Electron Reservoir Research Articles

A cluster-nanozyme-coenzyme system mimicking natural photosynthesis for CO2 reduction under intermittent light irradiation

Natural photosynthesis utilizes solar energy to convert water and atmospheric CO2 into carbohydrates through all-weather light/dark reactions based on molecule-based enzymes and coenzymes, inspiring extensive development of artificial photosynthesis. However, development of efficient artificial photosynthetic systems free of noble metals, as well as rational integration of functional units into a single system at the molecular level, remain challenging. Here we report an artificial system, the assembly system of Cu6 cluster and cobalt terpyridine complex, that mimics natural photosynthesis through precise integration of nanozyme complexes and ubiquinone (coenzyme Q) on Cu6 clusters. This biomimetic system efficiently reduces CO2 to CO in light reaction, achieving a production rate of 740.7 μmol·g−1·h−1 with high durability for at least 188 hours. Notably, our system realizes the decoupling of light and dark reactions, utilizing the phenol-evolutive coenzyme Q acting as an electron reservoir. By regulating the stabilizer of coenzyme Q, the dark reaction time can be extended up to 8.5 hours, which fully meets the natural day/night cycle requirements. Our findings advance the molecular design of artificial systems that replicate the comprehensive functions of natural photosynthesis.

Protonation of Dppbz- and Binap-Ligated Rhodathiaboranes Yielding Hydron, Hydride, and Hydrogen Exchange.

The reaction of the 11-vertex rhodathiaborane [8,8,8-(H)(PPh3)2-3-(NC5H5)-nido-7,8-RhSB9H10] (1) with 1,2-bis(diphenylphosphine)benzene (dppbz) and (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) affords [1,1-(η2-dppbz)-3-(NC5H5)-closo-1,2-RhSB9H8] (2) and [1,1-(η2-binap)-3-(NC5H5)-closo-1,2-RhSB9H8] (3). These 11-vertex closo-rhodathiaborane chelates result from PPh3 ligand substitution at the rhodium center and a nido-to-closo structural cluster transformation driven by H2 loss. Treating compounds 2 and 3 with triflic acid (TfOH) leads to the formation of cationic clusters 4 and 5. The hydrons bind to the polyhedral clusters, acquiring hydride character and providing chemical nonrigidity that manifests through metal vertex-to-thiaborane pseudo-rotations and concomitant hydron tautomerisms. The resulting cations react with hydrogen to form mixtures of hydrons, hydrogen, and hydridorhodathiaboranes in equilibrium. The reaction products are the result of heterolytic cleavage of the H-H bond, with full participation of the clusters and the addition of hydrogen atoms to the cages. In these reactions, there is a conversion of electrons and hydrons into hydrogen, and hydrogen into hydride ligands, demonstrating that these boron-based metal compounds act as electron reservoirs, capable of promoting multielectron processes.

Electronic communications between active sites on individual metallic nanoparticles in catalysis

Catalytic activity of metal particles is reported to originate from the appearance of nonmetallic states, but conductive metallic particles, as an electron reservoir, should render electron delivery between reactants more favorably so as to have higher activity. We present that metallic rhodium particle catalysts are highly active in the low-temperature oxidation of carbon monoxide, whereas nonmetallic rhodium clusters or monoatoms on alumina remain catalytically inert. Experimental and theoretical results evidence the presence of electronic communications in between vertex atom active sites of individual metallic particles in the reaction. The electronic communications dramatically lower apparent activation energies via coupling two electrochemical-like half-reactions occurring on different active sites, which enable the metallic particles to show turnover frequencies at least four orders of magnitude higher than the nonmetallic clusters or monoatoms. Similar results are found for other metallic particle catalysts, implying the importance of electronic communications between active sites in heterogeneous catalysis.

Quantumness of electron transport in quantum dot devices through Leggett–Garg inequalities: A non-equilibrium Green’s function approach

Although coherent manipulation of electronic states can be achieved in quantum dot (QD) devices by harnessing nanofabrication tools, it is often hard to fathom the extent to which these nanoelectronic devices can behave quantum mechanically. Witnessing their nonclassical nature would thus remain of paramount importance in the emerging world of quantum technologies, since the coherent dynamics of electronic states plays there a crucial role. Against this backdrop, we resort to the general framework of Leggett-Garg inequalities (LGI) as it allows for distinguishing the classical and quantum transport through nanostructures by way of various two-time correlation functions. Using the local charge detection at two different time, we investigate here theoretically whether any quantum violation of the original LGI exists with varying device configurations and parameters under both Markovian and non-Markovian dynamics. Two-time correlators within LGI are derived in terms of the non-equilibrium Green’s functions (NEGFs) by exactly solving the quantum Langevin equations. The present study of non-Markovian dynamics of quantum systems interacting with reservoirs is significant for understanding the relaxation phenomenon in the ultrafast transient regime to especially mimic what happens to high-speed quantum devices. We can potentially capture the effect of finite reservoir correlation time by accounting for level-broadening at the electrodes along with non-Markovian memory effects. Furthermore, the large bias restriction is no longer imposed in our calculations so that we can safely consider a finite bias between the electronic reservoirs. Our approach is likely to open up new possibilities of witnessing the quantumness for other quantum many-body systems as well that are driven out of the equilibrium.

Hierarchical Ag3VO4 Nanorods as an Excellent Visible Light Photocatalyst for CO2 Conversion to Solar Fuels

The potential of photocatalytic CO2 conversion is significant for the production of fuels and chemicals, while simultaneously mitigating CO2 emissions and addressing environmental concerns. Despite the current drawbacks of single metal-based photocatalysts, such as lower performance, uncontrollable selectivity, and instability, this study focuses on the synthesis of Ag3VO4 nanorods using the sol–gel method. The goal is to create a highly effective catalyst for visible light-responsive CO2 conversion. The successful synthesis of Ag3VO4 nanorods with a nanorod structure, functional under visible light, resulted in the highest yields of CH4 and dimethyl ether (DME) at 271 and 69 µmole/g-cat, respectively. The optimized Ag3VO4 nanorods demonstrated performance improvements, with CH4 and DME production 6.4 times and 4.5 times higher than when using V2O5 samples. This suggests that Ag3VO4 nanorods facilitate electron transfer to CO2, offer short pathways for electron transfer, and create empty spaces within the nanorods as electron reservoirs, enhancing the photoactivity. The prolonged stability of Ag3VO4 in the CO2 conversion system confirms that the nanorod structure provides controllable selectivity and stability. Therefore, the fabrication of nanorod structures holds promise in advancing high-performance photocatalysts in the field of photocatalytic CO2 conversion to solar fuels.

Enhancing the photoelectrochemical performance of TiO2 photoanode by employing carbon nanoparticles as electron reservoirs and photothermal materials.

Photoelectrochemical (PEC) water splitting is regarded as a potential technique for converting solar energy. However, the fast charge recombination and slow water oxidation kinetics significantly have hindered its practical application. It is found that an elevation in operation temperature can activate the charge transport in the photoanodes. Here, a strategy was performed that carbon nanoparticles were employed to TiO2 nanorods, acting as electron reservoirs as well as photothermal materials. More specifically, a record photocurrent density of 1.62mAcm-2 at 1.23V vs. RHE has been achieved, accompanied by a high charge separation efficiency of 96% and a long-term durability for 8h. The detailed experimental results reveal that under NIR light irradiation, the synergistic effect between electron storage and temperature rise leads to accelerated charge transport in the bulk and water oxidation kinetics on the surface. This research offers a new perspective on how to boost the PEC performance of photoelectrodes.

Undulating Free Energy Landscapes Buffer Redox Chains from Environmental Fluctuations.

Roller-coaster or undulating free energy landscapes, with alternating high and low potential cofactors, occur frequently in biological redox chains. Yet, there is little understanding of the possible advantages created by these landscapes. We examined the tetraheme subunit associated with Blastochloris viridis reaction centers, comparing the dynamics of the native protein and of hypothetical (in silico) mutants. We computed the variation in the total number of electrons in wild type (WT) and mutant tetrahemes connected to an electron reservoir in the presence of a time-varying potential, as a model for a fluctuating redox environment. We found that roller-coaster free energy landscapes buffer the redox cofactor populations from these fluctuations. The WT roller-coaster landscape slows forward and backward electron transfer in the face of fluctuations, and may offer the advantage of sustaining the reduction of essential cofactors, such as the chlorophyll special pair in photosynthesis, even though an undulating landscape introduces thermodynamically uphill steps in multistep redox chains.

Carbon dioxide photoreduction using a photocatalyst with prolonged charge-separated states and excess electron reservoirs

Carbon dioxide photoreduction using a photocatalyst with prolonged charge-separated states and excess electron reservoirs

Degradation of acid blue 41 with carbon quantum dots@MOF-808 nanocomposite as a biocompatible photocatalyst under visible light

CQDs@MOF-808 guest@host nanocomposite as a biocompatible photocatalyst has been synthesized using a ship-bottle approach involving the impregnation method for immobilization of glucose molecules as carbon quantum dots (CQDs) precursor into the MOF-808 pores to form Glucose@MOF-808 and further fabrication of carbon quantum dots (CQDs) via in-situ thermolysis route of glucose molecules loaded into the pores of MOF-808. The photocatalytic degradation efficiency of 86.62 % was calculated for CQDs@MOF-808 nanocomposite for degradation of Acid Blue 41 in 120 min under visible light irradiation, that was attributed to the presence of CQDs inside MOF-808 pores. The exceptional characteristics of CQDs include outstanding up-converted photoluminescence (UCPL) effects, photo-induced electron transfer, electron reservoir properties, and electron-hole separations, all contributing to the photocatalytic degradation of Acid Blue 41. The synthesized samples were characterized by PXRD, FT-IR, EDX, N2 adsorption–desorption isotherm, TEM, DRS, PL, EIS and Mott − Sckottky measurements.

Enhanced solar urea synthesis from CO2 and nitrate waste via oxygen vacancy mediated-TiOx support lead-free perovskite

The nitrogen fertilizer industry, particularly urea production, notably contributes to greenhouse gas emissions and energy consumption. Urea synthesis via solar energy encounters several challenges. Specifically, solar urea synthesis methods often exhibit low efficiency and yield, primarily stemming from inefficient energy conversion processes and intricate reaction pathways. Moreover, the kinetics of the urea synthesis reaction may be sluggish, thereby impacting the overall production rate. Therefore, in this study, we introduce a novel electron-reserve-enhanced Cs2CuBr4/TiOx-Ar (CCBT-Ar) structure for the photocatalytic synthesis of urea from CO2 and nitrate waste. Theoretical calculations and spectroscopic analysis underscore the critical role of oxygen vacancies (Ov) within the amorphous TiOx shell, enhancing reactant adsorption and catalyzing the rate-determining step (*OCONH2→*HOCONH2). However, the presence of Ov also results in significant carrier recombination, acting as trapping centers and reducing urea production activity. Importantly, we demonstrate that in-situ-grown carbon nanosheets, in conjunction with TiOx, function as efficient electron reservoirs, markedly mitigating trapping-induced recombination and facilitating electron redistribution. These reserved electrons can then actively participate in the urea synthesis process. As a result, the electron-reserve-enhanced structure exhibits robust solar urea yield and selectivity, even in challenging wastewater conditions. This work provides a rational and innovative approach to catalyst development in complex solar synthesis, offering promising avenues for the sustainable production of value-added chemicals while concurrently reducing carbon emissions.

Phase shift of coherent magnetization dynamics after ultrafast demagnetization in strongly quenched nickel thin films

The remagnetization process after ultrafast demagnetization can be described by relaxation mechanisms between the spin, electron, and lattice reservoirs. Thereby, collective spin excitations in form of spin waves and their angular momentum transfer play an important role on the longer timescales. In this work, we address the question whether the magnitude of demagnetization-the so-called quenching-affects the coherency and the phase of the excited spin waves. We present a study of coherent magnetization dynamics in thin nickel films after ultrafast demagnetization using the all-optical, time-resolved magneto-optical Kerr-effect technique. The largest coherent precession amplitude was observed for strongly quenched systems, indicating a well-defined precession phase for all pump pulses at a demagnetization of up to 90% in this system. Moreover, the phase of the excited spin-waves in Ni increases with the pump fluence, indicating a delayed start of the precession during the remagnetization. We compare these findings to recent studies in Ni80Fe20(permalloy), to evaluate the influence of the magneto-elastic coupling and non-linear spin-wave dynamics on the magnetization dynamics.

Fe(II)-Catalyzed Metal-Ligand Cooperative Approach for Selective C3-Alkylation of Indoles

Herein, we report a straightforward approach for synthesizing C3-alkylated indoles selectively via an iron-catalyzed alkylation of indoles using alcohols as the alkylating agents. A well-defined, air-stable, and easy-to-prepare Fe(II)-catalyst of a redox-active tridentate arylazo scaffold was used as a catalyst. Various C3-alkylated indoles were prepared selectively in moderate to good isolated yields by coupling indoles with different substituted alcohols. The methodology is compatible with the gram-scale synthesis. Control experiments were performed to unveil the mechanism, which revealed that the alkylation reaction proceeds via borrowing hydrogen pathway where the coordinated azo-aromatic ligand actively participates during catalysis, acting as an electron and hydrogen reservoir.

Electron Reservoir Effect of Adjacent Fe Nanoclusters Boosts Atomic Fe Active Sites on Porous Carbon for the Both Electrocatalytic Oxygen Reduction and CO2 Reduction Reaction.

Electrochemical oxygen reduction reaction (ORR) and carbon dioxide reduction reaction (CO2RR) are greatly significant in renewable energy-related devices and carbon-neutral closed cycle, while the development of robust and highly efficient electrocatalysts has remained challenges. Herein, a hybrid electrocatalyst, featuring axial N-coordinated Fe single atom sites on hierarchically N, P-codoped porous carbon support and Fe nanoclusters as electron reservoir (FeNCs/FeSAs-NPC), is fabricated via in situ thermal transformation of the precursor of a supramolecular polymer initiated by intermolecular hydrogen bonds co-assembly. The FeNCs/FeSAs-NPC catalyst manifests superior oxygen reduction activity with a half-wave potential of 0.91V in alkaline solution, as well as high CO2 to CO Faraday efficiency (FE) of surpassing 90% in a wide potential window from -0.40 to -0.85V, along with excellent electrochemical durability. Theoretical calculations indicate that the electron reservoir effect of Fe nanoclusters can trigger the electron redistribution of the atomic Fe moieties, facilitating the activation of O2 and CO2 molecules, lowering the energy barriers for rate-determining step, and thus contributing to the accelerated ORR and CO2RR kinetics. This work offers an effective design of electron coupling catalysts that have advanced single atoms coexisting with nanoclusters for efficient ORR and CO2RR.

Photoelectrochemical Oxidation of Glycerol over g-C3N4 Nanosheets Coupled with Metal-Assisted Hybrid Carbon Quantum Dots

Carbon quantum dots (CDs) are the most promising candidates of the carbon family with a size of less than 10nm. They owned superior properties such as high solubility in aqueous medium, low toxicity, biocompatibility, stable photoluminescence, spectral convertor, and act as electron reservoirs. These properties make CDs suitable for photo-electrochemical catalytic applications. Low quantum yield and activity in the visible light spectrum of CDs may restrict their applicability. To address this issue, doping and surface passivation of CDs is the only approach to improve their physicochemical characteristics, visible light absorption, and quantum yield by altering their size and structure. Metals are electron-efficient entities and act as electron donors. As a result, when metal ions are doped into CDs, the charge density and charge transition between the core of the CDs and the metal ions increases. This results in a greater improvement in the physicochemical properties of CDs as compared to non-metal doping[1]. Metal-assisted CDs i.e. hybrid CDs tend to modulate energy band positions, change the electronic structure, increase quantum yield, and generate new emissive traps in CDs. The photoluminescence property of CDs can be enhanced due to the surface plasmonic resonance (SPR) effects of metal nanoparticles (NPs). Hybrid CDs also show better catalytic performance as compared to the pristine CDs. It helps to enhance the active sites on the CDs surface to facilitate catalytic performance.By keeping these properties, the hybrid CDs were effectively utilized in the field of dye decolorization, degradation of water pollutants, storage materials, and as a sensor[2][3]. The photo-assisted electrochemical glycerol valorization is one of the prominent methods for producing value-added chemicals such as glycolic acid. However, it is a challenge to achieve high yield and selectivity of products. This research investigated the fabrication of heterojunction of g-C3N4 (CN) with CDs and Bi-assisted CDs (BiCD) as a sustainable photoactive material. The heterojunction was obtained by incorporating CDs and BiCD (5wt.% each) onto CN nanosheets by in-situ thermal polymerization treatment and named CDCN and BiCDCN. The prepared composite was analyzed by structural (XRD), functional (XPS) microscopic (FESEM, FETEM) spectroscopic (UV-Vis, PL, TRPL, EDS), and photoelectrochemical characterization techniques.The band gap of CN was obtained as 2.78 eV which was reduced to 2.69 eV for CDCN and 2.62eV for BiCDCN, increasing the absorbance in the visible light zone. The existence of CDs and BiCDs was confirmed by, FETEM investigation (Fig.1a). The XPS analysis of the composite revealed the presence of Bi 4f chemical state of bismuth metal. The calculated TRPL lifetime was 0.28ns for BiCDCN and 2.51 ns for CDCN which was lower than that of CN (9.31 ns) suggesting the rapid electron transfer ability of BiCDCN. In the presence of light and glycerol, the composite BiCDCN had the maximum photocurrent density of 12 mA/cm2, followed by CDCN (1.6 mA/cm2) and CN (1.3 mA/cm2) at 1.2 V. The photoelectrochemical oxidation of glycerol was performed at 0.8V for 3h. The detected products were glycolic acid, glyceric, glyoxylic acid, and oxalic acid. The addition of CD to CN increased the glycerol conversion and yield of glycolic acid & glyoxylic acid significantly. The composite exhibited 43% selectivity towards glycolic acid and 34% for glyoxylic acid. The glycerol conversion and yield of these two products were further enhanced by Bi doping. BiCDCN had a total glycerol conversion of 21%, followed by CDCN at 5.7% and CN at 3.8%. The BiCDCN had the highest yield of glycolic acid at 8.9 % and that for CDCN was 2.4 % and 1.2 % for CN (Fig.1b). The glyoxylic acid yield was 7.2%, 2.2%, and 0.8% for BiCDCN, CDCN, and CN, respectively. Figure 1

Sonoinduced Tumor Therapy and Metastasis Inhibition by a Ruthenium Complex with Dual Action: Superoxide Anion Sensitization and Ligand Fracture.

Photoresponsive ruthenium(II) complexes have recently emerged as a promising tool for synergistic photodynamic therapy and chemotherapy in oncology, as well as for antimicrobial applications. However, the limited penetration power of photons prevents the treatment of deep-seated lesions. In this study, we introduce a sonoresponsive ruthenium complex capable of generating superoxide anion (O2•-) via type I process and initiating a ligand fracture process upon ultrasound triggering. Attaching hydroxyflavone (HF) as an "electron reservoir" to the octahedral-polypyridyl-ruthenium complex resulted in decreased highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps and triplet-state metal to ligand charge transfer (3MLCT) state energy (0.89 eV). This modification enhanced the generation of O2•- under therapeutic ultrasound irradiation at a frequency of 1 MHz. The produced O2•- rapidly induced an intramolecular cascade reaction and HF ligand fracture. As a proof-of-concept, we engineered the Ru complex into a metallopolymer platform (PolyRuHF), which could be activated by low-power ultrasound (1.5 W cm-2, 1.0 MHz, 50% duty cycle) within a centimeter range of tissue. This activation led to O2•- generation and the release of cytotoxic ruthenium complexes. Consequently, PolyRuHF induced cellular apoptosis and ferroptosis by causing mitochondrial dysfunction and excessive toxic lipid peroxidation. Furthermore, PolyRuHF effectively inhibited subcutaneous and orthotopic breast tumors and prevented lung metastasis by downregulating metastasis-related proteins in mice. This study introduces the first sonoresponsive ruthenium complex for sonodynamic therapy/sonoactivated chemotherapy, offering new avenues for deep tumor treatment.

In situ tuning of platinum 5d valence states for four-electron oxygen reduction

The oxygen reduction reaction (ORR) catalyzed by efficient and economical catalysts is critical for sustainable energy devices. Although the newly-emerging atomically dispersed platinum catalysts are highly attractive for maximizing atomic utilization, their catalytic selectivity and durability are severely limited by the inflexible valence transformation between Pt and supports. Here, we present a structure by anchoring Pt atoms onto valence-adjustable CuOx/Cu hybrid nanoparticle supports (Pt1-CuOx/Cu), in which the high-valence Cu (+2) in CuOx combined with zero-valent Cu (0) serves as a wide-range valence electron reservoir (0‒2e) to dynamically adjust the Pt 5d valence states during the ORR. In situ spectroscopic characterizations demonstrate that the dynamic evolution of the Pt 5d valence electron configurations could optimize the adsorption strength of *OOH intermediate and further accelerate the dissociation of O = O bonds for the four-electron ORR. As a result, the Pt1-CuOx/Cu catalysts deliver superior ORR performance with a significantly enhanced four-electron selectivity of over 97% and long-term durability.

Ru3@Mo2CO2 MXene single-cluster catalyst for highly efficient N2-to-NH3 conversion.

Single-cluster catalysts (SCCs) representing structurally well-defined metal clusters anchored on support tend to exhibit tunable catalytic performance for complex redox reactions in heterogeneous catalysis. Here we report a theoretical study on an SCC of Ru3@Mo2CO2 MXene for N2-to-NH3 thermal conversion. Our results show that Ru3@Mo2CO2 can effectively activate N2 and promotes its conversion to NH3 through an association mechanism, in which the rate-determining step of NH2* + H* → NH3* has a low energy barrier of 1.29eV. Notably, with the assistance of Mo2CO2 support, the positively charged Ru3 cluster active site can effectively adsorb and activate N2, leading to 0.74 |e| charge transfer from Ru3@Mo2CO2 to the adsorbed N2. The supported Ru3 also acts as an electron reservoir to regulate the charge transfer for various intermediate steps of ammonia synthesis. Microkinetic analysis shows that the turnover frequency of the N2-to-NH3 conversion on Ru3@Mo2CO2 is as high as 1.45×10-2 s-1 site-1 at a selected thermodynamic condition of 48bar and 700K, the performance of which even surpasses that of the Ru B5 site and Fe3/θ-Al2O3(010) reported before. Our work provides a theoretical understanding of the high stability and catalytic mechanism of Ru3@Mo2CO2 and guidance for further designing and fabricating MXene-based metal SCCs for ammonia synthesis under mild conditions.

Enhanced paracetamol degradation via strong covalent coupling of Mo[sbnd]O[sbnd]C bonds in C/MoS2 nanocomposites for piezoelectric activation of peroxymonosulfate: Electron bridge and enrichment

Paracetamol (PCM) has been frequently detected in natural water bodies, posing potential threats to human health and the natural environment. In this work, we developed a strong covalent coupling system of MoOC within carbon doped MoS2 (C/MoS2) material to piezoelectrically activate peroxymonosulfate (PMS) for PCM degradation. The C/MoS2 was synthesized successfully using one-step hydrothermal method and exhibited 91.8 % of PCM degradation efficiency and 0.04042 min−1 of rate constant (3.29 times of pristine MoS2) within 60 min under ultrasonic vibration. According to characterization and theoretical computational results, the Mo atoms near sulfur vacancies exhibited unsaturation, enabling them to bond with oxygen atoms on carbon substrate, forming a strong covalent coupling structure primarily driven by MoOC bonds. MoOC bonds served as “electron bridges” that efficiently transported electrons from the piezoelectrically excited electron reservoir of MoS2 to the active sites at heterogeneous interfaces, creating electron-rich surface regions and simultaneously inhibiting the recombination of piezoelectric charge carriers, thereby essentially enhancing the intrinsic conductivity of MoS2. Furthermore, as active adsorption sites, MoOC bonds initially strongly adsorbed PMS, activating it into reactive oxygen species (ROS), subsequently absorbing O2 to realize the enrichment of oxides and further promote the PCM decomposition. This work offered new perspectives on the interface modification and development of efficient MoS2-based piezoelectric catalysts for water purification.

Topotactic Syntopogenous Sodium Vanadium Fluoride for High-Performance Sodium-Ion Batteries: Electron and Sodium-Ion Reservoirs in Perovskite/Diperovskite Superlattice.

In order to simultaneously accelerate ion and electron transfer in sodium-ion battery (SIB) cathodes, a topotactic superlattice was utilized, in which the atomically intrinsic lattice-matching effect from inner to external surface can boost the charge transfer due to the disappearance of the heterojunction interface. Herein, a topotactic syntopogenous Na3VF6/NaVF3 superlattice formulated as Na2.9V1.1F6 (NVF) was synthesized by a facile one-step low-temperature hydrothermal reaction. NVF nanoparticles show an excellent Na+ storage capacity (∼205 mAh g-1) in a high voltage window up to 4.2 V with ultralong cycling stability. That is associated with the mixed occupancy of V and Na in NVF. The multivalent V centers serve as electron reservoirs to inhibit phase transformation, and the Na-enriched Na3VF6 with better electron conductivity acts as a Na+ reservoir for effective electron transfer. Highly reversible (de)intercalation of Na+ is achieved in the channel of perovskite-type NaVF3 with structural integrity.

Defect tailoring in K-doped carbon nitride: Enabling efficient decoupling of light and dark reactions for timely and delayed on-demand solar hydrogen production

Decoupling hydrogen production from diurnal cycles is challenging in solar energy conversion. Recently, defect-modified K-doped carbon nitride has demonstrated the potential to realize this unique property. However, the concomitant undesirable defects during eutectic treatment, such as triazine ring insertion, impose substantial limitations on the decoupling performance. In this study, a one-step eutectic method assisted by CCl4 was developed, which removed the detrimental triazine-based defects while introducing beneficial nitrogen vacancies. The engineered structure efficiently enhances visible light absorption, and spatially separates the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The localized LUMO on N-K sites serves as an electron reservoir, facilitating carrier separation and inhibiting the recombination. Consequently, one of the highest timely light-driven activities among polymeric photocatalysts was achieved, reaching 2557 times the H2 production rate compared to the un-engineered counterpart. More significantly, the electron reservoir could store active electrons for several weeks, successfully enabling delayed on-demand solar H2 production and decoupling H2 evolution from diurnal cycles. This study effectively achieves both spatial and temporal separation of light absorption, solar storage, and release through defect tailoring, which is expected to advance the development of decoupled catalytic studies.