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The current limitations in utilizing metal-organic frameworks for (photo)electrochemical applications stem from their diminished electrochemical stability. In our study, we illustrate a method to bolster the activity and stability of (photo)electrocatalytically active metal-organic frameworks through ligand engineering. We synthesize four distinct mixed-ligand versions of zeolitic imidazolate framework-67, and conduct a comprehensive investigation into the structural evolution and self-reconstruction during electrocatalytic oxygen evolution reactions. In contrast to the conventional single-ligand ZIF, where the framework undergoes a complete transformation into CoOOH via a stepwise oxidation, the ligand-engineered zeolitic imidazolate frameworks manage to preserve the fundamental framework structure by in-situ forming a protective cobalt (oxy)hydroxide layer on the surface. This surface reconstruction facilitates both conductivity and catalytic activity by one order of magnitude and considerably enhances the (photo)electrochemical stability. This work highlights the vital role of ligand engineering for designing advanced and stable metal-organic frameworks for photo- and electrocatalysis., (© 2024. The Author(s).)

A novel series of Zn II - trans -A 2 B 2 porphyrins and benzoporphyrins bearing phenyl and thiophene-based meso -substituents was successfully synthesized and characterized by spectroscopic and electrochemical techniques. Systematic comparison among the compounds in this series, together with the corresponding A 4 analogs previously studied by our group, led to the understanding of the effects of π-conjugated system extension of a porphyrin core through β-fused rings, replacement of the phenyl with the thiophene-based meso -groups, and introduction of additional thiophene rings on thienyl substituents on photophysical and electrochemical properties. Oxidative electropolymerization through bithiophenyl units of both A 4 and trans -A 2 B 2 analogs was achieved, resulting in porphyrin- and benzoporphyrin-oligothiophene conjugated polymers, which were characterized by cyclic voltammetry and absorption spectrophotometry. Preliminary studies on catalytic performance toward electrochemical reduction of carbon dioxide (CO 2 ) was described herein to demonstrate the potential of the selected compounds for serving as homogeneous and heterogeneous electrocatalysts for the conversion of CO 2 to carbon monoxide (CO)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Production of green hydrogen (H 2 ) is a sustainable process able to address the current energy crisis without contributing to long-term greenhouse gas emissions. Many Ag-based catalysts have shown promise for light-driven H 2 generation, however, pure Ag-in its bulk or nanostructured forms-suffers from slow electron transfer kinetics and unfavorable Ag─H bond strength. It is demonstrated that the complexation of Ag with various chalcogenides can be used as a tool to optimize these parameters and reach improved photocatalytic performance. In this work, metal-organic-chalcogenolate assemblies (MOCHAs) are introduced as effective catalysts for light-driven hydrogen evolution reaction (HER) and investigate their performance and structural stability by examining a series of AgXPh (X = S, Se, and Te) compounds. Two catalyst-support sensitization strategies are explored: by designing MOCHA/TiO 2 composites and by employing a common Ru-based photosensitizer. It is demonstrated that the heterogeneous approach yields stable HER performance but involves a catalyst transformation at the initial stage of the photocatalytic process. In contrast to this, the visible-light-driven MOCHA-dye dyad shows similar HER activity while also ensuring the structural integrity of the MOCHAs. The work shows the potential of MOCHAs in constructing photosystems for catalytic H 2 production and provides a direct comparison between known AgXPh compounds., (© 2024 The Authors. Small published by Wiley‐VCH GmbH.)

The organic semiconductor 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), a widely used industrial pigment, has been identified as a diffusion-less Na-ion storage material, allowing for exceptionally fast charging/discharging rates. The elimination of diffusion effects in electrochemical measurements enables the assessment of interaction energies from simple cyclic voltammetry experiments through the theoretical work of Laviron and Tokuda. In this work, the two N-substituted perylenes, N , N '-dimethyl-3,4,9,10-perylenetetracarboxylic diimide (Me 2 PTCDI) and N , N '-diphenyl-3,4,9,10-perylenetetracarboxylic diimide (Ph 2 PTCDI), as well as the parent molecule 3,4,9,10-perylenetetracarboxylic diimide (H 2 PTCDI) are investigated as thin-film composite electrodes on carbon fibers for sodium-ion batteries. The composite electrodes are analyzed with Raman spectroscopy. Interaction parameters are extracted from cyclic voltammetry measurements. The stability and rate capability of the three PTCDI derivatives are examined through galvanostatic measurements in sodium-ion half-cell batteries and the influence of the interactions on those parameters is evaluated. In addition, self-consistent charge density function tight binding calculations of the different PTCDI systems interacting with graphite have been carried out. The results show that the binding motif displays notable deviations from an ideal ABA stacking, especially for the neutral state. In addition, data obtained for the electron-transfer integrals show that the difference in performance between different PTCDI thin-film batteries cannot be solely explained by the electron-transfer properties and other factors such as H-bonding have to be considered., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

CuAl layered double hydroxide (LDH) and polymeric carbon nitride (g-C 3 N 4 , GCNN) were assembled to construct a set of novel 2D/2D CuAl-LDH/GCNN heterostructures. These materials were tested towards H 2 and O 2 generation from water splitting using visible-light irradiation. Compared to pristine materials, the heterostructures displayed strongly enhanced visible-light H 2 evolution, dependent on the LDH content, which acts as a cocatalyst, replacing the benchmark Pt. The optimal LDH loading was achieved for 0.2CuAl-LDH/GCNN that exhibited an increased number of active sites and showed a trade-off between charge separation efficiency and light shading, resulting in a 32-fold increase in the amount of evolved H 2 compared with GCNN. In addition, the 0.2CuAl-LDH/GCNN heterostructure generated 1.5 times more O 2 than GCNN. The higher photocatalytic performance was due to efficient charge carriers' separation at the heterojunction interface via an S-scheme (corroborated by work function, steady-state and time-resolved photoluminescence studies), enhanced utilisation of longer-wavelength photons (>460 nm) and higher surface area available for the catalytic reactions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Today, many essential industrial processes depend on syngas. Due to a high energy demand and overall cost as well as a dependence on natural gas as its precursor, alternative routes to produce this valuable mixture of hydrogen and carbon monoxide are urgently needed. Electrochemical syngas production via two competing processes, namely carbon dioxide (CO 2 ) reduction and hydrogen (H 2 ) evolution, is a promising method. Often, noble metal catalysts such as gold or silver are used, but those metals are costly and have limited availability. Here, we show that metal-organic chalcogenolate assemblies (MOCHAs) combine several properties of successful electrocatalysts. We report a scalable microwave-assisted synthesis method for highly crystalline MOCHAs ([AgXPh] ∞ : X = Se, S) with high yields. The morphology, crystallinity, chemical and structural stability are thoroughly studied. We investigate tuneable syngas production via electrocatalytic CO 2 reduction and find the MOCHAs show a maximum Faraday efficiency (FE) of 55 and 45% for the production of carbon monoxide and hydrogen, respectively., (© 2023. The Author(s).)

Co-doping represents a valid approach to maximize the performance of photocatalytic and photoelectrocatalytic semiconductors. Albeit theoretical predictions in hematite suggesting a bulk n-type doping and a surface p-type doping would deliver best results, hematite co-doping with coupled cations possessing low and high oxidation states has shown promising results. Herein, we report, for the first time, Sb and Li co-doping of hematite photoanodes. Particularly, this is also a seminal work for the introduction of the highly reactive Sb 5+ directly into the hematite thin films. Upon co-doping, we have a synergistic effect on the current densities with a 67-fold improvement over the standard. Via a combined investigation with profuse photoelectrochemical measurements, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman analyses, we confirm the two doping roles of Sb 5+ and Li + as the substitutional and interstitial dopant, respectively. The improvements are attributed to a higher charge carrier concentration along with a lower charge transfer resistance at the surface., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The ordering effects in anthraquinone (AQ) stacking forced by thin-film application and its influence on dimer solubility and current collector adhesion are investigated. The structural characteristics of AQ and its chemical environment are found to have a substantial influence on its electrochemical performance. Computational investigation for different charged states of AQ on a carbon substrate obtained via basin hopping global minimization provides important insights into the physicochemical thin-film properties. The results reveal the ideal stacking configurations of the individual AQ-carrier systems and show ordering effects in a periodic supercell environment. The latter reveals the transition from intermolecular hydrogen bonding toward the formation of salt bridges between the reduced AQ units and a stabilizing effect upon the dimerlike rearrangement, while the strong surface-molecular interactions in the thin-film geometries are found to be crucial for the formed dimers to remain electronically active. Both characteristics, the improved current collector adhesion and the stabilization due to dimerization, are mutual benefits of thin-film electrodes over powder-based systems. This hypothesis has been further investigated for its potential application in sodium ion batteries. Our results show that AQ thin-film electrodes exhibit significantly better specific capacities (233 vs 87 mAh g -1 in the first cycle), Coulombic efficiencies, and long-term cycling performance (80 vs 4 mAh g -1 after 100 cycles) over the AQ powder electrodes. By augmenting the experimental findings via computational investigations, we are able to suggest design strategies that may foster the performance of industrially desirable powder-based electrode materials., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

In this work 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) is investigated as electrode material for organic Na-ion batteries. Since PTCDI is a widely used industrial pigment, it may turn out to be a cost-effective, abundant, and environmentally benign cathode material for secondary Na-ion batteries. Among other carbonyl pigments, PTCDI is especially interesting due to its high Na-storage capacity in combination with remarkable high rate capabilities. The detailed analysis of cyclic voltammetry measurements reveals a diffusion-less mechanism, suggesting that Na-ion storage in the PTCDI film allows for exceptionally fast charging/discharging rates. This finding is further corroborated by galvanostatic sodiation measurements at high rates of 17 C (2.3 A g -1 ), showing that 57 % of the theoretically possible capacity of PTCDI, or 78 mAh g -1 , are attained in only 3.5 min charging time., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

In this report, we present results on the electrocatalytic activity of conducting polymers [polyaniline (PANI) and polypyrrole (PPy)] toward the electrochemical oxygen reduction reaction (ORR) to hydrogen peroxide (H 2 O 2 ). The electropolymerization of the polymers and electrolysis conditions were optimized for H 2 O 2 production. On flat glassy carbon (GC) electrodes, the faradaic efficiency (FE) for H 2 O 2 production was significantly improved by the polymers. Rotating disc electrode (RDE) studies revealed that this is mainly a result of blocking further H 2 O 2 to the water reduction pathway by the polymers. PPy on carbon paper (CP) significantly increased the molar production of H 2 O 2 by over 250% at an average FE of above 95% compared to bare CP with a FE of 25%. Thus, the polymers are acting as catalysts on the electrode for the ORR, although their catalytic mechanisms differ from other electrocatalysts., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

We report the synthesis and electrochemical properties of freebase tetraphenyltetrabenzoporphyrin and its complexes of Zn(ii), Co(ii), Ni(ii), Cu(ii) and Sn(iv) towards electrochemical reduction of carbon dioxide (CO 2 ). Based on cyclic voltammetry, it is shown that central metals significantly affect the electrocatalytic performance in the reduction of CO 2 in terms of reduction potential and catalytic current enhancement. At an applied potential of -1.90 V vs. an Ag/AgCl quasi reference electrode for 20 h, the electrocatalytic reduction of CO 2 realized by Zn(ii)- and Cu(ii)-tetraphenyltetrabenzoporphyrins to carbon monoxide resulted in faradaic efficiencies of around 48% and 33%, respectively.

Flavins are known to be extremely versatile, thus enabling routes to innumerable modifications in order to obtain desired properties. Thus, in the present paper, the group of bio-inspired conjugated materials based on the alloxazine core is synthetized using two efficient novel synthetic approaches providing relatively high reaction yields. The comprehensive characterization of the materials, in order to evaluate the properties and application potential, has shown that the modification of the initial alloxazine core with aromatic substituents allows fine tuning of the optical bandgap, position of electronic orbitals, absorption and emission properties. Interestingly, the compounds possess multichromophoric behavior, which is assumed to be the results of an intramolecular proton transfer.

In this article, we present the improvement in device performance and stability as well as reduction in hysteresis of inverted mixed-cation-mixed-halide perovskite solar cells (PSCs) using a low temperature, solution processed titanium oxide (TiO x ) interlayer between [6,6]-phenyl-C 61 butyric acid methyl ester (PCBM) and an Al electrode. Upon applying a TiO x interlayer, device resistance was reduced compared to that of the control devices, which results in improved rectification of the characteristic current density-voltage ( J - V ) curve and improved overall performance of the device. PSCs with the TiO x interlayer show an open-circuit voltage ( V oc ) of around 1.1 V, current density ( J sc ) of around 21 mA cm -2 , fill factor (FF) of around 72% and enhanced power conversion efficiency (PCE) of 16% under AM1.5 solar spectrum. Moreover, devices with the TiO x interlayer show improved stability compared to devices without the TiO x interlayer. This finding reveals the dual role of the TiO x interlayer in improving device performance and stability.

We report on a self-assembled system comprising a molecular copper-porphyrin photoelectrocatalyst, 5-(4-carboxy-phenyl)-10,15,20-triphenylporphyrinatocopper(II) (CuTPP-COOH), covalently bound to self-organized, anodic titania nanotube arrays (TiO 2 NTs) for photoelectrochemical reduction of oxygen. Visible light irradiation of the porphyrin-covered TiO 2 NTs under cathodic polarization up to -0.3 V vs. Normal hydrogen electrode (NHE) photocatalytically produces H 2 O 2 in pH neutral electrolyte, at room temperature and without need of sacrificial electron donors. The formation of H 2 O 2 upon irradiation is proven and quantified by direct colorimetric detection using 4-nitrophenyl boronic acid ( p -NPBA) as a reactant. This simple approach for the attachment of a small molecular catalyst to TiO 2 NTs may ultimately allow for the preparation of a low-cost H 2 O 2 evolving cathode for efficient photoelectrochemical energy storage under ambient conditions., Competing Interests: The authors declare no conflict of interest.

A broad review of homogeneous and heterogeneous catalytic approaches toward CO 2 reduction using organic, organometallic, and bioorganic systems is provided. Electrochemical, bioelectrochemical and photoelectrochemical approaches are discussed in terms of their faradaic efficiencies, overpotentials and reaction mechanisms. Organometallic complexes as well as semiconductors and their homogeneous and heterogeneous catalytic activities are compared to enzymes. In both cases, their immobilization on electrodes is discussed and compared to homogeneous catalysts in solution., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Exposure to low-intensity radiation in the near-infrared (NIR) spectral region matching the optically transparent "phototherapeutic window" of biological tissues can be applied to directly populate spin-restricted excited states of light-responsive compounds. This unconventional and unprecedented approach is introduced herein as a new strategy to overcome some of the major unresolved problems observed in the rapidly emerging fields of photopharmacology and molecular photomedicine, where practical applications in living cells and organisms are still limited by undesired side reactions and insufficient light penetration. Water-soluble and biocompatible metal complexes with a significant degree of spin-orbit coupling were identified as target candidates for testing our new hypothesis. As a first example, a dark-stable manganese carbonyl complex acting as a visible-light-triggered CO-releasing molecule (Photo-CORM) is shown to be photoactivated by NIR radiation, although apparently no spectroscopically evident absorption bands are detectable in this low-energy region. This quite remarkable effect is ascribed to a strongly restricted, but obviously not completely forbidden optical population of the lowest triplet excited state manifold of the diamagnetic complex from the singlet ground state., Competing Interests: The authors declare no conflict of interest.

In the recent decade, CO 2 has increasingly been regarded not only as a greenhouse gas but even more as a chemical feedstock for carbon-based materials. Different strategies have evolved to realize CO 2 utilization and conversion into fuels and chemicals. In particular, biological approaches have drawn attention, as natural CO 2 conversion serves as a model for many processes. Microorganisms and enzymes have been studied extensively for redox reactions involving CO 2 . In this review, we focus on monitoring nonliving biocatalyzed reactions for the reduction of CO 2 by using enzymes. We depict the opportunities but also challenges associated with utilizing such biocatalysts. Besides the application of enzymes with co-factors, resembling natural processes, and co-factor recovery, we also discuss implementation into photochemical and electrochemical techniques.

Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO 2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO 2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO 2 . The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO 2 capture of ∼2.3 mmol g -1 . This is on par with the best solution-phase amine chemical capture technologies available today.

Two low molecular weight electroactive donor-acceptor-donor (DAD)-type molecules are reported, namely naphthalene bisimide (NBI) symmetrically core-functionalized with dithienopyrrole (NBI-(DTP) 2 ) and an asymmetric core-functionalized naphthalene bisimide with dithienopyrrole (DTP) substituent on one side and 2-ethylhexylamine on the other side (NBI-DTP-NHEtHex). Both compounds are characterized by low optical bandgaps (1.52 and 1.65 eV, respectively). NBI-(DTP) 2 undergoes oxidative electropolymerization giving the electroactive polymer of ambipolar character. Its two-step reversible reduction and oxidation is corroborated by complementary EPR and UV/Vis-NIR spectroelectrochemical investigations. The polymer turned out to be electrochemically active not only in aprotic solvents but also in aqueous electrolytes, showing a distinct photocathodic current attributed to proton reduction. Additionally, poly(NBI-(DTP) 2 ) was successfully tested as a photodiode material., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The current study reports the application of chalcopyrite semiconductor CuInS 2 (CIS) nanofibers for the reduction of CO 2 to CO with a remarkable Faradaic efficiency of 77 ± 4%. Initially the synthesis of CuInS 2 nanofibers was carried out by adaptable electrospinning technique. To reduce the imperfection in the crystalline fiber, polyacrylonitrile (PAN) was selected as template polymer. Afterward, the desired chemical structure of nanofibers was achieved through sulfurization process. Making continuous CuInS 2 nanofibers on the cathode surface by the electrospinning method brings the advantages of being economical, environmentally safe, and versatile. The obtained nanofibers of well investigated size and diameter according to the SEM (scanning electron microscope) were used in electrochemical studies. An improvement of Faradaic efficiency was achieved with the catalytic active CuInS 2 in nanofibrous structure as compared to the solution processed CuInS 2 . This underlines the important effect of the electrode fabrication on the catalytic performance. Being less contaminated as compared to solution processing, and having a well-defined composition and increased catalytically active area, the CuInS 2 nanofiber electrodes prepared by the electrospinning technique show a 4 times higher Faradaic efficiency. Furthermore, in this study, attention was paid to the stability of the CuInS 2 nanofiber electrodes. The electrochemical reduction of CO 2 to CO by using CIS nanofibers coated onto FTO electrodes was carried out for 10 h in total. The observed current density of 0.22 mA cm -2 and the stability of CIS nanofiber electrodes are found to be competitive with other heterogeneous electrocatalysts. Hence, we believe that the fabrication and application of nanofibrous materials through the electrospinning technique might be of interest for electrocatalytic studies in CO 2 reduction.

Photovoltaic technology requires light-absorbing materials that are highly efficient, lightweight, low cost and stable during operation. Organolead halide perovskites constitute a highly promising class of materials, but suffer limited stability under ambient conditions without heavy and costly encapsulation. Here, we report ultrathin (3 μm), highly flexible perovskite solar cells with stabilized 12% efficiency and a power-per-weight as high as 23 W g(-1). To facilitate air-stable operation, we introduce a chromium oxide-chromium interlayer that effectively protects the metal top contacts from reactions with the perovskite. The use of a transparent polymer electrode treated with dimethylsulphoxide as the bottom layer allows the deposition-from solution at low temperature-of pinhole-free perovskite films at high yield on arbitrary substrates, including thin plastic foils. These ultra-lightweight solar cells are successfully used to power aviation models. Potential future applications include unmanned aerial vehicles-from airplanes to quadcopters and weather balloons-for environmental and industrial monitoring, rescue and emergency response, and tactical security applications.

Limiting anthropogenic carbon dioxide emissions constitutes a major issue faced by scientists today. Herein we report an efficient way of controlled capture and release of carbon dioxide using nature inspired, cheap, abundant and non-toxic, industrial pigment namely, quinacridone. An electrochemically reduced electrode consisting of a quinacridone thin film (ca. 100 nm thick) on an ITO support forms a quinacridone carbonate salt. The captured CO2 can be released by electrochemical oxidation. The amount of captured CO2 was quantified by FT-IR. The uptake value for electrochemical release process was 4.61 mmol g(-1). This value is among the highest reported uptake efficiencies for electrochemical CO2 capture. For comparison, the state-of-the-art aqueous amine industrial capture process has an uptake efficiency of ca. 8 mmol g(-1)., (© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.)

We have developed a hole-blocking layer for bulk-heterojunction solar cells based on cross-linked polyethylenimine (PEI). We tested five different ether-based cross-linkers and found that all of them give comparable solar cell efficiencies. The initial idea that a cross-linked layer is more solvent resistant compared to a pristine PEI layer could not be confirmed. With and without cross-linking, the PEI layer sticks very well to the surface of the indium-tin-oxide electrode and cannot be removed by solvents used to process PEI or common organic semiconductors. The cross-linked PEI hole-blocking layer functions for multiple donor-acceptor blends. We found that using cross-linkers improves the reproducibility of the device fabrication process.