or fuels in dye-sensitised semiconductor photocatalysis (DSP). Perylene monoimide (PMI) dyes have emerged as promising organic dyes, but they have not previously been used in a functional assembly with TiO2 in aqueous solution. Here, five novel PMI dyes bearing carboxylic acid, phosphonic acid, acetylacetone, hydroxyquinoline or dipicolinic acid anchoring groups for attachment onto TiO2 are reported. We identified functional DSC and DSP systems with PMI-sensitised TiO2 in aqueous solution, which permitted a side-by-side comparison with respect to performance between the two systems. Structure-activity relationships allowed us to suggest anchor-condition-system associations to suit specific anchoring groups at various pH values, and with different electron mediators (redox couple or sacrificial electron donor) and catalysts in DSC and DSP schemes. A DSC sensitised with the hydroxyquinoline-modified PMI dye reached the highest short-circuit current density (J SC ≈ 1.4 mA cm-2) in aqueous electrolyte solution during irradiation with simulated solar light. This dye also achieved a turnover number (TONPMI) of approximately 4900 for sacrificial proton reduction after 24 h irradiation in a DSP scheme with Pt as a H2-evolving co-catalyst at pH 4.5. This performance was only surpassed by the carboxylic acid-bearing dye, which reached a new benchmark turnover number (TONPMI ≈ 1.1 × 104 after 72 h) for an organic dye in nanoparticulate DSP for solar fuel production. At higher pH (8.5), our results showed that the phosphonic acid group allows for higher performance due to a stronger anchoring ability. This study provides a platform for aqueous PMI dye-sensitised TiO2 chemistry and gives valuable insights into the performance of different anchoring groups in DSC and DSP systems.

Interfacing Formate Dehydrogenase with Metal Oxides for the Reversible Electrocatalysis and Solar-Driven Reduction of Carbon Dioxide.

The integration of enzymes with synthetic materials allows efficient electrocatalysis and production of solar fuels. Here, we couple formate dehydrogenase (FDH) from Desulfovibrio vulgaris Hildenborough (DvH) to metal oxides for catalytic CO2 reduction and report an in-depth study of the resulting enzyme-material interface. Protein film voltammetry (PFV) demonstrates the stable binding of FDH on metal-oxide electrodes and reveals the reversible and selective reduction of CO2 to formate. Quartz crystal microbalance (QCM) and attenuated total reflection infrared (ATR-IR) spectroscopy confirm a high binding affinity for FDH to the TiO2 surface. Adsorption of FDH on dye-sensitized TiO2 allows for visible-light-driven CO2 reduction to formate in the absence of a soluble redox mediator with a turnover frequency (TOF) of 11±1 s-1 . The strong coupling of the enzyme to the semiconductor gives rise to a new benchmark in the selective photoreduction of aqueous CO2 to formate.

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes.

The synthesis of renewable fuels from abundant water or the greenhouse gas CO2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dots, metal oxide surfaces, and semiconductors. The molecule-material hybrid systems are organized as "dark" cathodes, colloidal photocatalysts, and photocathodes, and their figures of merit are discussed alongside system stability and catalyst integrity. The final section extends the scope of this review to prospects and challenges in targeting catalysis beyond "classical" H2 evolution and CO2 reduction to C1 products, by summarizing cases for higher-value products from N2 reduction, C x>1 products from CO2 utilization, and other reductive organic transformations.

Inverse Opal CuCrO2 Photocathodes for H2 Production Using Organic Dyes and a Molecular Ni Catalyst.

Dye-sensitized photoelectrochemical (DSPEC) cells are an emerging approach to producing solar fuels. The recent development of delafossite CuCrO2 as a p-type semiconductor has enabled H2 generation through the coassembly of catalyst and dye components. Here, we present a CuCrO2 electrode based on a high-surface-area inverse opal (IO) architecture with benchmark performance in DSPEC H2 generation. Coimmobilization of a phosphonated diketopyrrolopyrrole (DPP-P) or perylene monoimide (PMI-P) dye with a phosphonated molecular Ni catalyst (NiP) demonstrates the ability of IO-CuCrO2 to photogenerate H2. A positive photocurrent onset potential of approximately +0.8 V vs RHE was achieved with these photocathodes. The DPP-P-based photoelectrodes delivered photocurrents of -18 µA cm-2 and generated 160 ± 24 nmol of H2 cm-2, whereas the PMI-P-based photocathodes displayed higher photocurrents of -25 µA cm-2 and produced 215 ± 10 nmol of H2 cm-2 at 0.0 V vs RHE over the course of 2 h under visible light illumination (100 mW cm-2, AM 1.5G, λ > 420 nm, 25 °C). The high performance of the PMI-constructed system is attributed to the well-suited molecular structure and photophysical properties for p-type sensitization. These precious-metal-free photocathodes highlight the benefits of using bespoke IO-CuCrO2 electrodes as well as the important role of the molecular dye structure in DSPEC fuel synthesis.

Photoreduction of CO2 with a Formate Dehydrogenase Driven by Photosystem II Using a Semi-artificial Z-Scheme Architecture.

Solar-driven coupling of water oxidation with CO2 reduction sustains life on our planet and is of high priority in contemporary energy research. Here, we report a photoelectrochemical tandem device that performs photocatalytic reduction of CO2 to formate. We employ a semi-artificial design, which wires a W-dependent formate dehydrogenase (FDH) cathode to a photoanode containing the photosynthetic water oxidation enzyme, Photosystem II, via a synthetic dye with complementary light absorption. From a biological perspective, the system achieves a metabolically inaccessible pathway of light-driven CO2 fixation to formate. From a synthetic point of view, it represents a proof-of-principle system utilizing precious-metal-free catalysts for selective CO2-to-formate conversion using water as an electron donor. This hybrid platform demonstrates the translatability and versatility of coupling abiotic and biotic components to create challenging models for solar fuel and chemical synthesis.

Redox-driven porphyrin based systems for new luminescent molecular switches.

In this work, we explore the possibility of tuning the fluorescence intensity of two porphyrin systems through the electrochemical oxidation of an appended ruthenium acetylide bridge. Two electrochemically switchable systems, a dyad (ZnP-Ru, 3) and a triad (ZnP-Ru-P2H, 5), were prepared and investigated. In the ZnP-Ru dyad, the fluorescence of the zinc porphyrin was switched reversibly between the ON and OFF state upon the oxidation of the ruthenium unit, the most probable quenching process involved after oxidation being the electron transfer from the singlet excited state of ZnP to the oxidized ruthenium center. In the ZnP-Ru-P2H triad, we show that both porphyrins' fluorescence are highly quenched independent of the redox state of the ruthenium bridge owing to the efficient photoinduced charge transfer within the ruthenium complex.

Solar H2 generation in water with a CuCrO2 photocathode modified with an organic dye and molecular Ni catalyst.

Dye-sensitised photoelectrochemical (DSPEC) cells have emerged in recent years as a route to solar fuel production. However, fuel-forming photocathodes are presently limited by photo-corrodible narrow band gap semiconductors or the small range of available wide bandgap p-type semiconductors such as NiO that display low performance with dyes. Here, we introduce CuCrO2 as a suitable p-type semiconductor for visible light-driven H2 generation upon co-immobilisation of a phosphonated diketopyrrolopyrrole dye with a Ni-bis(diphosphine) catalyst. The hybrid CuCrO2 photocathode displays an early photocurrent onset potential of +0.75 V vs. RHE and delivers a photocurrent of 15 µA cm-2 at 0.0 V vs. RHE in pH 3 aqueous electrolyte solution under UV-filtered simulated solar irradiation. Controlled potential photoelectrolysis at 0.0 V vs. RHE shows good stability and yields a Ni catalyst-based turnover number of 126 ± 13 towards H2 after 2 h. This precious metal-free system outperforms an analogous NiO|dye/catalyst assembly and therefore highlights the benefits of using CuCrO2 as a novel material for DSPEC applications.