Lithium-ion capacitors (LICs) are highly promising energy storage devices that combine the high-power density of supercapacitors with the high energy density of lithium-ion batteries. However, the irreversible lithium consumption during initial cycles degrades their key performance metrics, notably energy capacity and cycle life. This issue creates an urgent need for safe and efficient lithium replenishment techniques. In this work, we report a simple, efficient cathode-side pre-lithiation technology using dilithium dimethylmalonate (Li2DMMA) as the pre-lithiation agent. This rationally designed organic lithium salt features a high theoretical capacity (372 mAh g-1), low cost, and remarkable stability under ambient conditions. Its de-lithiation process occurs within a voltage range from 3.9 to 4.3V (vs. Li+/Li), and the cumulative irreversible capacity reaches 365.2 mAh g-1 over the first 5 cycles. Coupling with the activated carbon (AC) cathode lowers the de-lithiation potential of Li2DMMA, whose decomposition successfully pre-lithiated the soft carbon (SC) anode to safe and ideal potential of 0.086V (vs. Li+/Li), while leaving the AC cathode stability unaffected. The Li2DMMA//AC/SC LICs deliver an energy density of 87.2Whkg-1, a power density of 2.86kWkg-1, and a capacity retention of 84.45% after 10,000 cycles. This study provides practical guidelines for rational design of advanced cathode pre-lithiation agents with integrated performance.

While water electrolysis represents the most effective way for hydrogen production, its development is hindered by high activation energy barriers. Designing highly active and cost-effective electrocatalysts is crucial to address this limitation. This study successfully synthesized Fe-doped flower-like NiCoP microspheres with multilayer nanosheet architecture via hydrothermal synthesis and chemical vapor deposition (CVD) phosphidation. The multiscale hierarchical structure combined with Fe doping introduces abundant active sites and enhances the intrinsic activity of NiCoP, enabling the NCF P catalyst to exhibit exceptional bifunctional performance. The optimized NCF P-400 electrode achieves (The product obtained from Fe-doped NiCO-LDH after phosphorization at 400 degrees C) outstanding hydrogen evolution activity with an overpotential of 119 mV at 10 mA cm-2 and a Tafel slope of 110.6 mV dec-1. For oxygen evolution, it demonstrates a 252 mV overpotential at 100 mA cm-2 with a Tafel slope of 44.7 mV dec-1 and low charge transfer resistance. When employed in full water splitting, the electrode requires only 1.41 V cell voltage at 10 mA cm-2 and maintains stable operation for 120 h with negligible voltage fluctuation. This work provides new insights for designing efficient water electrolysis catalysts.

Ammonia is an indispensable chemical feedstock and an emerging carbon-free hydrogen carrier. Solar photo-thermo-catalytic ammonia synthesis, through the dual activation of photoelectric and photothermal effects, overcomes the trade-off between the high energy consumption of thermocatalysis and the low efficiency of photocatalysis, becoming a groundbreaking approach for efficient ammonia synthesis under mild conditions. This approach utilizes both short-wavelength light-excited hot electrons to reduce the activation energy of N2 dissociation and hydrogenation, and long-wavelength light-induced thermal energy to promote charge separation and accelerate the adsorption/desorption of reactants/products. Based on different synergistic modes between photoelectric and photothermal effects, this review systematically classifies the photo-thermo-catalytic ammonia synthesis into four categories: photo-assisted thermocatalysis (PATC), thermo-assisted photocatalysis (TAPC), photo-driven thermocatalysis (PDTC), and photo-thermal co-catalysis (PTCC). It elaborates on their unique mechanistic pathways, catalyst design strategies, and fundamentals of performance enhancement, and analyzes current challenges and future development directions. This review aims to provide a guideline for future investigations into mechanisms and catalyst design of photo-thermo-catalytic ammonia synthesis.

ABSTRACT Defect engineering is a promising strategy in heterogeneous catalysis, while understanding how the defective sites affect reactivity still remains ambiguous. Herein, we demonstrated an in‐depth experimental study of dynamic interaction of CO 2 molecules on defective In 2 S 3 surfaces by integrating operando X‐ray photoelectron spectroscopy with infrared spectroscopy. More specifically, the formation of S vacancy could promote the electron enrichment on adjacent In sites for facilitating CO 2 molecule adsorption, accompanying with the emergence of high oxidation states of surface In sites. Upon light illumination, the adsorbed CO 2 molecules undergo a sequential transformation into *COOH and *CO intermediates. However, an unexpected upside‐down inversion of *CO species on defective In sites from In–*CO to In–*OC has been firstly observed, severely restraining desorption of CO product from In 2 S 3 surfaces. Further tailoring the electronic structure of defective In sites by substituting residual S atom with O atom for inhibiting *CO inversion, a significant improvement of CO evolution activity has been achieved (18.3 µmol g −1 h −1 ), nearly five times higher than that of pristine In 2 S 3 (3.77 µmol g −1 h −1 ). This work provides the new insights on dynamic roles of defect‐derived active sites in determining catalytic activity, which might offer opportunities for fine control of catalytic process.

Regulating the coordination environment and defect structure of single-atom catalysts (SACs) is pivotal for advancing electrocatalytic CO2 reduction. Here, through controlled chemical etching and optimizing Ni2+ ion-exchange steps, we construct Ni-based SACs featuring asymmetric Ni-N-3 coordination coupled with adjacent carbon vacancies (Ni-N-3-C-V). The introduction of carbon vacancies elevates the spin state of the Ni center and enhances electron transfer, thereby promoting CO2 activation (*CO2). Transitioning from symmetric Ni-N-4 to low-coordination Ni-N-3 sites further tunes the d-band center, markedly reduces the free-energy barrier for *COOH formation, and facilitates *CO desorption. As a result, Ni-N-3-C-V exhibits outstanding CO2-to-CO performance, achieving a CO Faradaic efficiency of 97.9% at -0.8 V vs. RHE and maintaining >80% selectivity over a broad potential range. Density functional theory (DFT) calculations and operando spectroscopy elucidate the cooperative roles of carbon vacancies and asymmetric coordination in optimizing intermediate adsorption and reaction energetics. This work underscores the synergistic interplay between unsaturated coordination and defect engineering in tailoring local electronic structures, offering a robust strategy for enhancing the intrinsic activity of M-N-C SACs for efficient CO2 reduction.

Bismuth vanadate (BiVO4) is one of the most promising photoanode materials for photoelectrochemical (PEC) water splitting. However, severe charge recombination and sluggish surface water oxidation kinetics remain critical obstacles limiting its PEC performance and practical application. Herein, we demonstrate a one-step sulfidation strategy that simultaneously modulates the interfacial and surface electronic structures of NiFeOx-modified BiVO4 photoanodes to address key limitations and enhance the PEC activity. Notably, the resultant NiFeOSx/BiVO4 photoanodes achieve an exceptional photocurrent density of 5.68 mA cm−2 at 1.23 VRHE under one-sun illumination, representing a 3.64-fold enhancement over pristine BiVO4, while maintaining long-term stability. Comprehensive characterization and theoretical calculations clearly reveal that sulfidation strengthens the interfacial electronic coupling between NiFeOSx and BiVO4 via constructing S–O interfacial bonds, thereby reducing interfacial kinetic barriers and promoting charge separation and transfer. Moreover, the introduced low-electronegativity sulfur in NiFeOSx enhances hybridization between the S 3p and Ni/Fe 3d orbitals to induce charge redistribution and optimize the d-band center, which improves surface H2O adsorption/activation and accelerates oxygen evolution reaction kinetics. This work presents a simple yet effective route for simultaneous dual-scale electronic engineering of photoanodes towards high-performance PEC water splitting.

A novel WO3/P-g-C3N4/La2Ce2O7 ternary heterojunction photocatalyst was prepared via ball milling, calcination, and co-precipitation methods. The photocatalyst under consideration features a dual S-scheme carrier transfer mechanism (CTM) constructed by the S-scheme CTMs between the WO3 and the P-g-C3N4 components, as well as the P-g-C3N4 and the La2Ce2O7 components. The dual S-scheme CTM has been demonstrated to endow composite samples with strong redox capacity and efficient photo-generated carrier separation, thereby achieving excellent photocatalytic degradation performance for antibiotics and dyes. Consequently, the degradation efficiencies of tetracycline (TC), ciprofloxacin (CIP), methylene blue (MB), and rhodamine B (RhB) reached 87.041%, 93.007%, 94.139%, and 97.731%, respectively, within 30 min of photocatalysis. The results of the cyclic tests further confirmed structural and performance stability of the ternary photocatalyst, demonstrating its great potential for practical environmental remediation applications.

A La-ZnO/Bi2Fe4O9 composite photocatalyst, composed of La-doped ZnO and Bi2Fe4O9 components, was synthesized via hydrothermal synthesis, templating, and calcination processes. An S-scheme charge carrier transfer mechanism (CTM) was identified in the composite system, facilitating efficient charge separation and enhancing photocatalytic activity. The photocatalyst exhibits excellent performance in degrading tetracycline (TC) solution, attributed to the effective separation of photo-generated carriers and the high redox capacity originating from the S-scheme CTM. Furthermore, under the activation of peroxymonosulfate (PMS), its photocatalytic performance is significantly enhanced. Its universality was validated by the efficient degradation of ciprofloxacin (CIP), methyl orange (MO), and rhodamine B (RhB) solutions. Additionally, the photocatalyst demonstrates good stability in both photocatalytic activity and material structure during cyclic degradation experiments. The study highlights the considerable potential of this composite for environmental wastewater treatment applications.

Water electrolysis is a crucial technology for renewable energy conversion and storage, yet its progress is hindered by high overpotentials. The development of cost-effective, stable, non-precious metal catalysts with high activity is essential. In this study, a 3D flower-like NiCo-layered double hydroxide (LDH) structure is synthesized via a hydrothermal method, followed by Fe3+ doping through FeCl36H2O etching to produce Fe-doped NiCo-LDH (NCF-LDH). Under alkaline conditions, the NCF-LDH electrode demonstrates remarkable electrocatalytic performance for the oxygen evolution reaction (OER), attaining low overpotential of 263 mV at the current density of 50 mA cm− 2 and a Tafel slope of 71.9 mV dec− 1, accompanied by exceptional operational stability. The enhanced catalytic performance results from the synergistic effects of the 3D flower-like architecture, which provides a large specific surface area, exposing abundant active sites and promoting efficient charge transfer. Additionally, the Fe3+ induced lattice distortion and generation of vacancies disrupt the atomic arrangement, creating defect-rich sites that enhance OER activity.

In the field of photoelectrocatalytic (PEC) water splitting research, BiVO4/WO3 photoanodes exhibit excellent performance in facilitating the separation and transport of photogenerated electron-hole pairs. However, further improving charge transfer efficiency at the heterojunction interface and optimizing the kinetics of water oxidation reactions remain critical challenges. In this study, a Co-BiVO4-Mo/WO3 photoanode was successfully constructed by selectively introducing Mo at the interface and doping Co on the surface of the BiVO4/WO3 heterojunction, enabling precise control over the spatially graded distribution of the two dopants. The resulting photoanode achieved a photocurrent density of 3.423 mA cm-2 at 1.23 V vs. RHE, representing an approximately 1.6 times enhancement compared to the unmodified BiVO4/WO3 heterojunction (2.157 mA cm-2), 2.3 times higher than pristine BiVO4 (1.508 mA cm-2), and a nearly 3.8 times improvement over pristine WO3 (0.916 mA cm-2). The results demonstrate that the reversible interconversion between Mo4+ and Mo6+ at the heterojunction interface effectively promotes interfacial charge transfer. Meanwhile, the formed CoOOH on the photoanode surface significantly enhances surface reaction kinetics and improves photoanode stability. The gradient co-doping of Co and Mo at the interface and surface effectively enhances interfacial charge transfer kinetics and significantly improves structural stability. This well-designed gradient doping strategy provides a viable technical pathway for the rational design and controllable fabrication of high-performance PEC photoanodes for water oxidation.

Defect engineering is a promising strategy in heterogeneous catalysis, while understanding how the defective sites affect reactivity still remains ambiguous. Herein, we demonstrated an in-depth experimental study of dynamic interaction of CO2 molecules on defective In2S3 surfaces by integrating operando X-ray photoelectron spectroscopy with infrared spectroscopy. More specifically, the formation of S vacancy could promote the electron enrichment on adjacent In sites for facilitating CO2 molecule adsorption, accompanying with the emergence of high oxidation states of surface In sites. Upon light illumination, the adsorbed CO2 molecules undergo a sequential transformation into *COOH and *CO intermediates. However, an unexpected upside-down inversion of *CO species on defective In sites from In-*CO to In-*OC has been firstly observed, severely restraining desorption of CO product from In2S3 surfaces. Further tailoring the electronic structure of defective In sites by substituting residual S atom with O atom for inhibiting *CO inversion, a significant improvement of CO evolution activity has been achieved (18.3 µmol g-1 h-1), nearly five times higher than that of pristine In2S3 (3.77 µmol g-1 h-1). This work provides the new insights on dynamic roles of defect-derived active sites in determining catalytic activity, which might offer opportunities for fine control of catalytic process.

The ZnO polyhedra were initially prepared using ZIF-8 dodecahedra as the precursors. Following the decoration of Ag nanoparticles on the surface of ZnO polyhedra, the Ag nanoparticle-decorated ZnO/Ni3V2O8 composite photocatalyst was then synthesized by the hydrothermal method. The decorated Ag nanoparticles enhanced the absorption of visible light through the localized surface plasmon resonance (LSPR) effect, while also facilitating the separation of photoexcited carriers in the composite samples. Furthermore, the investigation revealed that the S-scheme carrier transfer mechanism (CTM) was identified between the ZnO and Ni3V2O8 components of the composite. Consequently, the combination of Ag/ZnO and ZnO/Ni3V2O8 heterojunctions results in the remarkable separation of photoexcited carriers in the Ag nanoparticle-decorated ZnO/Ni3V2O8 photocatalyst, thereby enhancing its photocatalytic performance in the degradation of tetracycline (TC) and ciprofloxacin (CIP) solutions. The high efficiency and universality in the degradation of environmental pollutants renders the prepared composite photocatalyst a promising candidate for application.

Photocatalytic CO2 reduction into carbonaceous fuels is regarded as a promising strategy to simultaneously alleviate the energy shortage and greenhouse effect. However, rapid charge recombination and sluggish CO2 reduction kinetics still severely restrict the photocatalytic CO2 conversion efficiency. Herein, we fabricated a twodimensional face-contact TiO2/Ag/CTF-Nv Z-scheme heterojunction featuring abundant N vacancies through a simple electrostatic self-assembly and annealing process for substantially enhancing CO2 photoreduction activity and selectivity. Specifically, in the absence of sacrificial reagent and photosensitizer, the TiO2/Ag/CTF-Nv achieves nearly 100% CO selectivity with a record evolution rate of 74.98 mu mol & centerdot;g-1 & centerdot;h-1, surpassing that of TiO2 and CTF-Nv by approximately 12.4 and 4.8 times, respectively. Systematic investigations involving operando experiments and theoretical calculations clearly demonstrate that N vacancies with strong electron-trapping characteristics can accelerate Z-scheme charge transfer by directing electron migration from TiO2 to CTF-Nv, further increasing the charge separation efficiency. Moreover, the N vacancies with high electron density serve as active sites to promote interfacial electrons transfer to CO2, improve CO2 chemisorption/activation capacity, and decrease energy barrier for CO evolution. This work offers novel insight into the construction of defect-modulated Z-scheme heterojunction for significantly improving photocatalytic CO2 reduction performances.

A novel WO3/P-g-C3N4/La2Ce2O7 ternary heterojunction photocatalyst was prepared via ball milling, calcination, and co-precipitation methods. The photocatalyst under consideration features a dual S-scheme carrier transfer mechanism (CTM) constructed by the S-scheme CTMs between the WO3 and the P-g-C3N4 components, as well as the P-g-C3N4 and the La2Ce2O7 components. The dual S-scheme CTM has been demonstrated to endow composite samples with strong redox capacity and efficient photo-generated carrier separation, thereby achieving excellent photocatalytic degradation performance for antibiotics and dyes. Consequently, the degradation efficiencies of tetracycline (TC), ciprofloxacin (CIP), methylene blue (MB), and rhodamine B (RhB) reached 87.041%, 93.007%, 94.139%, and 97.731%, respectively, within 30 min of photocatalysis. The results of the cyclic tests further confirmed structural and performance stability of the ternary photocatalyst, demonstrating its great potential for practical environmental remediation applications.

The efficient spatial separation of charges is crucial for augmenting the photocatalytic efficiency of H2 evolution. Herein, a CoOx@CdS core-shell heterostructure was fabricated via the photodeposition of amorphous CoOx on the surface of 3D CdS for highly efficient photocatalytic hydrogen evolution (PHE). Amorphous CoOx extends the optical absorption range, suppresses photocorrosion and enhances the specific surface area of CoOx@CdS. Consequently, optimized 2%CoOx@CdS exhibits superior PHE activity (16.30 mmol h-1 g-1) and outstanding photostability beyond 70 h, which is 2.9 times greater than that of pure CdS. The markedly enhanced photoactivity of optimized 2%CoOx@CdS is primarily due to the establishment of the core-shell architecture, wherein CoOx serves as a medium for the extraction of photogenerated holes. This structure efficiently accelerates charge separation and electron transfer at the CoOx@CdS interface. Specifically, CoOx acts as a hole collector, promoting more efficient photogenerated charge separation. Thus, this work presents a straightforward approach for the construction of the CoOx@CdS core-shell heterostructure as a robust photocatalyst for the transformation of solar energy.

Hydroxylated carbon quantum dots (OH-CQDs) modified g-C3N4 hollow microspheres were prepared using a supramolecular precursor self-assembly method. The incorporation of OH-CQDs into the precursor resulted in the formation of a hollow flower-like microsphere structure composed of g-C3N4 nanoflakes in the final samples, which exhibited a morphology that was roughly inherited from that of the supramolecular precursor. The incorporation of an optimal quantity of OH-CQDs did not result in a deterioration of the g-C3N4 product morphology; rather, it led to an enhancement in its microsphere structure. The modified nanostructure of g-C3N4 resulted in a significant increase in reaction sites and promoted the adsorption of organic dye molecules on the surface of the g-C3N4 photocatalyst during degradation reactions. Furthermore, despite the reduction in carrier concentration of g-C3N4 resulting from the decoration with OH-CQDs, the impedance was significantly diminished and the photocurrent density was also markedly improved. It can thus be concluded that the decoration of OH-CQDs has significantly enhanced the mobility of g-C3N4, thereby contributing to the improvement of the photocatalytic performance of the g-C3N4 photocatalyst.

Abstract The slow photogenerated carrier dynamics on the surface of photocatalyst have seriously hindered the progress of photocatalysis technology and the development of its industrial application. In this work, a Ni 5 P 4 /MnCdS ohmic junction with interfacial Ni─S chemical bond is constructed by electrostatic self‐assembly and hydrothermal method for highly efficient interfacial charge transfer. MnCdS nanosheets are successfully synthesized using solvothermal method and loaded onto metal rich Ni 5 P 4 nanoflowers. Ni 5 P 4 /MnCdS with atomically close contact interface through Ni─S bonds, resulting in a strong electronic coupling effect that regulates the direction of electron movement. The Ni 5 P 4 nanoflowers with a layered structure have outstanding porous properties, increasing the contact area with enhancing electron transfer efficiency. XPS and FTIR spectra confirmed the interfacial Ni─S chemical bond is formed. In situ XPS and density functional theory calculations (DFT) prove the successful construction of Ni 5 P 4 /MnCdS ohmic junction with strong electronic coupling effect, which effectively improved the charge separation and electron transfer. Consequently, the 3%Ni 5 P 4 /MnCdS achieved the highest hydrogen evolution rate of 25.24 mmol g −1 h −1 , exceeding the 3%Pt/MnCdS. This work provides valuable insights into the development of ohmic junctions by constructing interfacial chemical bonds.

The precise quantities of melamine and cyanuric acid were subjected to a ball milling process, with the objective of forming supramolecule precursors. Following the calcination of the precursors, g-C3N4 nanoflakes were obtained. Subsequently, a g-C3N4/La2Ce2O7 composite photocatalyst was then yielded by growing La2Ce2O7 nanoparticles on the surface of g-C3N4 nanoflakes via the co-deposition method. The composite with the Type-II carrier transfer mechanism (CTM) exhibited a photocatalytic capacity on the degradation of tetracyclines (TC) and ciprofloxacin (CIP) solutions. Moreover, the investigation into the influence of La2Ce2O7 mass percentage on the photocatalytic performance of the g-C3N4/La2Ce2O7 composite revealed that a 15 % La2Ce2O7 mass percentage sample yielded the optimum photocatalytic performance. Consequently, within a 30-min timeframe, the degradation efficiencies of TC and CIP solutions were 72.085 % and 46.214 %, respectively, under the photo-catalytic action of the sample. Furthermore, with the introduction of the donor dopant of P element, the Fermi level of the g-C3N4 component was elevated, resulting in a shift of the CTM of the composite to the S-scheme. Consequently, the photocatalytic performance of the composite was further enhanced. It is evident that the doped sample exhibited much improved photocatalytic activity, which resulted in enhanced degradation efficiencies of 92.894 % and 73.809 % for these two solutions, respectively.

Suppressing photogenerated carrier recombination remains a pivotal challenge in photocatalyst design. In this work, we strategically integrate Co3O4 as a hole-extracting layer and Ni as an electron-trapping cocatalyst onto graphitic carbon nitride (g-C3N4), establishing a work-function-gradient-driven charge transport pathway along the Co3O4 -> g-C3N4 -> Ni directional cascade, resulting enhanced carrier concentration and charge migration kinetics. The optimized 1.5 %Ni-1 %Co3O4-C3N4 achieves a remarkable photocatalytic hydrogen evolution rate of 16.71 mu mol h- 1, surpassing 1 %Co3O4-C3N4 (5.17 mu mol h- 1), 1.5 %Ni-C3N4 (1.64 mu mol h- 1) and g-C3N4 (0.12 mu mol h- 1) by 3.2, 10.2 and 139.2 times, with robust stability over multiple cycles. Photoelectric characterizations confirm accelerated charge separation via synergistic electron transfer by Ni electron sinks and Co3O4 hole extractor. Density functional theory reveals work function gradient of Co3O4, g-C3N4, and Ni driving unidirectional electron flow from Co3O4 to Ni active sites via g-C3N4 as bridge, while an upward-shifted Ni d-band center and optimized hydrogen adsorption energy (Delta G*H) of 1.5 %Ni-1 %Co3O4-C3N4 enhance *H reduction kinetics. This work establishes a work-function-gradient based strategy for advancing solar-to-hydrogen conversion technologies.