Electron Cloud Density Research Articles

Electronic effect tuned ion-dipole interactions for low-temperature electrolyte design of LiFePO4-based lithium-ion batteries

Poor low-temperature performance is one of the major challenges hindering the widespread use of lithium-ion batteries. Modulation of Li+ solvation structure to facilitate desolvation process is an important strategy in electrolyte engineering under low temperature. Herein, different electronic effect groups including electron-withdrawing groups (CH2Cl) and electron-donating groups (CH3), are introduced in the weakly solvated solvent tetrahydrofuran (THF), respectively, to compare their effects on the ion-dipole interaction in the electrolyte and thus the regulation of Li+ solvation structure. Theoretical calculations combined with characterization demonstrates that the introduction of electron-withdrawing groups CH2Cl in the solvent can reduce the electron cloud density of oxygen in the THF solvent molecule, weaken the binding energy between Li+ and the solvent, and lead to more anions participating in solvation shell of Li+ and coordinating with Li+, thus accelerating the desolvation kinetics of Li+. This electrolyte-design strategy based on electronic effect tuned ion-dipole interactions has notably increased the cycling stability of the LiFePO4||Li half-cell at −20 °C, that is, it not only increases the capacity by about 10 mAh g−1 at the rate of 0.2 C, but also maintains the capacity retention rate at 97.4 % after 100 cycles. This study reveals an important electrolyte design strategy at the molecular level.

Unlocking the Anion Effect on Steerable Production of 5‐Hydroxymethylfurfural

AbstractHomogeneous metal salt catalysts play a pivotal role in industrial production of 5‐hydroxymethylfurfural (HMF). Herein, we first proposed the anion effect on steerable production of HMF using metal salts with different anions as catalyst in a biphasic system of tetrahydrofuran (THF)/NaCl aqueous solution (NaCl aq). Notably, the anions affected the catalytic activity of the metal salts, leading to an order of magnitude difference in the HMF yields, i.e., AlBr3 (74.0 mol %)>AlCl3 (60.8 mol %)>Al2(SO4)3 (35.2 mol %)>Al(NO3)3 (14.9 mol %). The anion effect on steerable production of HMF could be attributed to the proximity effect and electron tension. Anions form close‐range interactions with glucose molecules by proximity effect to promote electron transfer, facilitating the isomerization of glucose to fructose. Besides, anions induce a reduction of the electron cloud density of glucose carbon atoms, generating electron tension that rapidly transforms glucose from the ground state to the transition state, thereby increasing the HMF yield. Based on the revelation of anions effect and evaluation of techno‐economic process, we expect to provides theoretical guidance for high‐throughput screening of metal salt catalysts in industrial biorefinery.

Unlocking the Anion Effect on Steerable Production of 5-Hydroxymethylfurfural.

Homogeneous metal salt catalysts play a pivotal role in industrial production of 5-hydroxymethylfurfural (HMF). Herein, we first proposed the anion effect on steerable production of HMF using metal salts with different anions as catalyst in a biphasic system of tetrahydrofuran (THF)/NaCl aqueous solution (NaCl aq). Notably, the anions affected the catalytic activity of the metal salts, leading to an order of magnitude difference in the HMF yields, i.e., AlBr3 (74.0 mol %)>AlCl3 (60.8 mol %)>Al2(SO4)3 (35.2 mol %)>Al(NO3)3 (14.9 mol %). The anion effect on steerable production of HMF could be attributed to the proximity effect and electron tension. Anions form close-range interactions with glucose molecules by proximity effect to promote electron transfer, facilitating the isomerization of glucose to fructose. Besides, anions induce a reduction of the electron cloud density of glucose carbon atoms, generating electron tension that rapidly transforms glucose from the ground state to the transition state, thereby increasing the HMF yield. Based on the revelation of anions effect and evaluation of techno-economic process, we expect to provides theoretical guidance for high-throughput screening of metal salt catalysts in industrial biorefinery.

In Situ Molecular Reconfiguration of Pyrene Redox-Active Molecules for High-Performance Aqueous Organic Flow Batteries.

Aqueous organic flow batteries (AOFBs) hold great potential for large-scale energy storage, however, scalable, green, and economical synthetic methods for stable organic redox-active molecules (ORAMs) are still required for their practical applications. Herein, pyrene-based ORAMs are obtained via an in situ organic electrolysis strategy in a flow cell. It is revealed that the water attacking pyrenes restructured molecules to produce a variety of isomers and dimers during the electrolysis, which can be modulated by regulating the local electron cloud density and steric hindrance of pyrene precursors. As a result, the molecularly reconfigured pyrene-based catholytes, even without any further purification, achieved a high electrolyte utilization of ≈96% and volumetric capacity above 50AhL-1. Inspiringly, remarkable cell stability with almost no capacity decay for ≈70 days is achieved, benefiting from the robust aromatic structure of the pyrene cores. The insights into the in situ electrosynthesis of pyrene-based ORAMs provided in the work will provide guidance for designing ultra-stable ORAMs for AOFB applications.

Highly stable and electron-rich Ni single atom catalyst for directed electroreduction of CO2 to CO

Transition metal-nitrogen-carbon (M−N−C) are considered as promising candidates for the electrochemical conversion of inert CO2 into high value-added CO products. However, previous reports have focused on Ni single-atom sites (Ni SAs) and the role of Ni nanoparticles (Ni NPs) in CO2 electroreduction reaction (CO2RR) has been overlooked. Herein, we prepared a series of Ni, N-codoped porous carbon (NiNC-T, T represents the temperature) catalysts by combining Ni phthalocyanine pyrolysis and acid etching strategy, which either contain only Ni SAs or both Ni SAs and Ni NPs. Notably, the NiNC-1100 catalyst with both Ni SAs and Ni NPs exhibited 99 % CO faradaic efficiency (FECO) at −0.66 V versus reversible hydrogen electrode (vs. RHE) and FECO above 98 % over a wide potential range (−0.66 V ∼ −1.06 V). Moreover, the FECO of NiNC-1100 remained above 95 % after 100 h of continuous electrocatalysis, which was significantly superior to that of the most advanced Ni single atom electrocatalysts. The systematic characterization results showed that the introduction of Ni NPs can promote the adsorption and activation of CO2 by increasing the electron cloud density of Ni SAs, thus enhancing the CO2RR catalytic performance.

Electron-withdrawing effect of polyoxometalates in Cu(I)-based metal–organic frameworks for enhanced azide-alkyne “click” reaction

Boosting the nucleophilicity of Cu(I) sites is an essential strategy to enhance the efficiency of Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. In this work, a Lindquist-type polyoxometalate (POM)-based metal–organic framework, [CuI4(W6O19)2(L)]·2H2O (NEAU-1), was synthesized via an in-situ solvothermal method. Single-crystal X-ray diffraction results reveal that NEAU-1 exhibits a sandwich structure, with POMs intercalated between the two-dimensional layers formed by resorcin[4]arene ligands and Cu(I) ions. NEAU-1 possesses abundant Cu(I) active sites and high chemical stability, making it an effective heterogeneous catalyst for the CuAAC reaction. More importantly, the presence of POMs effectively reduces the electron cloud density around Cu(I) sites, significantly lowering the energy barrier for the formation of copper-acetylide compounds and facilitating subsequent nucleophilic reactions. The synergistic catalytic effect of POMs and Cu(I) can achieve a conversion rate of over 99 % for benzyl azide and phenylacetylene within 40 min. This work presents a sustainable molecular-level strategy to enhance the activity of the CuAAC reaction.

Fluoropyridine modulated local charge distribution of carbon nitride to facilitate photocatalytic oxidative γ-valerolactone production

Synthesis of γ-valerolactone (GVL) from renewable biomass resources under mild reaction condition with metal-free catalysis is attractive but challenging. Herein, a novel porous fluoropyridine-incorporated carbon nitride (FPCN) was constructed and applied for photocatalytic oxidation of biomass-based 5-methyltetrahydrofurfural alcohol (5-MTHFA) to GVL. The catalyst exhibits excellent photocatalytic activity (93% 5-MTHFA conversion), with an 81% GVL yield, which is significantly higher than that of pyridine-incorporated carbon nitride and pure g-C3N4. Catalyst characterization and density functional theory (DFT) calculations showed that the porous structure of FPCN provides more exposed active sites for catalytic reaction, and the incorporated fluoropyridine rings effectively modulate the localization of electron cloud density, resulting in an enhanced photogenarated carrier separation efficiency and adsorption capacity for 5-MTHFA. Mechanistic studies reveal that photocatalytic oxidation process of 5-MTHFA mainly involves hydroxyl group oxidation and decarboxylation. This work provides new insight into designing carbon nitride-based photocatalysts for the efficient selective oxidation of renewable biomass to produce fine chemicals.

Living anionic copolymerization of 1,3-pentadiene isomers with alpha-methylstyrene in the presence of 2,2-di(2-tetrahydrofuryl)propane

The synthesis of statistical copolymers of alpha-methylstyrene (AMS) and 1,3-pentadiene (PD) isomers in the presence of 2,2-di(2-tetrahydrofuryl)propane (DTHFP) by living carbanionic polymerization was investigated in this paper. To the best of our knowledge, either AMS or PD monomer was rather difficult to homopolymerize in non-polar solvents without the help of polar additives even at high temperature due to its low ceiling temperature or relatively high electron cloud density of the conjugated CC double bond. However, the combination of RLi initiator and DTHFP regulator (0.1<DTHFP/Li < 0.5) allowed the rapid synthesis of the well-defined poly(AMS-stat-PD) with controlled molar masses (up to 32.5 kDa) and relatively narrow molecular weight distributions (1.10 < ĐMs < 1.52). Calculation of reactivity ratios by the Kelen–Tüdos method suggested that AMS copolymerized much more readily to with (Z)-1,3-pentadiene (ZP) than with (E)-1,3-pentadiene (EP) under the same conditions, whereas the EP/AMS copolymer exhibited much lower dispersity. 1H NMR results indicated that the polymer chain was found to be a mixture of 1,2-addition and 1,4-addition units, in the absence of 3,4-units. Kinetic experiments also showed that the apparent activation energy of EP/AMS copolymerization was slightly higher than that of the ZP/AMS case. To ensure complete conversion of the monomer, the feed ratio of AMS (fAMS) must be controlled to be within 0.3. In addition, the incorporation rate of AMS into the polymer chain increased with the increase in the feed ratio of AMS monomer. DSC curves showed that the Tg of the resulting copolymers increased gradually and could reach up to 25 °C (FAMS = 47). Based on the observation of the anionic statistical copolymerization behavior, an interpretation of the formation mechanism is presented here.

Improving the electrochemical performance of nickel-cobalt organic framework by hybridizing with carbon quantum dots

To improve the electrochemical properties of nickel-cobalt metal-organic skeleton materials, two carbon quantum dots (CQDs), namely, CQD-CA and N-doped CQD-CAn, were prepared by using citric acid as carbon source and then introduced into NiCo-MOF to prepare CQDs/NiCo-MOF composites. Through the application of physical characterization and electrochemical analysis methods, such as SEM, TEM, XRD, XPS and BET, it was found that NiCo-MOF@CA and NiCo-MOF@CAn exhibited a nano thinner lamellar structure, higher specific surface area, larger pore structure, and excellent electron transport ability. Especially, by introducing CQDs, the charge could transfer from oxygen to Ni and Co, and there was some higher electron cloud density around active metals Ni and Co in NiCo-MOF@CAn than in NiCo-MOF, effectively activating the metal center Ni and Co. As the result, the specific capacitance of NiCo-MOF@CAn reached 1917.7 F·g−1 at the potential scan rate 5 mV·s−1, significantly higher than that of NiCo-MOF (1173.4 F·g−1) and NiCo-MOF@CA (1489.3 F·g−1). The method might provide an alternative strategy for modulating the morphology, porous structure and the partial electron structure of the target materials by introducing various CQDs.

Purification and Kinetics of Chlorogenic Acid from Eucommia ulmoides Oliver Leaves by Macroporous Resins Combined with First-Principles Calculation

Background: A simple and effective method to separate chlorogenic acid from Eucommia ulmoides leaves with macroporous resin was studied in this paper. Methods: In order to optimize the separation process of chlorogenic acid from Eucommia ulmoides leaves, dynamic adsorption and desorption experiments were carried out on a glass column filled with XDA-8 resin. Based on the First-principles calculation, the possible adsorption models were simulated. Results: Among the six macroporous resins, XDA-8 showed good adsorption/desorption capacity and a high adsorption/desorption ratio for chlorogenic acid. After being treated with XDA-8 resin once, the content of chlorogenic acid from the extraction increased by 525%, and the recovery of chlorogenic acid reached 85.36%. Conclusion: At 25°C, the adsorption behavior of chlorogenic acid on XDA-8 resin was consistent with the Langmuir isotherm model and pseudo-second-order kinetic model. Furthermore, by calculating the charge changes of the O atom at each position in the chlorogenic acid molecule and the H atom at the adsorption site in polystyrene molecule with resin skeleton, and combining with the electron cloud density distribution diagram of chlorogenic acid and resin skeleton, the adsorption of chlorogenic acid by XDA-8 resin is mainly due to the charge transfer, which causes the electron cloud to overlap.

Conversion of 5‐Hydroxymethylfurfural and Carbohydrates to 2,5‐Diformylfuran Over MoOx/Biochar Catalysts

AbstractHere, a series of nitrogen‐doped carbon (NC) supported transition metal oxide catalysts were prepared by pyrolysis of chitosan‐metal salt mixtures for the efficient synthesis 2,5‐diformylfuran (DFF) from 5‐hydroxymethylfurfural (HMF) and fructose. Among them, supported molybdenum‐based species on nitrogen‐doped carbon (Mo/NC) exhibited excellent activity and selectivity for selective oxidation of HMF to DFF. The presence of nitrogen species reduces the electron cloud density around the Mo species, thereby improving the catalytic activity. Moreover, the interaction between active MoO2 species on the catalyst surface and NC ensured the stability of the catalyst, resulting in no significant loss of activity after four catalytic cycles. 99.5 % and 55.1 % yields of DFF with full conversion were obtained from HMF and fructose respectively over Mo/NC‐chitosan‐600 in DMSO under ambient air. In order to enhance DFF yield from fructose, sulfonate groups were introduced into Mo/NC‐chitosan‐600 catalyst, leading to the highest DFF yield of 70.2 %. In addition, this catalyst also allowed 10.0%, 22.9% and 33.3% DFF yields from glucose, sucrose and inulin, respectively.

Engineering electron cloud density of phenazine for high-voltage and long-life alkaline batteries

Alkaline aqueous batteries, with intrinsic high safety and potential for high voltage, have always been a hot research topic. Despite several generations of development of anode materials, they still face the challenge of poor cycling stability. Imines have a significant advantage in stability compared to other n-type materials, but their potential is not low enough compared to metal anodes. Herein, a symmetrically structured, extended π-conjugated imine compound, namely cyano-substituted dotriaconta tetrazaoctacyclo (4CNDTZ), was synthesized for the first time and evaluated as the anode materials for alkaline aqueous batteries. 4CNDTZ exhibits a remarkable capacity of 250 mAh g-1 at 0.2 A g-1, coupled with a remarkably low plateau potential of -0.81 V (vs. SHE), significantly below that of conventional alkaline battery anodes. Advanced characterization techniques alongside theoretical calculations confirm that the active sites crucial for its performance are the CN and CN groups, driving an oxidation–reduction process involving the transfer of 4 K⁺ and 4 electrons. When coupled with Ni(OH)2 cathode, the full cells exhibit a discharge voltage plateau of 1.17 V, allowing the full cells to achieve an energy density of up to 170 Wh kg-1 and sustain stable operation through 10,000 cycles.

Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH.

Dark aqueous-phase reactions involving the nitrosation and nitration of aromatic organic compounds play a significant role in the production of light-absorbing organic carbon in the atmosphere. This process constitutes a crucial aspect of tropospheric chemistry and has attracted growing research interest, particularly in understanding the mechanisms governing nighttime reactions between phenols and nitrogen oxides. In this study, we present new findings concerning the rapid dark reactions between phenols containing electron-donating groups and inorganic nitrite in acidic aqueous solutions with pH levels <3.5. This reaction generates a substantial amount of nitroso- and nitro-substituted phenolic compounds, known for their light-absorbing properties and toxicity. In experiments utilizing various substituted phenols, we demonstrate that their reaction rates with nitrite depend on the electron cloud density of the benzene ring, indicative of an electrophilic substitution reaction mechanism. Control experiments and theoretical calculations indicate that the nitrosonium ion (NO+) is the reactive nitrogen species responsible for undergoing electrophilic reactions with phenolate anions, leading to the formation of nitroso-substituted phenolic compounds. These compounds then undergo partial oxidation to form nitro-substituted phenols through reactions with nitrous acid (HONO) or other oxidants like oxygen. Our findings unveil a novel mechanism for swift atmospheric nitrosation and nitration reactions that occur within acidic cloud droplets or aerosol water, providing valuable insights into the rapid nocturnal formation of nitrogen-containing organic compounds with significant implications for climate dynamics and human health.

Regulating the Electronic Structure of Pd Nanoparticles on NH3‐pretreated Nano‐flake TiO2 for Efficient Hydrogenation of Nitrile Butadiene Rubber

The heterogeneous selective hydrogenation of nitrile butadiene rubber (NBR) is an efficient method to generate high value‐added hydrogenated NBR. Nevertheless, the inherent large molecular size and high spatial hindrance of polymers lead to poor activity and metal loss. Herein, we report a simple support ammonia pretreatment strategy for the synthesis of efficient N‐doped Pd catalyst and applied for the NBR hydrogenation. The results reveal that N doping enhances electrons transfer from the support to Pd more effectively than oxygen‐rich vacancy carrier, thereby substantially enhancing the electron cloud density and stability of the Pd sites. The formation of more electron‐rich Pd sites not only significantly enhances the adsorption‐activation ability of C=C and H2, but also lowers the apparent activation energy of the reaction. As a result, the Pd/N‐TiO2‐R demonstrates best activity with a hydrogenation degree (HD) of 98% and a TOF value of 335 h‐1, significantly higher than that of Pd/TiO2‐R (HD=83%, 282 h‐1) and Pd/TiO2 (HD=74%, 204 h‐1). This strategy will provide new inspiration to improve the activity and stability of Pd/TiO2 catalysts for the hydrogenation of unsaturated polymers.

Highly‐Dispersed Single‐Crystalline Ni‐Rich Cathodes with Low Li/O Loss for High‐Power and Long‐Life Li‐Ion Batteries

AbstractHighly‐dispersed single‐crystalline Ni‐rich cathodes with low Li/O loss are the key for high‐power Li‐ion batteries, but it is still a big challenge because an additional 60–110 °C higher synthesis temperature is required in comparison with the polycrystalline counterparts. Herein, a highly‐ordered and monodisperse single‐crystalline LiNi0.83Co0.12Mn0.05O2 (NCM83) cathode with an average size of 3.24 µm is reported by a Sr/Nb synergically controlling the grain surface energy strategy based on the Vegard's slopes of various ions. The solid‐phase lithiation temperature is reduced by ≈80 °C, greatly reducing Li/Ni disorder and oxygen vacancies with rapid Li‐ion diffusion kinetics and high structure stability. The introduced Sr/Nb ions remarkably increase the electron cloud density near the Fermi level, while alleviating the H2‐H3 phase transition with reduced lattice shrinkage. The as‐prepared single‐crystalline NCM83 cathode exhibits obvious increased capacity retention of 60% at 10C (vs. 0.1C) in coin‐type half‐cells and 89% after cycling 1000 times at 0.5C in pouch‐type full‐cells. The work sheds light on the low‐temperature synthesis of monodisperse and uniform single‐crystalline Ni‐rich cathodes for high‐power and long‐life Li‐ion batteries.

D/A heterojunction photocatalysts interspersed onto biochar to couple photocatalysis and adsorption for visible light-responsive efficient removal of pollutants

Phenol has various applications in industry, due to its hazardousness, solubility, and volatility, it persists in water and poses a risk to human health. People are excited by the progress of photodegradation technology that facilitates water pollution treatment. The effect of side-chain engineering is proven to enhance photodegradation performance by improving optoelectronic properties. Therefore, here is a strategy that introduces functional groups to change the electron cloud density, achieving excellent optoelectronic properties evidenced by efficient exciton dissociation, separation, and fine-tuned energy level. Subsequently, by coupling of photocatalysis and adsorption, the donor/acceptor (D/A) heterojunction photocatalysts (PBDB-T: BTTIC-TT, PBDB-T: BTTIC-Ph) are designed via loading on coconut-shell carbon to process phenol. The results indicate that the champion photocatalyst PBDB-T: BTTIC-TT possesses superior optoelectronic properties, which can be attributed to the stronger electron-withdrawing ability of thieno[3,2-b]thiophene than benzene. Consequently, the synergistic efficiency of adsorption and photocatalysis of phenol (10, 20 mg/L) are removed within 10 mins over 90 % which is still valid after twenty cycles. Surprisingly, a high concentration of phenol (100 mg/L) also exhibited excellent removal efficiency of over 80 % within 60 min.

Metabolic characteristic profiling of 1-amino-3,3-dimethyl-1-oxobutan-2-yl-derived indole and indazole synthetic cannabinoids in vitro

Characterizing the metabolic profiles of synthetic cannabinoids (SCs), a type of new psychoactive substances, is of particular importance for forensic detection and analysis. Although the metabolism of individual SCs derived from 1-amino-3,3-dimethyl-1-oxobutan-2-yl (ADB-SCs) has been reported, their metabolites also undergo a continuous change and combination of their tail and core regions. Therefore, elucidating the metabolic characteristics and effects of these structures is essential to enhance our understanding. In this study, the human liver microsome was used as the model for studying the in vitro phase I metabolism of 12 ADB-SCs, and the metabolites obtained were analyzed using ultra-high performance liquid chromatography–tandem four-level rod-electrostatic field orbital ion trap mass spectrometry to determine type, structure, and relative contents. The results indicated that hydroxylation and N-dealkylation were the major metabolic pathways in 12 ADB-SCs. The effects of the core and tail on the metabolism of these ADB-SCs were studied using theoretical calculations. For N-dealkylation metabolism, the strong electron-withdrawing conjugative effect of the –N= moiety in the pyrazole ring, steric hindrance of the tail, and electronic effect of substituents on the tail significantly affected metabolism. Further, it changed the relative contents of N-dealkylation metabolites. For hydroxylation, the reaction types were inconsistent at different parts. For instance, the phenyl group of the core is electrophilic, and its electron cloud density determines whether the phenyl group can be hydroxylated at the specific metabolic sites. Meanwhile, hydroxylation of the neopentyl moiety of the linked group involves the oxidation of aliphatic C–H bonds, whereas amide–hydroxylamine tautomerism affects hydroxylation metabolism. When the alkyl chain in the tail contains functional groups (such as –F and >CC<), oxidative defluorination or dihydrodiol metabolites are produced. Taken together, we systematically determined d the effect of functional groups in the core and tail of ADB-SCs on their metabolism, validating confirmed the feasibility of ADB-SC metabolism prediction based on their structural characteristics.

Study on Catalytic Performance in CO2 Hydrogenation to Methanol over Au–Cu/C3N4 Catalysts

In this paper, Au and Cu nanoparticles were successfully loaded onto porous g-C3N4 material through a hydrothermal synthesis method. By adjusting the proportion of Cu, Au-5%Cu/C3N4, Au-10%Cu/C3N4, and Au-15%Cu/C3N4, catalysts were prepared and used for the catalytic reduction of CO2 to methanol. Characterization analysis using high-resolution XPS spectra showed that with an increase in the doping amount of Cu, the electron cloud density on the Cu surface initially increased and then decreased. Electrons from Au atoms transferred to Cu atoms, leading to the accumulation of a more negative charge on the Cu surface, promoting the adsorption of partially positively charged C in CO2, which is more beneficial for catalyzing CO2. Among them, Au-10%Cu/C3N4 exhibited good reducibility and strong basic sites, as demonstrated by H2-TPR and CO2-TPD, with the conversion rates for CO2, methanol yield, and methanol selectivity being 11.58%, 41.29 g·kg−1·h−1 (0.39 μmol·g−1s−1), and 59.77%, respectively.

Hollow and Porous N‐Doped Carbon Framework as Lithium‐Sulfur Battery Interlayer for Accelerating Polysulfide Redox Kinetics

AbstractLithium‐sulfur batteries (LSBs) have become one of the most powerful candidates for next‐generation battery technologies due to their high theoretical energy density and low cost. However, the notorious shuttle effect of soluble lithium polysulfides (LiPSs) and sluggish conversion reaction kinetics cause low sulfur utilization and inferior cycle life. Rational catalyst design on hierarchical pore structures and composition optimization is highly desired to realize synergetic enrichment, accommodation, and catalytic redox capacity of sulfur species. In this consideration, the hollow and porous N‐doped carbon framework is prepared, in which Co nanoparticles (NPs) are evenly embedded (denoted as Co‐HMCF) to modulate electron cloud density of carbons. Electrochemical tests and density functional theory (DFT) calculations demonstrate that Co‐HMCF could simultaneously deliver superior catalytic activity in accelerating LiPSs conversion as well as Li2S nucleation/decomposition to improve overall sulfur redox kinetics. Consequently, the Co‐HMCF interlayer significantly improves the battery performance, including high discharge capacity output (1538 mAh g−1 at 0.2 C), stable long‐term cycle (0.047% capacity decay per cycle for 800 cycles at 1.0 C), and exceptional rate capacity (582 mAh g−1 at 5.0 C).

Oxygen-bridged Schottky junction in ZnO–Ni3ZnC0.7 promotes photocatalytic reduction of CO2 to CO: Steering charge flow and modulating electron density of active sites

Developing carbon dioxide (CO2) photocatalysts from transition metal carbides (TMCs) with abundant active sites, modulable electron cloud density, as well as low cost and high stability is of great significance for artificial photosynthesis. Building an efficient electron transfer channel between the photo-excitation site and the reaction-active site to extract and steer photo-induced electron flow is necessary but challenging for the highly selective conversion of CO2. In this study, we achieved an oxygen-bridged Schottky junction between ZnO and Ni3ZnC0.7 (denoted as Znoxide–O–ZnTMC) through a ligand-vacancy strategy of MOF. The ZnO–Ni3ZnC0.7 heterostructure integrates the photo-exciter (ZnO), high-speed electron transport channel (Znoxide–O–ZnTMC), and reaction-active species (Ni3ZnC0.7), where Znoxide–O–ZnTMC facilitates the transfer of excited electrons in ZnO to Ni3ZnC0.7. The Zn atoms in Ni3ZnC0.7 serve as electron-rich active sites, regulating the CO2 adsorption energy, promoting the transformation of *COOH to CO, and inhibiting H2 production. The ZnO–Ni3ZnC0.7 shows a high CO yield of 2674.80 μmol g–1h–1 with a selectivity of 93.40 % and an apparent quantum yield of 18.30 % (λ = 420 nm) with triethanolamine as a sacrificial agent. The CO production rate remains at 96.40 % after 18 h. Notably, ZnO–Ni3ZnC0.7 exhibits a high CO yield of 873.60 μmol g–1h–1 with a selectivity of 90.20 % in seawater.