Back Reactions Research Articles

Anchoring MnWO4 Nanorods on LaTiO2N Nanoplates for Boosted Visible Light-Driven Overall CO2 Reduction.

The photocatalytic conversion of CO2 into hydrocarbon fuel holds immense potential for achieving a carbon closed loop and carbon neutrality. Developing efficient photocatalysts plays a pivotal role in enabling the widespread application of photocatalytic CO2 reduction on a large scale. Herein, a novel S-scheme MnWO4/LaTiO2N heterojunction composite is successfully synthesized by a hydrothermal method. This composite catalyst demonstrates excellent photocatalytic activity in the reduction of CO2 to CO and CH4 using water molecules as electron donors under visible light irradiation, and the optimized 30% MnWO4/LaTiO2N composite displays significantly enhanced CO and CH4 yields of 3.94 and 0.81 μmol g-1 h-1, respectively, and the corresponding utilized photoelectron number reaches 14.7 μmol g-1 h-1, which is approximately 7.7 and 12.9 times that of LaTiO2N and MnWO4. The enhancement in photocatalytic activity of the composites can be ascribed to the construction of an S-scheme heterojunction, which exhibits improved charge transfer dynamics, retains the strongest redox capacity, and effectively suppresses back reactions. In situ Fourier-transform infrared imaging provides evidence, to a certain extent, for the existence of a temporal gradient order in the generation of multiple products during the photocatalytic reduction of CO2.

Triplet-Sensitized Switching of High-Energy-Density Norbornadienes for Molecular Solar Thermal Energy Storage with Visible Light.

Norbornadiene-based photoswitches have emerged as promising candidates for harnessing and storing solar energy, holding great promise as a viable solution to meet the growing energy demands. Despite their potential, the effectiveness of their direct photochemical conversion into the resulting quadricyclanes has room for improvement owing to (i) moderate quantum yields, (ii) poor overlap with the solar spectrum and (iii) photochemical back reactions. Herein, we present an approach to enhance the performance of such molecular solar thermal energy storage (MOST) systems through the triplet-sensitized conversion of aryl-substituted norbornadienes. Our study combines deep spectroscopic analyses, irradiation experiments, and quantum mechanical calculations to elucidate the energy transfer mechanism and inherent advantages of the resulting MOST systems. We demonstrate remarkable quantum yields using readily available sensitizers under both LED and solar light irradiation, significantly surpassing those achieved through direct excitation with photons of higher energy. In contrast to the conventional approach, light-induced back reactions of the high-energy products do not play any role, allowing quantitative switching within minutes. These results not only underscore the potential of triplet-sensitized MOST systems to leverage the high energy storage capabilities of multistate photoswitches but they might also stimulate the broader usage of sensitization strategies in photochemical energy conversion.

Triplet‐Sensitized Switching of High‐Energy‐Density Norbornadienes for Molecular Solar Thermal Energy Storage with Visible Light

Norbornadiene‐based photoswitches have emerged as promising candidates for harnessing and storing solar energy, holding great promise as a viable solution to meet the growing energy demands. Despite their potential, the effectiveness of their direct photochemical conversion into the resulting quadricyclanes has room for improvement owing to (i) moderate quantum yields, (ii) poor overlap with the solar spectrum and (iii) photochemical back reactions. Herein, we present an approach to enhance the performance of such molecular solar thermal energy storage (MOST) systems through the triplet‐sensitized conversion of aryl‐substituted norbornadienes. Our study combines deep spectroscopic analyses, irradiation experiments, and quantum mechanical calculations to elucidate the energy transfer mechanism and inherent advantages of the resulting MOST systems. We demonstrate remarkable quantum yields using readily available sensitizers under both LED and solar light irradiation, significantly surpassing those achieved through direct excitation with photons of higher energy. In contrast to the conventional approach, light‐induced back reactions of the high‐energy products do not play any role, allowing quantitative switching within minutes. These results not only underscore the potential of triplet‐sensitized MOST systems to leverage the high energy storage capabilities of multistate photoswitches but they might also stimulate the broader usage of sensitization strategies in photochemical energy conversion.

(Invited) Two-Dimensional Metal–Organic Framework Acts As a Hydrogen Evolution Cocatalyst for Overall Photocatalytic Water Splitting

Water-splitting semiconductor photocatalysts require hydrogen evolution reaction (HER) cocatalysts, the majority of which are robust metals and metal oxides. Metal complexes feature designability and reaction selectivity. This feature should be appreciated in the application as HER cocatalysts by suppressing unfavorable back reactions; however, low stability hampers their application. In this research, we demonstrate that a fully π-conjugated and conductive two-dimensional metal–organic framework (2D MOF), which possesses both virtues of metals/metal oxides and metal complexes, serves as an ideal HER cocatalyst candidate. NiBHT, a kind of 2D MOF, is deposited on the photocatalyst SrTiO3:Al with CoO x as an oxygen evolution cocatalyst to show long-term overall one-step water splitting with an apparent quantum efficiency (AQE) of 6.5% at 350 nm. In comparison to Pt as a representative HER cocatalyst, NiBHT turns out to be a suppressor of back reactions related to oxygen reduction reactions, which is proven both experimentally and theoretically.

Efficient and stable visible-light-driven Z-scheme overall water splitting using an oxysulfide H2 evolution photocatalyst

So-called Z-scheme systems permit overall water splitting using narrow-bandgap photocatalysts. To boost the performance of such systems, it is necessary to enhance the intrinsic activities of the hydrogen evolution photocatalyst and oxygen evolution photocatalyst, promote electron transfer from the oxygen evolution photocatalyst to the hydrogen evolution photocatalyst, and suppress back reactions. The present work develop a high-performance oxysulfide photocatalyst, Sm2Ti2O5S2, as an hydrogen evolution photocatalyst for use in a Z-scheme overall water splitting system in combination with BiVO4 as the oxygen evolution photocatalyst and reduced graphene oxide as the solid-state electron mediator. After surface modifications of the photocatalysts to promote charge separation and redox reactions, this system is able to split water into hydrogen and oxygen for more than 100 hours with a solar-to-hydrogen energy conversion efficiency of 0.22%. In contrast to many existing photocatalytic systems, the water splitting activity of the present system is only minimally reduced by increasing the background pressure to 90 kPa. These results suggest characteristics suitable for applications under practical operating conditions.

Fast photochromism of helicene-bridged imidazole dimers.

The unique optical and magnetic properties of organic biradicaloids on polycyclic aromatic hydrocarbons are of fundamental interest in the development of novel organic optoelectronic materials. Open-shell π-conjugated molecules with helicity have recently attracted a great deal of attention due to the magnetic-field-dependence and spin-selectivity arising from the combination of helical chirality and electron spins. However, the molecular design for helical biradicaloids is limited due to the thermal instability and high reactivity. Herein, we achieved fast photochromic reactions and reversible photo-generation of biradical species using helicene-bridged imidazole dimers. A [9]helicene-bridged imidazole dimer exhibits reversible photochromism upon UV light irradiation. The transient species produced reversibly by UV light irradiation exhibited ESR spectra with a fine structure characteristic of a triplet radical pair, indicating the reversible generation of the biradical. The half-life of the thermal recombination reaction of the biradical was estimated to be 29 ms at 298 K. Conversely, a substantial activation energy barrier was confirmed for the intramolecular recombination reaction in the [7]helicene-bridged imidazole dimer, attributed to the extended pitch length of [7]helicene. The temperature dependence of the thermal back reactions revealed that the [7]helicene and [9]helicene moieties functioned as 'soft' and 'hard' molecular bridges, respectively. These findings pave the way for future advances in the development of photoswitchable helical biradicaloids.

Photodoping-based broadband photochromism of semiconductor nanocrystals under air operated by a supramolecular gel.

We herein report photodoping and thereby photochromism of semiconductor nanocrystals under air in a temperature-responsive supramolecular gel and its back reactions induced by direct heating or near-infrared photothermal conversion. We also present their application to the spatiotemporal patterning of photoluminescence.

Tandem Semiconductor Microwire Slurries for Solar Hydrogen Generation

Meeting the industry goal of $2/kg for solar H2 is a daunting task that will require novel, highly efficient systems which eliminate many of the components and balance-of-systems costs inherent with photovoltaics + electrolyzers. Technoeconomic models have consistently shown that a photoactive slurry reactor for water-splitting could offer the cheapest route to storing solar energy as hydrogen fuel. However, abundant challenges with this approach have thus far limited such particle-based reactors to prohibitively low efficiencies. This talk will highlight our progress toward the development of a tandem semiconductor particle system designed to address the weaknesses of slurry reactors and achieve a high solar-to-hydrogen (STH) efficiency for particle systems. A proof-of-concept tandem structure uses silicon microwires as the base of the particle, with a wider bandgap TiO2 layer grown on top to gain the additional photovoltage necessary to split water. Semiconductor architecture development and performance will be discussed along with early modeling efforts. In-situ magnetic alignment of the particles has been demonstrated for possible improved tandem light management. In addition, slurry optical characterization and photoelectrochemical performance will be discussed as a function of slurry parameters including bubble flowrate, particle concentration, spectral conditions, and light management strategies. Slurry conditions for minimizing back reactions will be discussed as well.

Molecular Wind-Up Meter for the Quantification of London Dispersion Interactions.

ConspectusThe experimental quantification of interactions on the molecular level provides the necessary basis for the design of functional materials and chemical processes. The interplay of multiple parameters and the small quantity of individual interactions pose a special challenge for such endeavors. The common method is the use of molecular balances, which can exist in two different states. Thereby, a stabilizing interaction can occur in one of the states, favoring its formation and thus affecting the thermodynamic equilibrium of the system. One challenge is determining the change in this equilibrium since various analytical methods could not be applied to fast-changing equilibria. A new and promising method for quantifying molecular interactions is the use of Molecular Wind-up Meters (MWM) in which the change in kinetics, rather than the effect on thermodynamics, is investigated. An MWM is transformed with an energy input (e.g. irradiation) into a metastable state. Then, the rate of thermal transformation back to the ground state is measured. The strength of interactions present in the metastable state controls the kinetics of the back reactions, allowing direct correlation. The advantage of this approach lies in the high sensitivity (energy differences can be larger by 1 order of magnitude) and, in general, allows the use of a broader range of solvents and analytical methods. An Azobenzene-based MWM has been established as a powerful tool to quantify London dispersion interactions. London dispersion (LD) represents the attractive part of the van der Waals potential. Although neglected in the past due to its weak character, it has been shown that the influence of LD on the structure, stability, and reactivity of matter can be decisive. Especially in larger molecules, its energy contribution increases overproportionately with the number of atoms, which has sparked increasing interest in the use of so-called dispersion energy donors (DED) as a new structural element. Application of the azobenzene-based MWM not only allowed the differentiation of bulkiness, but also systematically addressed the influence of the length of n-alkyl chains. Additionally, the solvent influence on LD was studied. Based on the azobenzene MWM, an increment system has been proposed, allowing a rough estimate of the effect of a specific DED.

Continuous Anhydrous Synthesis of Oxymethylene Dimethyl Ethers by Reaction of Dimethyl Ether with Molecular Formaldehyde.

A novel gaseous synthesis route to oxymethylene dimethyl ethers (OMEn, n = 3-5) starting from CO2 and green H2 by using molecular formaldehyde (FA) and dimethyl ether (DME) is presented. The anhydrous reaction runs in a pressure free, gaseous, and continuous reaction setup. Hetero-geneous cata-lysts including zeolites and ion exchange resins (IER) are investigated, if they catalyze this reaction. While IER is almost inactive, zeolites with a 3D pore structure and an acidity exceeding ρm,H+(NH3,ads) = 250 µmol·gcat.-1 proved to be catalytically active. DME conversions of up to 2.76 mol-% are observed. The observed product gas stream compositions confirm thermo-dynamic considerations with back reactions / OMEn decomposition occurring as part of the equilibria under the investigated reaction conditions (90…180 °C). However, feed gas ratio variations (FA:DME = 1:2 to 1:9.5) highlighted the possibility to shift the product selectivity in favor of OMEn and suppress FA disproportionation to methyl formate. FA trimerization to trioxane is almost completely suppressed by running the reaction at 120 °C. The results presented here provide an important and unprecedented contribution to understand the complex reaction network in the OMEn synthesis reaction necessary to establish an energy efficient sustainable OMEn production process.

H2 Production from NH3 in a BaTiO3 Moderated Ferroelectric Packed-Bed Plasma Reactor

Plasma decomposition reactions are used for various gas phase chemical processes including the decomposition of ammonia. In this work we show that pure ammonia can be effectively decomposed at atmospheric pressure and ambient temperature using a packed-bed plasma reactor moderated with BaTiO3 ferroelectric pellets without catalyst. The decomposition rate and energy efficiency of this ferroelectric barrier discharge reactor have been monitored as a function of applied voltage (up to a maximum value of 2.5 kV) and flow rate. For each operating condition reaction efficiencies have been correlated with the parameters defining the electrical response of the reactor. It is found that plasma current and volume inside the reactor and hence the energy efficiency of the process and the decomposition rate vary with the applied voltage and the flow of ammonia (a maximum decomposition rate of 14% and an energy efficiency of 150 LH2/kWh has been determined under optimized operation conditions). The role of back reactions (i.e. N2 + 3H2 → 2NH3) in decreasing reactor performance is another key effect affecting the overall efficiency for the ammonia decomposition. The possibilities of ferroelectric barrier discharge reactors to induce the decomposition of ammonia and the importance of keeping the operating temperature below the Curie temperature of the ferroelectric material are highlighted.

Selective control of donor-acceptor Stenhouse adduct populations with non-selective stimuli

Selective control of donor-acceptor Stenhouse adduct populations with non-selective stimuli

Validation of non-equilibrium kinetics in CO2–N2 plasmas

This work explores the effect of N2 addition on CO2 dissociation and on the vibrational kinetics of CO2 and CO under various non-equilibrium plasma conditions. A self-consistent kinetic model, previously validated for pure CO2 and CO2–O2 discharges, is further extended by adding the kinetics of N2. The vibrational kinetics considered include levels up to v = 10 for CO, v= 59 for N2 and up to v 1= 2 and v 2= v 3= 5, respectively for the symmetric stretch, bending and asymmetric stretch modes of CO2, and account for electron-impact excitation and de-excitation (e–V), vibration-to-translation (V–T) and vibration-to-vibration energy exchange (V–V) processes. The kinetic scheme is validated by comparing the model predictions with recent experimental data measured in a DC glow discharge operating in pure CO2 and in CO2–N2 mixtures, at pressures in the range 0.6–4 Torr (80.00–533.33 Pa) and a current of 50 mA. The experimental results show a higher vibrational temperature of the different modes of CO2 and CO and an increased dissociation fraction of CO2, that can reach values as high as 70%, when N2 is added to the plasma. On the one hand, the simulations suggest that the former effect is the result of the CO2–N2 and CO–N2 V–V transfers and the reduction of quenching due to the decrease of atomic oxygen concentration; on the other hand, the dilution of CO2 and dissociation products, CO and O2, reduces the importance of back reactions and contributes to the higher CO2 dissociation fraction with increased N2 content in the mixture, while the N2(B3Πg) electronically excited state further enhances the CO2 dissociation.

Bismuth-Based Multi-Component Heterostructured Nanocatalysts for Hydrogen Generation

Developing a unique catalytic system with enhanced activity is the topmost priority in the science of H2 energy to reduce costs in large-scale applications, such as automobiles and domestic sectors. Researchers are striving to design an effective catalytic system capable of significantly accelerating H2 production efficiency through green pathways, such as photochemical, electrochemical, and photoelectrochemical routes. Bi-based nanocatalysts are relatively cost-effective and environmentally benign materials which possess advanced optoelectronic properties. However, these nanocatalysts suffer back recombination reactions during photochemical and photoelectrochemical operations which impede their catalytic efficiency. However, heterojunction formation allows the separation of electron–hole pairs to avoid recombination via interfacial charge transfer. Thus, synergetic effects between the Bi-based heterostructured nanocatalysts largely improves the course of H2 generation. Here, we propose the systematic review of Bi-based heterostructured nanocatalysts, highlighting an in-depth discussion of various exceptional heterostructures, such as TiO2/BiWO6, BiWO6/Bi2S3, Bi2WO6/BiVO4, Bi2O3/Bi2WO6, ZnIn2S4/BiVO4, Bi2O3/Bi2MoO6, etc. The reviewed heterostructures exhibit excellent H2 evolution efficiency, ascribed to their higher stability, more exposed active sites, controlled morphology, and remarkable band-gap tunability. We adopted a slightly different approach for reviewing Bi-based heterostructures, compiling them according to their applicability in H2 energy and discussing challenges, prospects, and guidance to develop better and more efficient nanocatalytic systems.

Triplet states in the reaction center of Photosystem II.

In oxygenic photosynthesis sunlight is harvested and funneled as excitation energy into the reaction center (RC) of Photosystem II (PSII), the site of primary charge separation that initiates the photosynthetic electron transfer chain. The chlorophyll ChlD1 pigment of the RC is the primary electron donor, forming a charge-separated radical pair with the vicinal pheophytin PheoD1 (ChlD1+PheoD1-). To avert charge recombination, the electron is further transferred to plastoquinone QA, whereas the hole relaxes to a central pair of chlorophylls (PD1PD2), subsequently driving water oxidation. Spin-triplet states can form within the RC when forward electron transfer is inhibited or back reactions are favored. This can lead to formation of singlet dioxygen, with potential deleterious effects. Here we investigate the nature and properties of triplet states within the PSII RC using a multiscale quantum-mechanics/molecular-mechanics (QM/MM) approach. The low-energy spectrum of excited singlet and triplet states, of both local and charge-transfer nature, is compared using range-separated time-dependent density functional theory (TD-DFT). We further compute electron paramagnetic resonance properties (zero-field splitting parameters and hyperfine coupling constants) of relaxed triplet states and compare them with available experimental data. Moreover, the electrostatic modulation of excited state energetics and redox properties of RC pigments by the semiquinone QA- is described. The results provide a detailed electronic-level understanding of triplet states within the PSII RC and form a refined basis for discussing primary and secondary electron transfer, charge recombination pathways, and possible photoprotection mechanisms in PSII.

Ultrathin electron and proton-conducting membranes for nanoscale integrated artificial photosystems

Ultrathin separation membranes of ten nanometer thickness capable of separating small molecules for avoiding back reactions while providing adequate electron and proton transport enable the development of nanoscale integrated artificial photosystems.

New A3B-type naphthyl Zn(II) porphyrins as DSSC dyes: Effect of anchoring group and co-adsorption for enhanced efficiency

Two new Zn(II) porphyrin dyes ZnNPCA and ZnNPHy bearing three naphthyl groups and one carboxyphenyl/hydroxyphenyl anchoring group in an A3B meso substitution pattern was synthesized utilizing a mixed condensation approach. The redshifted absorption bands to 427 nm as impacts on the extended conjugation with three naphthyl substituents. Similarly, the emission spectrum also exhibits a redshift than ZnTPP-COOH dye. The anodic shift was found in the reduction potential of the naphthyl dyes with the carboxylic acid anchor (ZnNPCA), facilitating the more favourable electron injection. Moreover, the naphthyl porphyrin dyes positively interacted with semiconducting TiO2, whose binding mode was further established using FT-IR. While interacting with titania, the more broadening absorption spectra exhibit strong electronic coupling and will benefit the electron injection. The high dye loading amount obtained for ZnNPCA dye was 13.1 × 10−8 mol cm2, which is more significant towards light harvesting. DSSC devices were fabricated using porphyrin-sensitized photoanodes. ZnNPCA showed better efficiency than ZnNPHy owing to higher dye loading onto the titania surface. Furthermore, the influence of co-adsorbent DCA on the photovoltaic performance of the fabricated DSSC devices was investigated. As a result, a maximum efficiency of 1.85% was achieved for ZnNPCA/DCA device. In addition, electrochemical impedance spectroscopy results revealed a higher electron lifetime (6.14 ms) for this device, supporting better suppression of back reactions.

(Invited) Semipermeable Oxide Coatings for Selective Z-Scheme Photocatalytic Water Splitting

Similar to natural photosynthesis, Z-scheme photocatalytic water splitting relies on two different light absorbing components that are coupled by a redox active mediator that shuttles charge between them. Such a two-absorber system possesses several advantages over single absorber photocatalytic system, including higher theoretical solar-to-hydrogen conversion efficiency, relaxed band alignment requirements, and the potential for inherently safe operation whereby H2 and O2 evolution occur in separated compartments. However, a major disadvantage and challenge for Z-scheme photocatalysis is that the presence of a redox mediator introduces two undesirable back-reactions on top of parasitic H2 oxidation and O2 reduction reactions that can occur in a single absorber photocatalytic system. Previous research efforts have identified the use of semi-permeable oxide coatings as an attractive approach to suppress these thermodynamically favored redox reactions while still permitting the desired water splitting and mediator redox reactions to occur. Here, we present a combined experimental and computational approach based on model thin films that is used to (i) probe the performance limits of oxide-encapsulated photocatalysts, (ii) quantify the effects of coating defects on performance, and (iii) guide the rational design of coatings aimed at maximizing the solar-to-hydrogen conversion efficiency of a target photocatalytic system. This work specifically focusses on the development of silicon and titanium oxide coatings for Z-scheme water splitting based on a Fe(II)/Fe(III) mediator, showing that the best coatings can achieve selectivities > 90 % towards the H2 and O2 evolution reactions over undesired Fe(II)/Fe(III) back reactions. Another key finding from this work is that coating defects can have a significant influence on the performance of encapsulated electrodes, as revealed by scanning electrochemical microscopy (SECM) measurements that were used to locally quantify the parasitic back reaction rates around individual defects to determine their impact on the global selectivity of an encapsulated electrode.

Relieving string tension by making baby universes in a dynamical string tension braneworld model

String tension fundamentally determines the properties of strings; yet its value is often assigned arbitrarily, creating a fine-tuning problem. We describe a mechanism for dynamically generating string tension in a flat or almost flat spacetime, using the ‘modified measures formalism’, which in turn naturally generates a new type of stringy braneworld scenario. Such a scenario allows strings to achieve near infinite tension confining the strings to two very close expanding surfaces, but the infinite tensions also threaten to distort the near-flat embedding spacetime through large back reactions. We argue that this danger can be neutralized via the creation of a baby universe — a growing region of embedding spacetime that divorces from the ambient embedding spacetime, while our universe is still a brane separating two nearly flat spacetimes. The avoidance of a minimum length and a maximum Hagedorn temperature in the context of dynamical string tension generation is also discussed.

CuWO4 as a novel Z-scheme partner to construct TiO2 based stable and efficient heterojunction for photocatalytic hydrogen generation

Synthesis of highly efficient, stable, visible active CuWO4 nanoparticles through a simple methodology, paves a feasible path for enhancing the efficiency of TiO2. A novel nanocomposite of CuWO4 NP loaded TiO2 NR heterojunction was mounted through a direct Z-scheme mechanism. Optimized composite CWT-3, advances the photocatalytic hydrogen production rates of TiO2 to 106.7 mmol h−1 g−1cat. CuWO4 incorporation as OEP compensates inefficiency of WO3 and other Z-scheme combinations reported so far, on limiting the charge carrier recombination followed by the generation of a greater number of excitons. Specific amounts of catalyst loading, study on the effect of sacrificial reagents, and understanding the effect of the light source, are the three pivotal steps that helped here to hamper the density of overall back reactions. The formation of Z-scheme heterojunction was evidently confirmed on determining the position of CBM and VBM, PL and photoelectrochemical analysis. Recyclability studies further proved the stable and efficient outcomes of CWT-3 for five consecutive cycles. Based on photocatalytic activity, employing BDF by-product glycerol as an optimized sacrificial reagent serves the oxidation demands and triggered 53.26% solar to hydrogen conversion efficiency under natural sunlight irradiation.