Slow Reaction Rate Research Articles

RuBisCO activity assays: a simplified biochemical redox approach for in vitro quantification and an RNA sensor approach for in vivo monitoring

BackgroundRibulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) is the most abundant soluble protein in nature. Extensive studies have been conducted for improving its activity in photosynthesis through approaches like protein engineering. Concurrently, multiple biochemical and radiolabeling assays have been developed for determining its activity. Although these existing assays yield reliable results, they require addition of multiple external components, rendering them less convenient and expensive. Therefore, in this study, we have developed two relatively cheaper, convenient, and easily reproducible assays for quantitative and qualitative estimation of RuBisCO activity.ResultsWe simplified a contemporary NADH based spectrophotometric RuBisCO assay by using cyanobacterial cell lysate as the source for Calvin cycle enzymes. We analyzed the influence of inorganic carbon substrates, CO2 and NaHCO3, and varying protein concentrations on RuBisCO activity. Ribulose-1,5-bisphosphate (RuBP) consumption rates for the cultures grown under 5% CO2 were 5–7 times higher than the ones grown with 20 mM NaHCO3, at different protein concentrations. The difference could be due to the impaired activity of carbonic anhydrase in the cell lysate, which is required for the conversion of HCO3− to CO2. The highest RuBisCO activity of 2.13 nmol of NAD+/ µg of Chl-a/ min was observed with 50 µg of protein and 5% CO2. Additionally, we developed a novel RNA-sensor based fluorescence assay that is based on the principle of tracking the kinetics of ATP hydrolysis to ADP during the conversion of 3-phosphoglycerate (3-PG) to 1,3-bisphosphoglycerate (1,3-BPG) in the Calvin cycle. Under in vitro conditions, the fluorometric assay exhibited  ~ 3.4-fold slower reaction rate (0.37 min−1) than the biochemical assay when using 5% CO2. We also confirmed the in vivo application of this assay, where increase in the fluorescence was observed with the recombinant strain of Synechocystis sp. PCC 6803 (SSL142) expressing the ADP-specific RNA sensor, compared to the WT. In addition, SSL142 exhibited three-fold higher fluorescence when supplemented with 20 mM NaHCO3 as compared to the cells that were grown without NaHCO3 supplementation.ConclusionsOverall, we have developed a simplified biochemical assay for monitoring RuBisCO activity and demonstrated that it can provide reliable results as compared to the prior literature. Furthermore, the biochemical assay using 5% CO2 (100% relative activity) provided faster RuBP consumption rate compared to the biochemical assay utilizing 20 mM NaHCO3 (30.70% relative activity) and the in vitro fluorometric assay using 5% CO2 (29.64% relative activity). Therefore, the absorbance-based biochemical assay using 5% CO2 or higher would be suitable for in vitro quantification of the RuBisCO activity. On the other hand, the RNA-sensor based in vivo fluorometric assay can be applied for qualitative analysis and be used for high-throughput screening of RuBisCO variants. As RuBisCO is an enzyme shared amongst all the photoautotrophs, the assays developed in this study can easily be extended for analyzing the RuBisCO activities even in microalgae and higher plants.

Polyurethane Foam Chemical Recycling: Fast Acidolysis with Maleic Acid and Full Recovery of Polyol.

Chemical recycling of polyurethane (PU) waste is essential to displace the need for virgin polyol production and enable sustainable PU production. Currently, less than 20% of PU waste is downcycled through rebinding to lower value products than the original PU. Chemical recycling of PU waste often requires significant input of materials like solvents and slow reaction rates. Here, we report the fast (<10 min) and solvent-free acidolysis of a model toluene diisocyanate (TDI)-based flexible polyurethane foam (PUF) at <200 °C using maleic acid (MA) with a recovery of recycled polyol (repolyol) in 95% isolated yield. After workup (hydrolysis of repolyl ester and separations), the repolyol exhibits favorable physical properties that are comparable to the virgin polyol; these include 54.1 mg KOH/g OH number and 624 cSt viscosity. Overall, 80% by weight of the input PUF is isolated into two clean-cut fractions containing the repolyol and toluene diamine (TDA). Finally, end-of-life (EOL) mattress PUF waste is recycled successfully with high recovery of repolyol using MA acidolysis. The solvent-free and fast acidolysis with MA demonstrated in this work with both model and EOL PUF provides a potential pathway for sustainable and closed-loop PU production.

Ru Regulated Electronic Structure of Pdx Cuy Nanosheets for Efficient Hydrogen Evolution Reaction in Wide pH Range.

The development of highly effective catalysts for hydrogen evolution reaction (HER) in a wide pH range is crucial for the sustainable utilization of green energy utilization, while the slow kinetic reaction rate severely hinders the progress of HER. Herein, the reaction kinetic issue is solved by adjusting the electronic structure of the Ru/Pdx Cuy catalysts. The champion catalyst displays a remarkable performance for HER with the ultralow overpotential (27, 28, and 97mV) in 1.0m KOH, 0.5m H2 SO4 , and 1.0m PBS at 10mA cm-2 and high the mass activity (3036 A g-1 ), respectively, superior to those of commercial Pt/C benchmarks and most of reported electrocatalysts, mainly due to its low reaction activation energy. Density functional theory (DFT) calculations indicate that Ru doping contributes an electron-deficient 3d band, which promotes water adsorption. Additionally, this also leads to an upward shift of the d-band center of Pd and a downward shift of the d-band center of Cu, further optimizing the adsorption/dissociation of H2 O and H* . Results from this work may provide an insight into the design and synthesis of high-performance pH-universal HER electrocatalysts.

Weathering Incongruence in Mountainous Mediterranean Climates Recorded by Stream Lithium Isotope Ratios

AbstractLithium isotope ratios (δ7Li) of rivers are increasingly serving as a diagnostic of the balance between chemical and physical weathering contributions to overall landscape denudation rates. Here, we show that intermediate weathering intensities and highly enriched stream δ7Li values typically associated with lowland floodplains can also describe small upland watersheds subject to cool, wet climates. This behavior is revealed by stream δ7Li between +22.4 and +23.5‰ within a Critical Zone observatory located in the Cévennes region of southern France, where dilute stream solute concentrations and significant atmospheric deposition otherwise mask evidence of incongruence. The water‐rock reaction pathways underlying this behavior are quantified through a multicomponent, isotope‐enabled reactive transport model. Using geochemical characterization of soil profiles, bedrock, and long‐term stream samples as constraints, we evolve the simulation from an initially unweathered granite to a steady state weathering profile which reflects the balance between (a) fluid infiltration and drainage and (b) bedrock uplift and soil erosion. Enriched stream δ7Li occurs because Li is strongly incorporated into actively precipitating secondary clay phases beyond what prior laboratory experiments have suggested. Chemical weathering incongruence is maintained despite relatively slow reaction rates and moderate clay accumulation due to a combination of two factors. First, reactive primary mineral phases persist across the weathering profile and effectively “shield” the secondary clays from resolubilization due to their greater solubility. Second, the clays accumulating in the near‐surface profile are relatively mature weathering byproducts. These factors promote characteristically low total dissolved solute export from the catchment despite significant input of exogenous dust.

Schottky-assisted S-scheme heterojunction photocatalyst CdS/Pt@NU-1000 for efficient visible-light-driven H2 evolution

Coupling metal-organic frameworks (MOFs) with inorganic semiconductors to construct S-scheme heterojunction photocatalysts is an effective way to facilitate photocarriers transfer and separation, as well as enhance redox ability for photocatalytic water-splitting into H2. However, the poor electrical conductivity of MOFs, fast recombination of photogenerated electron-hole pairs, and slow surface redox reaction rates on photocatalysts lead to inefficient consumption of all charge carriers thus impeding further improvement of photocatalytic activity. Thus, optimizing the separation, transfer, and utilization efficiencies of interfacial charge carriers in MOFs-based S-scheme heterojunction may pave the way for achieving excellent photocatalytic activity. Herein, a novel Schottky-assisted S-scheme heterojunction photocatalyst CdS/Pt@NU-1000 was prepared by the combination of Pt-embedded NU-1000 with CdS. The optimized photocatalyst CdS/0.7Pt@NU-1000 exhibits the highest visible-light-driven H2 evolution rate with 3.604 mmol g–1 h–1, which is 12.7 and 18.8 folds of that for single CdS and NU-1000, respectively. The splendid photocatalytic performance benefited from the broadened light absorption, and the synergistic effect of the formed Schottky junction and S-scheme heterojunction. Furthermore, the formation of the S-scheme system was validated by density functional theory (DFT) calculations, in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS), and electron paramagnetic resonance (EPR) test. This work can provide some guidance for the design of efficient heterojunction photocatalysts by optimizing interfacial charge transfer.

ProPhos: A Ligand for Promoting Nickel-Catalyzed Suzuki-Miyaura Coupling Inspired by Mechanistic Insights into Transmetalation.

Nickel-catalyzed Suzuki-Miyaura coupling (Ni-SMC) offers the potential to reduce the cost of pharmaceutical process synthesis. However, its application has been restricted by challenges such as slow reaction rates, high catalyst loading, and a limited scope of heterocycles. Despite recent investigations, the mechanism of transmetalation in Ni-SMC, often viewed as the turnover-limiting step, remains insufficiently understood. We elucidate the "Ni-oxo" transmetalation pathway, applying PPh2Me as the ligand, and identify the formation of a nickel-oxo intermediate as the turnover-limiting step. Building on this insight, we develop a scaffolding ligand, ProPhos, featuring a pendant hydroxyl group connected to the phosphine via a linker. The design preorganizes both the nucleophile and the nickel catalyst, thereby facilitating transmetalation. This catalyst exhibits fast kinetics and robust activity across a wide range of heteroarenes, with a catalyst loading of 0.5-3 mol %. For arene substrates, the catalyst loading can be further reduced to 0.1 mol %.

Hybrid Electrolyte Based on PEO and Ionic Liquid with In Situ Produced and Dispersed Silica for Sustainable Solid-State Battery

This work introduces the synthesis of hybrid polymer electrolytes based on polyethylene oxide (PEO) and electrolyte solution bis(trifluoromethane)sulfonimide lithium salt/ionic liquid 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (LiTFSI/EMIMTFSI) with in situ produced and dispersed silica particles by the sol–gel method. Conventional preparation of solid polymer electrolytes was followed by desolvation of lithium salt in a polymer matrix of PEO, which, in some cases, additionally contains plasticizers. This one-pot synthesis is an alternative route for fabricating a solid polymer electrolyte for solid-state batteries. The presence of TFSI- reduces the crystallinity of the PEO matrix (plasticizing effect), increases the dissociation and solubility of LiTFSI in the PEO matrix because of a highly delocalized charge distribution, and reveals excellent thermal, chemical, and electrochemical stability. Tetraethylorthosilicate (TEOS) was chosen due to the slow reaction rate, with the addition of (3-glycidyoxypropyl)trimethoxysilane (GLYMO), which contributes to the formation of a silica network. FTIR studies confirmed the interactions between the silica, the polymer salt, and EMIMTFSI. Impedance spectroscopy measurements were performed in a wide range of temperatures from 25 to 70 °C. The electrochemical performance was explored by assembling electrolytes in LiCoO2 (LCO), NMC(811), and LiFePO4 (LFP) coin half-cells. The HPEf15 shows a discharge capacity of 143 mA/g for NMC(811) at 0.1 C, 134 mA/g for LCO, and 139 mA/g for LFP half-cells at 0.1 C and 55 °C. The LFP half-cell with a discharge capacity of 135 mA/g at 0.1 C (safety potential range of 2.8 to 3.8) obtained a cyclability of 97.5% at 55 °C after 100 cycles. Such a type of electrolyte with high safety and good electrochemical performance provides a potential approach for developing a safer lithium-ion battery.

The Electrocatalytic Oxygen Evolution Reaction Activity of Rationally Designed NiFe-Based Glycerates

The electrocatalytic oxygen evolution reaction (OER) is an arduous step in water splitting due to its slow reaction rate and large overpotential. Herein, we synthesized glycerate-anion-intercalated nickel–iron glycerates (NiFeGs) using a one-step solvothermal reaction. We designed various NiFeGs by tuning the molar ratio between Ni and Fe to obtain Ni4Fe1G, Ni3Fe1G, Ni3Fe2G, and Ni1Fe1G, which we tested for their OER performance. We initially analyzed the catalytic performance of powder samples immobilized on glassy carbon electrodes using a binder. Ni3Fe2G outperformed the other NiFeG compositions, including NiFe layered double hydroxide (LDH). It exhibited an overpotential of 320 mV at a current density of 10 mA cm–2 in an electrolytic solution of pH 14. We then synthesized carbon paper (CP)-modified Ni3Fe2G as a self-supported electrode (Ni3Fe2G/CP), and it exhibited a high current density (100 mA cm−2) at a low overpotential of 300 mV. The redox peak analysis for the NiFeGs revealed that the initial step of the OER is the formation of γ-NiOOH, which was further confirmed by a post-Raman analysis. We extensively analyzed the catalyst’s stability and lifetime, the nature of the active sites, and the role of the Fe content to enhance the OER performance. This work may provide the motivation to study metal-alkoxide-based efficient OER electrocatalysts that can be used for alkaline water electrolyzer applications.

Silica dopant effect on the performance of calcium carbonate/calcium oxide based thermal energy storage system

The CaCO3 is being studied for its application in thermal energy storage. However, it has drawbacks of slow reaction rate during calcination and incomplete reversible carbonation which limit its use. In this paper, SiO2 has been studied as a dopant for CaCO3 to improve its cyclic performance. The CaCO3 samples were loaded with different concentrations of SiO2 and its effect on the thermal energy density of CaCO3 was determined. Afterwards, the effect of the dopant on the heat storage process of the synthesized composite along with kinetics of decarbonation reaction was investigated. Cyclic tests were performed to determine the reusability of the material. It was found that the addition of dopant helped to increase the rate of decarbonation reaction, thereby making the heat storage process more efficient as compared to pure CaCO3. The activation energy values are 255.9 kJ/mol, 280.1 kJ/mol, 244.9 kJ/mol, and 234.8 kJ/mol for 5%, 15%, 30%, and 0% doped SiO2 samples, respectively. Furthermore, thermal energy storage density increases when the amount of dopant decreases in the samples such as the 30% and 5% doped samples have gravimetric energy storage densities of 339.85 J/g and 759.24 J/g, respectively. It was observed that the large quantities (15% and 30%) of dopant had introduced a new phase of Ca3SiO5 during CaCO3 decomposition.

Simple Routes to Stable Isotope-Coded Native Glycans.

Understanding the biological role of protein-linked glycans requires the reliable identification of glycans. Isomer separation and characterization often entail mass spectrometric detection preceded by high-performance chromatography on porous graphitic carbon. To this end, stable isotope-labeled glycans have emerged as powerful tools for retention time normalization. Hitherto, such standards were obtained by chemoenzymatic or purely enzymatic methods, which introduce, e.g., 13C-containing N-acetyl groups or galactose into native glycans. Glycan release with anhydrous hydrazine opens another route for heavy isotope introduction via concomitant de-N-acetylation. Here, we describe that de-N-acetylation can also be achieved with hydrazine hydrate, which is a more affordable and less hazardous reagent. Despite the slower reaction rate, complete conversion is achievable in 72 h at 100 °C for glycans with biantennary glycans with or without sialic acids. Shorter incubation times allow for the isolation of intermediate products with a defined degree of free amino groups, facilitating introduction of different numbers of heavy isotopes. Mass encoded glycans obtained by this versatile approach can serve a broad range of applications, e.g., as internal standards for isomer-specific studies of N-glycans, O-glycans, and human milk oligosaccharide by LC-MS on either porous graphitic carbon or─following permethylation─on reversed phase.

Geochemical interactions in geological hydrogen Storage: The role of sandstone clay content

Hydrogen holds promise as a clean energy alternative, crucial for achieving global decarbonization goals and net-zero carbon emissions. Its low volumetric energy density necessitates underground storage in sandstone formations to maintain year-round supply. The efficacy of such storage hinges on the geochemical interplay between hydrogen and the host sandstone. Despite the slow reaction rates in sandstone, the influence of its clay composition on hydrogen interaction remains underexplored. In this study, we specifically investigate the geochemical interactions of hydrogen with clay-bearing sandstone formations under controlled conditions, simulating storage scenarios. This study evaluates the impact of clay on hydrogen-sandstone geochemistry after 75 days of injection at 1500 psi and 75 °C into Berea and Bandera gray sandstone cores, utilizing microcomputed tomography to assess changes in pore structure. Our results reveal that, even in sandstones with high clay content, there is negligible alteration in porosity and mineral content, as well as minimal clay and quartz dissolution or expansion over storage time, indicating stability in these formations. These findings provide crucial insights for selecting suitable geological formations for hydrogen storage, supporting the global shift towards sustainable energy systems Our study contributes to the global efforts in decarbonization by providing essential guidance on the feasibility of using clay-bearing sandstone formations for efficient and sustainable hydrogen storage.

A Sequential Transition Metal and Organocatalytic Approach to the Enantioselective Synthesis of C2-Spiroindoline Systems.

We report herein an organocatalyzed enantioselective spirocyclization strategy to access valuable C2-spiroindoline scaffolds bearing a quaternary stereocenter via an aza-Michael addition reaction, wherein the acid additive plays the role of dual functionality. The substrates for this key step were put together by an exo-selective, Pd-catalyzed γ-arylation of silyldienol ethers of the corresponding cyclohexenones. A close alliance between a low catalyst loading and a slow reaction rate yields C2-spiroindolines with good enantioselectivity.

Reactions of CH2OO, CH3CHOO, and (CH3)2COO with Methane through the Formation of Intermediate Complex

Criegee intermediates, which are the products of the ozonolysis of alkenes, play a key role in many chemical and physical processes in the atmosphere. Their reactions with other atmospheric compounds are responsible for the formation of hydroxyl, methyl, hydrogen radicals, nitric and sulfuric acids, and others. Methane is an active greenhouse gas whose concentration has increased rapidly in the last several decades. In this work, we consider the interaction between these two important atmospheric compounds. We choose the three simple Criegee intermediate (CI) molecules: formaldehyde oxide (CH2OO), acetaldehyde oxide (CH3CHOO), and acetone oxide ((CH3)2COO). Some reactions between methane and these Cis have been studied earlier as possible pathways for deactivating methane as well as a source of methanol formation due to molecular collisions in the atmosphere. In the present study, we extend the consideration to the case when an intermediate energetically stable complex is formed after collision. We found that this complex could easily decompose to form an OH radical and another unstable fragment, which can quickly dissociate into CH3 radicals, atomic hydrogen, acetone, acetaldehyde, propaldehyde, methyl alcohol, water, and others, depending on the type of CI being reacted with. These compounds can actively interact with other atmospheric components and change their physical and chemical properties. In addition, CI with a methyl substituent is shown to have increased energy in transition states and minima, resulting in slower reaction rates.

Research progress on the influencing factors and enhancement mechanism of CH4/CO2 mixture separation process by hydrate‐based technology: A review

AbstractThe separation of mixed gas by hydrate method can realize the efficient separation of CO2 gas from biological gas. However, the long period, slow rate, and low selectivity of hydration reaction have become the critical problems restricting the efficient separation of the gas mixture by hydrate method. In this review, the formation characteristics of CH4/CO2 mixed gas hydrate are systematically summarized, and the kinetic process and influencing factors of CH4/CO2 mixed gas hydrate formation are comprehensively analyzed. On this basis, the influence mechanism and law of temperature, pressure, gas–liquid ratio, gas component ratio, additives, and other factors on the CH4/CO2 mixed gas hydrate formation progress were described in detail, and the enhancement mechanism of CH4/CO2 mixed gas hydrate formation under the influence of different factors was analyzed. Finally, the shortcomings and future development directions of the purification and separation technology of CH4/CO2 mixed gas by hydrate method are pointed out. Further research is needed to understand the kinetic mechanism and enhancement mechanism of the CH4/CO2 mixture separation process by hydrate method. The relative results will provide valuable guidance for the separation of mixture gas by a hydrate‐based method.

The enhancement of waste PET particles enzymatic degradation with a rotating packed bed reactor

Polyethylene terephthalate (PET) is widely used, and biodegradation of waste PET results in a residue-free process, generating recyclable products, thereby contributing to the advancement of a more recyclable plastics lifecycle. Extensive research has been conducted on the modification and evolution of enzyme for PET degradation. As a solid-liquid heterogeneous reactions of PET degradation, the slow diffusion rate of the enzyme from liquid to solid PET surface leading to a slow reaction rate. Enhancement of mass transfer would accelerate PET degradation. Rotating packed bed (RPB) is a mass transfer enhancement reactor, but shear strength generated by the enzyme molecule knocking on rotator of RPB leads to enzyme denaturation. To address this issue, shear strength resistance agents were introduced in this study. With the protection of β-cyclodextrin combined with kieselguhr, PET particle degradation rate of 95% was achieved under the optimum conditions in 24 h, which was improved by 30% compared to that in stirred tank reactor. The results of this work demonstrated that the mass transfer greatly influenced the PET biodegradation process. RPB combined with the function of shear strength resistance agents could greatly improve the efficiency of the biodegradation process. This study provides a reference for the scaling up of PET degradation, and holds significant promise in the broader context of combatting plastic pollution challenges and advancing sustainable solutions for plastic waste.

Ionic liquid Supported Quinuclidine Catalyzed Morita-Baylis-Hillman Reaction

Abstract: The Morita-Baylis-Hillman (MBH) reaction is an important method for forming carboncarbon bonds between carbonyl-containing compounds and activated olefins. However, the slow reaction rate with electron-rich electrophilic partners has limited its wider use. To overcome this drawback, the effects of pyridinium-based ionic liquids mediated quinuclidine catalytic system for MBH reactions were studied. The method is simple, involving neat and open-flask conditions, and is compatible with a wide range of reagents. We offered general pyridinium-based ionic liquids-mediated quinuclidine catalysis mechanism that is responsible for the observed rate increase. The synthetic versatility of the MBH adducts is demonstrated by the synthesis of important building blocks for the natural product (-)-sitophilure. The authors anticipate that this pyridinium-based ionic liquids-mediated quinuclidine protocol could serve as a general methodology for the MBH reaction. In summary, the study presents a simple and effective method to enhance the reaction rate of the MBH reaction. The authors believe this method has the potential for broader applications and may contribute to developing new synthetic strategies for organic synthesis. We successfully recycled the catalytic system up to 7 runs without losing any catalytic activity.

Photoredox Nickel‐Catalysed Stille Cross‐Coupling Reactions

AbstractThe Stille cross‐coupling reaction is one of the most common strategies for the construction of C−C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium‐catalysed Stille reactions, cost‐effective nickel‐catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped. Herein, we present a pioneering instance of nickel‐catalysed enantioconvergent Stille cross‐coupling reactions of racemic stannane reagents, resulting in the formation of C−C bonds in good to high yields with excellent stereoselectivity. This strategy provides a practical, scalable, and operationally straightforward method for the synthesis of C(sp3)−C(sp3), C(sp3)−C(sp2), and C(sp3)−C(sp) bonds under exceptionally mild conditions (without additives and bases, ambient temperature). The innovative use of synergistic photoredox/nickel catalysis enables a novel single‐electron transmetalation process of stannane reagents, providing a new research paradigm of Stille reactions.

Photoredox Nickel-Catalysed Stille Cross-Coupling Reactions.

The Stille cross-coupling reaction is one of the most common strategies for the construction of C-C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium-catalysed Stille reactions, cost-effective nickel-catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped. Herein, we present a pioneering instance of nickel-catalysed enantioconvergent Stille cross-coupling reactions of racemic stannane reagents, resulting in the formation of C-C bonds in good to high yields with excellent stereoselectivity. This strategy provides a practical, scalable, and operationally straightforward method for the synthesis of C(sp3 )-C(sp3 ), C(sp3 )-C(sp2 ), and C(sp3 )-C(sp) bonds under exceptionally mild conditions (without additives and bases, ambient temperature). The innovative use of synergistic photoredox/nickel catalysis enables a novel single-electron transmetalation process of stannane reagents, providing a new research paradigm of Stille reactions.

Precise redox strategy to fabricate CuO/Cu2O hetero-electrodes for ultrafast electrochemical nitrate reduction into valuable ammonia resources

Electrochemical reduction of nitrate is a highly promising method for removing nitrate from water bodies. However, slow reaction rates have been a major challenge in its practical application. In this study, a novel CuO/Cu2O@CC hetero-electrode was developed by using a precise redox strategy, where CuO and Cu2O were simultaneously introduced to provide catalytic active sites for the reduction of nitrate into ammonia. This compositing design could significantly enlarge the electrochemically active surface area, reduce the electron transfer resistance and increase hydroxyl oxygen content on the electrode surface. The effect of operating parameters (cathodic potential, initial pH, supporting electrolyte concentration, initial NO3–−N concentration and coexisting Cl– concentration) on nitrate reduction was studied to optimize the reduction efficiency. Under −1.4 V (vs. Ag/AgCl) cathodic potentials and initial pH = 7 parameters, CuO/Cu2O@CC 3 achieved a remarkable 92.9% removal of 100 mg L–1 initial nitrate and a high ammonia selectivity of 78.33% in 1 h using 0.5 mol L–1 K2SO4 as supporting electrolyte, with a pseudo-first-order kinetic constant of 2.5856 h–1. Additionally, based on the experimental results, a reaction mechanism for the heterostructures electrode was proposed. The successful construction of CuO/Cu2O hetero-electrode provides a unique insight into the electrochemical reduction of nitrate.

Modeling and simulation in rate performance of solid-state lithium-ion batteries at low temperatures

Solid-state lithium-ion batteries (SSBs) not only improve the energy density of batteries, but also solve the unavoidable battery safety problems of liquid electrolytes. However, the rate capability of SSBs cannot meet the needs of practical applications due to the defects of low ionic conductivity and slow reaction rate of solid-solid interface, which becomes one of the bottlenecks restricting its development. Moreover, SSBs usually suffer from capacity reduction and security problems under low temperatures. This paper established a two-dimensional model of SSBs based on a multi-physical field simulation software, and studied the rate performance of SSBs under low temperatures. The distribution of lithium ion concentration in both electrolyte and cathode, diffusion coefficient of lithium ion and high rate discharge behavior of SSBs at low temperature were discussed in details. The simulation results exhibit that the rate capability of SSBs at low temperature can be improved by appropriately reducing the thickness of solid-state electrolyte. When the electrolyte thickness is fixed as 0.6 μm, the discharge capacities decrease from 0.345 Ah m−2 to 0.343 Ah m−2 as the discharge rates increase from 3C to 8C, together with a high capacity retention ratio of 99.5 %. Besides, SSBs can still maintain a high and flat discharge platform even at the high rate of 8C. This study proposes a method to improve the rate performance of solid state battery at low working temperatures, which has a theoretical guiding significance and engineering value for the structure design of SSBs.