Successive Reaction Research Articles

Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures.

The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100ps) and electron (∼1ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures.

Research Progress of Heavy-Metal-Free Quantum Dot Light-Emitting Diodes

At present, heavy-metal-free quantum dot light-emitting diodes (QLEDs) have shown great potential as a research hotspot in the field of optoelectronic devices. This article reviews the research on heavy-metal-free quantum dot (QD) materials and light-emitting diode (LED) devices. In the first section, we discussed the hazards of heavy-metal-containing quantum dots (QDs), such as environmental pollution and human health risks. Next, the main representatives of heavy-metal-free QDs were introduced, such as InP, ZnE (E=S, Se and Te), CuInS2, Ag2S, and so on. In the next section, we discussed the synthesis methods of heavy-metal-free QDs, including the hot injection (HI) method, the heat up (HU) method, the cation exchange (CE) method, the successful ionic layer adsorption and reaction (SILAR) method, and so on. Finally, important progress in the development of heavy-metal-free QLEDs was summarized in three aspects (QD emitter layer, hole transport layer, and electron transport layer).

Formation of a potential barrier by a ZnSXSe1−X electron-blocking layer to improve the efficiency of CdSe0.3S0.7/CdSe quantum dot sensitized solar cells

We designed and fabricated multilayer quantum dots sensitized solar cells (QDSCs) with TiO2 NPs/CdSe0.3S0.7/CdSe/ZnSXSe1−X, X = S/S + Se = 0, 0.7, 0.8, 0.9, and 1 photoelectrodes to achieve optimum power conversion efficiency (PCE). In the corresponding structure, incoming light is absorbed by the CdSe0.3S0.7 and CdSe quantum dots (QDs), while the ZnSXSe1−X QDs act as an electron blocking layer or passivation layer, forming an energy barrier that restricts electron mobility from the light absorbers to the polysulfide electrolyte. The beneficial effect of the alloyed ZnSXSe1−X layer is the adjustability of its nanoparticle size/bandgap energy proportional to variations in the concentration of anionic precursors X, according to optical results. The PCE value of the reference cell with the TiO2 NPs/CdSe0.3S0.7/CdSe photoanode is 4.15 %. Following the coating of ZnSe, ZnS0.7Se0.3, ZnS0.8Se0.2, ZnS0.9Se0.1, and ZnS QDs via two successive ionic layer adsorption and reaction (SILAR) cycles (2Sc) on the CdSe0.3S0.7/CdSe co-sensitized photoelectrode increasing stability and improving the PCE value to 4.9 %, 5.40 %, 5.70, 5.25 %, and 5.05 %, respectively. Next, by modifying the thickness of the champion cell's passivation layer, the QDSCs with TiO2 NPs/CdSe0.3S0.7/CdSe/ZnS0.8Se0.2 (3Sc) photoelectrode exhibit maximum photovoltaic performance parameters of short circuit current density (JSC) = 26.25 mA/cm2, open circuit voltage (VOC) = 560 mV, fill factor (FF) = 0.42 % and PCE = 6.15 %. This improvement in performance is the result of decreased internal energy loss and recombination of charge carriers at the interface between the electrolyte and photoelectrode, which increases electron collection efficiency and electron injection efficiency in the visible region according to the external and internal quantum efficiency curves.

Exceeding Three-Electron Reactions in Polyanionic Cathode To Achieve High-Energy Density for Sodium-Ion Batteries.

Activating multielectron reactions of sodium superionic conductor (NASICON)-type cathodes toward higher energy density remains imperative to boost their application feasibility. However, multisodium storage with high stability is difficult to achieve due to the sluggish reaction kinetics, irreversible phase transitions, and negative structural degradation. Herein, a kind of NASICON-type Na2.5V1.5Ti0.5(PO4)3/C (NVTP-0.5) hierarchical microsphere consisting of abundant primary nanoparticles is designed, realizing a reversible 3.2-electron reaction with high stability. The optimized NVTP-0.5 cathode demonstrates an ultrahigh discharge capacity of 192.42 mAh g-1, energy density of up to 497.3 Wh kg-1 at 20 mA g-1, and capacity retention ratio of 94.1% after 1000 cycles at 1 A g-1. Additionally, the NVTP-0.5 cathode delivers excellent tolerance to extreme temperatures while also achieving a high-energy density of 400 Wh kg-1 (based on the cathode mass) in a full-cell configuration. Systematic in situ/ex situ analysis results confirm the multisodium storage processes of NVTP-0.5 involving successive redox reactions (V2+/V3+, Ti3+/Ti4+, and V3+/V4+ redox couples) and reversible structure evolution (solid-solution and biphasic mechanisms), which contribute to the high capacity and excellent cycling stability. This work indicates that the rational regulation of components with different functions can unlock more possibilities for the development of NASICON-type cathodes.

Modified successive ionic layer adsorption and reaction for interconnected bismuth vanadate nanograins: Highly active visible light harvesting photoanodes

A modified successive ionic layer adsorption and reaction (SILAR) method is developed for depositing interconnected bismuth vanadate (BiVO4) nanoparticles with improved visible light harvesting activity. Facile control of preparative parameters like deposition cycles, anionic precursor, pH and deposition temperature significantly altered BiVO4 surface morphology. BiVO4 thin films prepared with Na3VO4 anionic precursor show dispersed nanoparticles type morphology and that deposited with NaVO3 precursor displays 3D interconnected nanoparticles morphology. The BiVO4 photoanodes with 3D interconnected nanoparticles morphology exhibits an excellent photocurrent density of 5.19 mA cm−2 at 1.23 V vs. RHE with superior photostability and improved applied bias photon to current efficiency (ABPE) (1.50 %) compared to dispersed nanostructured BiVO4 photoanodes. The excellent photoelectrochemical (PEC) characteristics of BiVO4 photoanodes with 3D interconnected nanoparticle morphology can be ascribed to porous morphology, optimum thickness, narrow band gap energy and favorable electronic band structure for water splitting. The current study illustrates the usefulness of the modified SILAR approach for depositing 3D interconnected BiVO4 nanoparticle morphology in a single step that is superior and efficient to previously reported multistep processes.

Coating effect of metal organic complex (Co-DTPMP) layer on enhancing PEC water oxidation performance of BiVO4 photoanode

Photoelectrochemical (PEC) water splitting is a promising method for transforming solar energy into clean and sustainable energy. However, PEC is severely limited, and they cannot achieve the predicted photocurrent density owing to the severe photochemical deterioration of the electrode and the recombination of photogenerated carriers. In this study, BiVO4/Co-diethylenetriamine Penta (methylene phosphonic acid) (BVO/Co-DTPMP) co-catalyst was successfully prepared as a nanoporous photoanode. Diethylenetriamine Penta (methylene phosphonic acid) was crosslinked with Co ions and coated on the BiVO4 surface by successive ionic layer adsorption and reaction (SILAR) to reduce fast recombination, which correlated with the BiVO4 photoanode. Various characterization and PEC measurements were conducted, revealing that the co-catalyst thin layer enhanced the charge separation and electrons transfer which significantly affected on the PEC performance of BiVO4, and the current density by BVO/Co-DTPMP was 4 mA cm−2 at 1.23 V vs. RHE. Furthermore, the co-catalyst exhibited improved charge transport and long-term stability.

A core/shell Bi2S3/BiVO4 nanoarchitecture for efficient photoelectrochemical water oxidation.

The construction of nanostructured heterostructure is a potent strategy for achieving high-performance photoelectrochemical (PEC) water splitting. Among these, constructing BiVO4-based heterostructure stands out as a promising method for optimizing light-harvesting efficiency and reducing severe charge recombination. Herein, we present a novel approach to fabricate a type II heterostructure of core/shell Bi2S3/BiVO4 using electrolytic deposition and successive ionic layer adsorption and reaction (SILAR) methods. We identify the type II heterostructure and the difference in fermi energy using UV-Vis spectroscopy, X-ray photoelectron spectroscopy, and PEC measurements. This redistribution of charges due to the fermi energy difference induces an interfacial built-in electric field from BiVO4 to Bi2S3, reinforcing the photogenerated hole transfer kinetics from BiVO4 to Bi2S3. The Bi2S3/BiVO4 heterostructure exhibits a superior photocurrent (6.0 mA cm-2), enhanced charge separation efficiency (85%), and higher open-circuit photovoltage (350 mV). Additionally, the heterostructure displays a prolonged average lifetime of charge (1.63 ns), verifying this heterojunction could boost interfacial carriers' migration via an additional nonradiative quenching pathway. Furthermore, the lower photoluminescence (PL) intensity demonstrates the interfacial built-in electric field is beneficial for boosting charge migration.

Formation of Volatile Pyrazinones in the Asparagine Maillard Reaction Systems and Novel Pyrazinone Formation Pathways in the Amidated-Alanine Maillard Reaction Systems.

Maillard reaction (MR) plays a pivotal role in the food flavor industry, including a cascade of reactions starting with the reaction between amino compounds and reducing sugars, and thus provides various colors and flavors. A new group of volatile compounds called pyrazinones found in MR are now getting more attention. In this study, eight volatile pyrazinones were found in the asparagine MR systems, in which 3,5-dimethyl- and 3,6-dimethyl-2(1H)-pyrazinones were reported for the first time. The major formation pathways were the reactions between asparagine and α-dicarbonyls, with decarboxylation as a critical step. Besides, novel alternative pathways involving alanine amidation and successive reactions with α-dicarbonyls were explored and successfully formed eight pyrazinones. The major differences between alanine-amidated pathways and decarboxylation pathways are the amidation step and absence of the decarboxylation step. For the alanine-amidated pathways, the higher the temperature, the better the amidation effect. The optimal amidation temperature was 200 °C in this study. The reaction between the alanine amide and α-dicarbonyls after amidation can happen at low temperatures, such as 35 and 50 °C, proposing the possibility of pyrazinone formation in real food systems. Further investigations should be conducted to investigate volatile pyrazinones in various food systems as well as the biological effects and kinetic formation differences of the volatile pyrazinones.

Highly stable flexible ozone gas sensors using Mn3O4 nanoparticles-decorated IGZO thin films through the SILAR method

Metal or semiconductor nanoparticles (NPs) can enhance the device performance of gas sensors due to their high surface area and unique electronic properties. However, this method requires additional thermal bonding with high temperatures to secure the NPs, making it unsuitable for flexible substrates. In this study, we develop a room-temperature flexible ozone (O3) gas sensor using Mn3O4 NPs on an amorphous InGaZnO (a-IGZO) film. The Mn3O4 NPs are synthesized by a successive ionic layer adsorption and reaction (SILAR) method at low temperatures. The sensor with Mn3O4 NPs exhibits a gas response of 4.06 against 5 ppm O3 gas at room temperature, which is much higher than that of its pristine counterpart. It also shows excellent selectivity for O3 over toxic gases and maintains stability over 60 days, with reproducible folding even after 500 bending cycles. Thus, the combination of SILAR-synthesized Mn3O4 NPs and a-IGZO films provides an effective way to fabricate flexible O3 gas sensors.

Fabrication and Characterization of ZnWO4/CoWO4 Heterojunction for Multispectral Photodetection on Flexible Substrate

Flexible photodetectors hold significant interest across diverse applications, such as imaging, communication, healthcare, and environmental monitoring. This work reports a broad-band photodetector comprising Zinc tungstate (ZW) and Cobalt tungstate (CW) on a flexible paper substrate. CW thin film was fabricated by a facile successive ionic layer adsorption and reaction(SILAR) technique and the ZW nanoparticles, synthesised via simple co-precipitation method, were drop casted on it to form a heterojunction. Structural characterization of the materials was conducted using X-ray diffraction (XRD), Raman spectroscopy, and Fourier-transform infrared spectroscopy (FTIR), while scanning electron microscopy was employed for detailed morphology analysis. CW is a p type semiconductor with its bandgap of 2.6eV, exhibits impressive sensitivity across both visible and infrared segments of the electromagnetic spectrum. In contrast, ZW which is n type contributes UV-responsive, attributes effectively broadening the overall spectral sensitivity from Ultraviolet (UV) to Infrared (IR) spectra within a single compact device. The photodetector demonstrates remarkable responsivity of 1.66mA/W (UV), 24.58mA/W (Visible), and 0.024mA/W (IR) under respective light intensities of 0.6mW/cm², 0.4mW/cm², and 4.41mW/cm. The detectivity metrics are equally impressive, measuring at 9.9×1010 Jones (UV), 5.01×1011 Jones (Visible), and 4.48×1010 Jones (IR). The successful combination of Zinc tungstate and Cobalt tungstate on a paper substrate represents an advancement in photodetector technology, offering enhanced sensitivity, extended spectral range, and the potential for seamless integration into wearable electronics and portable devices.

Effect of Banana Peels Extract Ratio on The Sustainable Eco-Friendly Synthesis of Zinc Oxide Nanoparticles

In this work, environmentally friendly zinc oxide nanoparticles was produced using sustainable green technology. With several loading amounts, such as 5%, 10%, 50%, and 100%, the banana peel extract was utilized as a capping agent. This was followed by calcinations at 400 ºC for 3 h in a muffle furnace. To evaluate the physical and chemical change of the synthesized nanoparticles, XRD, FTIR, UV-VIS and SEM/EDAX was used. The characterization results reveald that the all the green synthesized ZnO NPs samples strongly supports the well-crystallinity with high phase purity. The average crystallite size of the prepared samples was calculated using Debye-Scherer's formula and the results shows that with an increase in extract amount, the average crystallite size was shrinking. The FTIR result verified the successful chemical reaction between zinc salt and banana peel extract. The UV-VIS results showed the effect of size quantisization phenomena at 100% extract adding. Finally, the SEM images for all the prepared samples confirm the spherical shape.

A role for conformational changes in enzyme catalysis

The role played by conformational changes in enzyme catalysis is controversial. In addition to examining specific enzymes, studying formal models can help identify the conditions under which conformational changes promote catalysis. Here, we present a model demonstrating how conformational changes can break a generic trade-off due to the conflicting requirements of successive steps in catalytic cycles, namely high specificity for the transition state to accelerate the chemical transformation and low affinity for the products to favor their release. The mechanism by which the trade-off is broken is a transition between conformations with different affinities for the substrate. The role of the effector that induces the transition is played by a substrate “handle,” a part of the substrate that is not chemically transformed but whose interaction with the enzyme is nevertheless essential to rapidly complete the catalytic cycle. A key element of the model is the formalization of the constraints causing the trade-off that the presence of multiple states breaks, which we attribute to the strong chemical similarity between successive reaction states—substrates, transition states, and products. For the sake of clarity, we present our model for irreversible one-step unimolecular reactions. In this context, we demonstrate how the different forms that chemical similarities between reaction states can take impose limits on the overall catalytic turnover. We first analyze catalysts without internal degrees of freedom and then show how two-state catalysts can overcome their limitations. Our results recapitulate previous proposals concerning the role of conformational changes and substrate handles in a formalism that makes explicit the constraints that elicit these features. In addition, our approach establishes links with studies in the field of heterogeneous catalysis, where the same trade-offs are observed and where overcoming them is a well-recognized challenge.

Solution-processed Sb2O3: A promising electrode material for high-performance supercapacitors and electrocatalysts

Easy accessibility, wide range of redox states, affordable cost, and simple synthesis methods of metal oxides have gained a significant interest in the domains of electrochemical supercapacitors and electrocatalysts. The successive ionic layer adsorption and reaction (SILAR) chemical synthesis approach has been introduced to preparing nanocrystalline antimony oxide (Sb2O3) for both energy storage and water splitting applications. The Sb2O3 electrode demonstrates a remarkable specific capacitance of 3011 F/g at a current density of 2 A/g in a 1 M solution of potassium hydroxide (KOH). The current design of the Sb2O3//Bi2O3 (bismuth oxide) asymmetric electrochemical supercapacitor device has endowed a specific capacitance of 391 F/g, a maximum energy density of 78.2 Wh/Kg at a power density of 1000 W/Kg, and an outstanding capacitance retention of 77 % even after 5000 redox cycles. The Sb2O3 electrode demonstrates outstanding performance in the oxygen evolution process at a current density of 10 mA cm2, with an overpotential of 206 mV. The Sb2O3 as an electrocatalyst also exhibits exceptional results in the hydrogen evolution reaction with an overpotential of 124 mV/dec. Both of these electrochemical processes are distinguished by the evolution of oxygen which is capable of facilitating the process of water splitting to obtain clean energy for day by day growing population.

Enhancement of Biodiesel Production via Ultrasound Technology: AMathematical Study.

Biodiesel is one of the alternative renewable energy sources that has received a lot of attention since it is clean, green energy. Different sources can be used for the production of biodiesel, but the most appropriate and economical method relies on the transesterification of methanol with the nonedible vegetable oil from the fruit of the Jatropha curcas plant. Molar ratio, vessel diameter, catalyst concentration, and ultrasound all have a substantial influence on the synthesis of biodiesel by the transesterification process. Among these factors, the diameter of the vessel and the ultrasonic effect through mass transfer limitations have a significant impact on successful reaction completion. In this research work, we have developed a mathematical model to analyze the three-step transesterification process and side saponification reaction in the presence of a potassium hydroxide catalyst. The model considers the influence of mixing intensity variations, including ultrasound, on the mass transfer in different phases. The mass transfer rate is calculated using the modified Dittus-Boelter correlation. An optimal control approach through the minimum principle by Pontryagin is applied to maximize the production of biodiesel at minimal cost. The novelty of this research, which we have derived from our analytical as well as numerical results, considering industrial processes, is that more than 97% biodiesel yield conversion is to be obtained at 50 kHz ultrasound frequency, a 6:1 methanol-to-Jatropha-oil molar ratio, and 1 m of vessel diameter within 50 min using optimal control theory.

A comparative analysis of solid-state quantum dot-sensitized solar cells employing various hole transport layers, metal contacts, and a sensitizer comprising PbS/CdS/ZnS quantum dots

Quantum dots, as a sensitizer in quantum dot-sensitized solar cells (QDSSCs), hold the promise of revolutionizing solar energy conversion. This research mainly focuses on employing PbS/CdS/ZnS quantum dots (QDs) as both light harvesters and passivation layers in QDSSCs, which are directly synthesized onto the pre-deposited TiO2 substrate through the Successive Ionic Layer Adsorption and Reaction (SILAR) technique. Particularly, the sample with a composition of 2 cycles of PbS, 6 cycles of CdS, and 2 cycles of ZnS (2/6/2) exhibited a wide-ranging and intense absorption spectrum, attributed to the reduction in band gap with escalation in number of SILAR cycles. The prepared samples underwent analysis through characterization methods, including SEM and XRD, and the elemental composition was examined using EDX spectroscopy. Subsequently, the 2/6/2 sample was employed as a sensitizer, with P3HT and PEDOT:PSS serving as the hole transport layers (HTL). For the metal contacts, thermally evaporated gold (Au), silver (Ag), and Ag paste were used in the fabrication of six distinct devices. FTO/TiO2/PbS/CdS/ZnS/P3HT/Au shows the best performance demonstrating PCE of 2.17 %, Jsc of 7.9 mA/cm2 Voc of 0.54 V and FF of 0.51. However, overall efficiency dropped significantly for other configurations. Additionally, impedance spectroscopic analysis revealed a notably low series resistance for the P3HT/Au configuration.

Biosynthesis of Enfumafungin-type Antibiotic Reveals an Unusual Enzymatic Fusion Pattern and Unprecedented C-C Bond Cleavage.

Enfumafungin-type antibiotics, represented by enfumafungin and fuscoatroside, belong to a distinct group of triterpenoids derived from fungi. These compounds exhibit significant antifungal properties with ibrexafungerp, a semisynthetic derivative of enfumafungin, recently gaining FDA's approval as the first oral antifungal drug for treating invasive vulvar candidiasis. Enfumafungin-type antibiotics possess a cleaved E-ring with an oxidized carboxyl group and a reduced methyl group at the break site, suggesting unprecedented C-C bond cleavage chemistry involved in their biosynthesis. Here, we show that a 4-gene (fsoA, fsoD, fsoE, fsoF) biosynthetic gene cluster is sufficient to yield fuscoatroside by heterologous expression in Aspergillus oryzae. Notably, FsoA is an unheard-of terpene cyclase-glycosyltransferase fusion enzyme, affording a triterpene glycoside product that relies on enzymatic fusion. FsoE is a P450 enzyme that catalyzes successive oxidation reactions at C19 to facilitate a C-C bond cleavage, producing an oxidized carboxyl group and a reduced methyl group that have never been observed in known P450 enzymes. Our study thus sets the important foundation for the manufacture of enfumafungin-type antibiotics using biosynthetic approaches.

Selective Sparse Sampling of Water Droplets in Oil with Acoustic Tweezers.

In microfluidics, water droplets are often used as independent biochemical microreactor units, enabling the implementation of massively parallel screening assays where only a few of the reacting water droplets yield a positive result. However, sampling the product of these few successful reactions is an unsolved challenge. One possible solution is to use acoustic tweezers, which are lab-free, easily miniaturized, and biocompatible manipulation tools, and existing acoustic tweezers manipulating particles or cells, and water droplet manipulation in oil with an acoustic tweezer is absent. The first challenge in attempting to recover a few water droplets from a large batch is the selective manipulation of water droplets in an oil system. In this paper, we trap and manipulate single water droplets in oil using integrated single-beam (focused beam/vortex beam) acoustic tweezers for the first time. We find that water droplets with a diameter smaller than half a wavelength are trapped by acoustic vortices, while larger ones are better captured by focused acoustic beams. It is the first step to extract the target water droplet microreactors (positive ones) in an oil system and analyze their content. Compared to previous techniques, such as fluorescence-activated cell sorting (FACS), our technique is sparse, meaning that the sampling time is proportional to the number of droplets required and very insensitive to the total number of microreactors, making it well suited for large-scale screening assays.

Synthesis of a Highly Efficient Mesoporous Green Catalyst from Waste Avocado Peels for Biodiesel Production from Used Cooking–Baobab Hybrid Oil

Valorization of waste biomass materials for fuels and other energy products has become one of the effective ways of escalating and improving the bioeconomy. The development of a novel biomass solid catalyst obtained from waste avocado peels and its potentials in transesterification of a bi-hybrid oil of used cooking–baobab oil (UC-BO) was investigated in this study. The catalyst was produced by calcining the burnt char of the dried avocado peels. The produced calcined avocado peels catalyst (CAP) was further characterized using analytical equipment, such as FT-IR, XRD, SEM, EDX, and TGA, to ascertain its catalytic properties. The results revealed that CAP contains some vital elements, such as Mg, P, Cl, Ca, Si, Na, and a high percentage of K content, present in form of oxides, carbonates, chlorides, and mixed metal compounds. The catalyst displayed effective catalytic potential in converting the UC-BO to biodiesel with 100% yield under an optimized condition of 51 min reaction time (RT), 14.5:1 of methanol to oil ratio (MTOR), and 2.73 wt% of catalyst loading (CL) at a constant temperature of 60 °C. The CAP exhibited excellent recyclability potential, achieving 92.85% biodiesel yield after five successive reaction cycles without notable catalytic activity reduction. The fuel properties investigated were all established within the biodiesel quality specifications of EN 14241 and ASTM D6751, demonstrating that it is a practical substitute for petroleum fuel.

Structure and Ultrafast X-ray Diffraction of the Hydrated Metaphosphate.

We study the pathway of metaphosphate hydration when a metaphosphate anion is dissolved in liquid water with an explicit water model. For this purpose, we propose a sequential Monte Carlo algorithm incorporated with the ab initio quantum mechanics/molecular mechanics (QM/MM) method, which can reduce the amount of ab initio QM/MM sampling while retaining the accuracy of the simulation. We demonstrate the numerical calculation of the standard enthalpy change for the successive addition reaction PO3-·2H2O + H2O ⇌ PO3-·3H2O in the liquid phase, which helps to clarify the hydration pathway of the metaphosphate. With the obtained hydrated structure of the metaphosphate anion, we perform ab initio calculations for its relaxation dynamics upon vibrational excitation and characterize the energy transfer process in solution with simulated ultrafast X-ray diffraction signals, which can be experimentally implemented with X-ray free-electron lasers.

Quest for a Desolvated Structure Unveils Breathing Phenomena in a MOF Leading to Greener Catalysis in a Solventless Setup: Insights from Combined Experimental and Computational Studies.

The crystal structure of the metal-organic framework (MOF), {Mn2(1,4-bdc)2(DMF)2}n (1) (1,4-bdcH2, 1,4-benzenedicarboxylic acid; DMF, N,N-dimethylformamide), is known for a long time; however, its desolvated structure, {Mn2(1,4-bdc)2}n (1'), is not yet known. The first-principles-based computational simulation was used to unveil the structure of 1' that shows the expansion in the framework, leading to pore opening after the removal of coordinated DMF molecules. We have used 1' that contains open metal sites (OMSs) in the structure in cyanosilylation and CO2 cycloaddition reactions and recorded complete conversions in a solventless setup. The pore opening in 1' allows the facile diffusion of small aldehyde molecules into the channels, leading to complete conversion. The reactions with larger aldehydes, 2-naphthaldehyde and 9-anthracenecarboxaldehyde, also show 99.9% conversions, which are the highest reported until date in solventless conditions. The in silico simulations illustrate that larger aldehydes interact with Mn(II) OMSs on the surfaces, enabling a closer interaction and facilitating complete conversions. The catalyst shows high recyclability, exhibiting 99.9% conversions in the successive reaction cycles with negligible change in the structure. Our investigations illustrate that the catalyst 1' is economical, efficient, and robust and allows reactions in a solventless greener setup, and therefore the catalysis with 1' can be regarded as "green catalysis".