This review summarizes recent advances in phase-interface modulation via water-state control towards efficient photocatalytic CO 2 reduction, N 2 fixation, and H 2 O 2 synthesis.

Electrocatalytic nitrite reduction reaction (NO2-RR) to synthesize ammonia (NH3) has been constrained by sluggish kinetics of water dissociation and the weak adsorption of nitrite. In this work, we develop an in-situ reconstruction strategy that transforms Ni-doped BiO2-x (NiBiO2-x) to Bi/NiBiO2-x, which exhibits excellent activity and selectivity for NO2-RR to synthesize NH3. Diverse ex-situ and in-situ characterizations reveal potential-driven structural transformation from NiBiO2-x to Bi/NiBiO2-x, which features dual Ni2+-Bi0 active sites. The Ni2+site is able to reduce the water dissociation barrier from 0.79 to 0.41 eV, while concurrently the Bi0 site can strengthen NO2-adsorption to promote *NO2H intermediate formation. Consequently, the in-situ constructed Bi/NiBiO2-x catalyst with Ni2+-Bi0 catalytic pairs enable an excellent NO2-RR performance, achieving a NH3 Faradaic efficiency (FENH3) of 94.5% at-0.6 V vs. RHE. The present study opens the new direction to in-situ construct highperformance electroreduction catalysts for small molecule synthesis.

Volatile organic compounds (VOCs) degradation using bismuth-based photocatalysts is often limited by rapid charge recombination. To address this, this study presents a one-step CTAB-assisted hydrothermal synthesis of ultrathin BiOCl/Bi2MoO6 Z-scheme heterojunctions for enhanced photocatalytic degradation of gaseous toluene. The optimized catalyst (CBBM2) exhibits a remarkable 83.9 % degradation efficiency under visible light within 150 min, as well as excellent cyclic stability (81.4 % after four cycles). Characterizations confirm that CTAB induces oxygen vacancies and reduces nanosheet thickness to 37 nm, facilitating charge separation and migration, as evidenced by a 4-fold increase in photocurrent density. Crucially, electron paramagnetic resonance (EPR) spectroscopy confirms the direct Z-scheme pathway by detecting the simultaneous generation of center dot OH and center dot O2radicals. This leading to a 6.8-fold higher kinetic rate than pristine BiOCl. This work offers a promising strategy for designing efficient bismuth-based photocatalysts for VOC removal.

ABSTRACT Conventional low‐spin Co 3 O 4 suffers from weak orbital hybridization with oxygenates ( * NO x and * H 2 O), leading to slow reaction kinetics for ammonia synthesis during electrochemical nitrate reduction (NO 3 RR). Herein, we demonstrate the precise spin‐state engineering of octahedral Co 3+ sites in spinel Co 3 O 4 through a facile yet effective thermally induced lattice distortion. Spectroscopic and theoretical investigations reveal this lattice distortion reshapes the localized d‐orbital energy levels, thereby fundamentally driving a transition from the thermodynamically stable low‐spin configuration to a highly active high‐spin state. Mechanistically, the unpaired e g electrons of high‐spin Co 3+ strengthen orbital hybridization with oxygen‐containing intermediates ( * NO x and * H 2 O). This enhanced binding not only promotes the adsorption and cleavage of these species but also ensures a sustained supply of protons via accelerated water dissociation, thereby synergistically accelerating the NO 3 RR toward NH 3 . Consequently, the optimized high‐spin Co 3 O 4 delivers an exceptional Faradaic efficiency of 93.36% and an NH 3 yield rate of 1.17 mmol/h/cm 2 . Moreover, techno‐economic analysis shows a two‐electrode membrane‐electrode assembly (MEA) reactor coupling NO 3 RR with GOR (NO 3 RR//GOR) enables favorable economic performance with a total revenue of 7651 USD/t NH 3 . This work presents a facile synthetic route toward highly active electrocatalysts via distortion‐driven spin‐state regulation, providing a promising strategy for sustainable electrochemical ammonia synthesis.

Copper ion (Cu2+) quantification in complex food and environmental matrices remains challenging because of matrix interference and the need for rapid, portable analysis. Herein, we report ACL-Cu, an activatable chemiluminescent 1,2-dioxetane probe for selective Cu2+ detection. Under mildly alkaline conditions (pH 8.0), Cu2+ triggers intramolecular cyclization of ACL-Cu, producing green chemiluminescence centered at similar to 550 nm with an approximately 26-fold signal enhancement relative to the probe alone. ACL-Cu showed high selectivity toward Cu2+ over common metal ions and anions, and quantitative analysis on the IVIS platform gave a linear response over 0.2-3.0 mu M with a limit of detection of 43 nM. A handheld portable device also enabled Cu2+ quantification over the same linear range, with a detection limit of 76 nM and an assay time of <= 10 min. In porcine liver and lake water samples spiked prior to pretreatment, ACL-Cu provided concentration-dependent responses and accurate quantification, affording recoveries of 91.7-97.0% for IVIS and 90.0-96.0% for portable device, with relative standard deviations below 2.35%. These results demonstrate that ACL-Cu is a reliable chemiluminescent platform for Cu2+ determination in complex real samples and holds promise for food safety and environmental monitoring.

The electrochemical CO2 reduction reaction (CO2RR) to formic acid (HCOOH) is constrained by slow kinetics and limited selectivity due to inefficient proton-coupled electron transfer (PCET). Herein, we synthesized Cu-doped BiO2-x (CuBiO) nanosheets to facilitate proton transfer through reconstruction of the hydrogen-bond (HB) network, thereby accelerating the PCET process. The in-situ measurements reveal that part of the 4-coordinated hydrogen-bonded water (4-HB & centerdot;H2O) transforms into 2-coordinated hydrogen-bonded water (2-HB & centerdot;H2O) over CuBiO during CO2RR. This reconstruction forms a linear proton transport pathway which efficiently promotes proton transport during PCET steps and concurrently inhibits the competing hydrogen evolution reaction. Density functional theory (DFT) calculations further elucidate that the Cu doping not only facilitates water dissociation into protons while inhibiting proton dimerization, but also enhances CO2 activation and reduces the energy barrier for of *CO2 -> *OCHO. Ultimately, the CuBiO-6 displays highly efficient conversion of CO2 to HCOOH with a Faradaic efficiency (FE) of 92.4% and maintains stable operation for over 22 h. These findings provide a novel strategy to accelerate the PCET through regulation of interfacial HB network towards efficient CO2RR to HCOOH.

Carbon-based aqueous zinc-ion batteries (CAZBs) require stable operation under extremely low temperatures for practical applications, but they are hindered by sluggish Zn2 + transport within the diffusion layer and desolvation barriers in the Helmholtz layer. Here, a bio-inspired interface engineering strategy-derived from the high-volume, high-speed, and high-efficiency signal processing capability of the cerebral cortex-is employed to construct hierarchical carbon spheres with sulcus-gyrus architectures (HCSs-sg). Such HCSs-sg can effectively imitate the dense neuron distribution in the cerebral cortex and lead to a sharp increase in pseudocapacitive active sites. This biomimetic configuration generates directional micro-electric fields and ionic concentration gradients, which synergistically accelerate Zn2 + transport through diffusion-driven migration and coulombic forces. Simultaneously, the high-curvature sulcus-gyrus exhibits enhanced Zn2 + adsorption energy and reduced desolvation barriers, thereby facilitating efficient desolvation and rapid charge transfer at subzero temperatures. As a result, the optimized product delivers a specific capacity of 70 mAh g- 1 at 0.1 A g- 1 under -25°C and maintains a stable coulombic efficiency of nearly 100% over 10 000 cycles at 1 A g- 1. This biomimetic interface engineering approach can provide a potential design route for aqueous battery applications under extreme-temperature conditions.

The construction of a built-in electric field and precise modulation of active sites are pivotal for enhancing the efficiency of catalytic reactions, yet achieving synergistic enhancement through a simple modification remains a challenge. Herein, we report a facile NaSCN assisted thermal treatment strategy to graft cyano groups onto the terminal amino sites of g-C3N4 (CN). The introduced cyano groups not only enhance the intrinsic polarization of the material, as confirmed by a 1.83-fold increase in the dipole moment and a superior piezoelectric coefficient (d33 = 67.2 pm/V), but also create a strong internal electric field that synergizes with the piezoelectric field to promote charge separation and transfer. Consequently, the optimized NHCN-3 catalyst achieves an outstanding piezo-photocatalytic H2O2 generation rate of 158.2 mM/g/h, which is 22.6 times greater than that of CN. Moreover, combined in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) and density functional theory (DFT calculations) indicate a dual-site reaction mechanism: the terminal carbon atom adjacent to the grafted cyano group in the modified material reduces the energy barrier for H2O cleavage into the *OH intermediate, while the neighboring -NH- group promotes the reaction by adsorbing a hydrogen atom and transforming into -NH2 + species. This research provides new ideas for the multi-site cooperative effect and regulation of the H2O2 reaction pathway, laying the foundation for the design of high-performance piezophotocatalysts.

Layered photocatalysts are attractive for artificial photosynthesis, but their performance is often limited by inefficient charge transport across interlayer gaps and sluggish surface reaction kinetics. Herein, we propose a single-atom interlayer bridge strategy by introducing Au single atoms into layered Bi4O5Br2 (AuIB-BOB) to address the above limitations. The incorporated Au atoms substitute Bi sites and are stabilized by a mixed O/Br coordination environment with an average local structure of Au1O3Br2, forming a covalent bridge between the Br- and [Bi4O5]2+ layers to provide an excellent pathway for cross-layer charge transport. Thus, holes that would otherwise remain confined in the Br- layer are extracted and delivered to the surface O-oxidation sites, while photogenerated electrons are retained and utilized at the surface Bi-reduction sites. This directional charge redistribution considerably suppresses charge recombination, prolonging the average carrier lifetime from 19.5 to 109.7 ps. Meanwhile, the bridge-mediated charge transport activates the intrinsic Bi reduction sites and O oxidation sites synchronously, promoting CO2 adsorption/activation and H2O oxidation-related processes. Without sacrificial agents or photosensitizers, AuIB-BOB achieves a CO2-to-CO evolution rate of 58.21 µmol g-1 h-1 in pure water. This work provides an atomic-level paradigm for regulating cross-layer charge transfer and unlocking intrinsic redox sites in layered photocatalysts.

To enhance the photocatalytic degradation of oxytetracycline, N-modified TiO2/carbon composites were synthesized using cotton stalk as a biotemplate. XPS indicated N modification of TiO2, with carbon present on the surface. UV–Vis DRS revealed that the composites exhibited enhanced visible light absorption. Electron-hole separation efficiency and photoresponse were proven by the PEC measurements. T/C/NM-0.10 achieved a removal ratio of 95% for oxytetracycline hydrochloride in 30 min, and radical capture experiments indicated that ·O2− as the primary active species in the photocatalytic degradation process. After five cycles, the composites maintained an 87% removal ratio.

The pervasive accumulation of plastic waste exacerbates environmental degradation and undermines resource circularity. Selective thermal catalysis emerges as a transformative pathway for valorizing waste plastics into value-added chemicals, yet persistent challenges in catalytic activity and product selectivity demand systematic resolution. This review decodes cutting-edge advances in thermal depolymerization by converging two critical dimensions: atomic-scale active site engineering-where rational design of coordination features and interfacial architectures regulates C-C cleavage energetics and intermediate adsorption-and macromolecular-scale manipulation of polymer transient states-leveraging nanoconfinement effects, chain folding dynamics, and thermal fragmentation to accelerate conversion kinetics. We further highlight breakthroughs in operando characterization techniques that resolve time-evolving reaction coordinates across catalytic systems. By establishing multiscale structure-activity relationships linking catalyst configurations to polymer dynamics, this analysis derives design paradigms for next-generation upcycling systems. These principles enable economically viable, industrially scalable plastic valorization while charting a strategic trajectory toward carbon-circular economies.

Self-supported nanoarrays have emerged as a promising alternative electrocatalyst for alkaline H2O splitting, owing to their accessible active sites and strongly coupled interfaces with current collectors for improved mass transfer and stability. Herein, self-supported crystalline/amorphous NiO/Ni(OH)2 nanosheet arrays on nickel foam (NF) are fabricated via an in-situ dissolution-deposition hydrothermal growing of Ni(OH)2 nanosheets without additional metal sources assisted by a common Lewis base, EDTA, followed by a rapid calcination at 300 degrees C in air. The as-prepared EDTA-NF-12 h exhibits high OER and HER performance under alkaline conditions, requiring 235 mV and 158 mV, respectively, to reach 10 mA cm-2, and the decent performance can be maintained for 24 h without obvious degradation. The dual interfaces, i.e., the dense crystalline/amorphous interfaces within the NiO/Ni(OH)2 nanosheet arrays, as well as the intimate interfaces between nanoarrays and NF, both serve as reaction active sites, facilitate electron transfer, and endow the catalyst with high activity and stability. Furthermore, by applying EDTA-Ni2+ and other Lewis bases with varying basicities instead of EDTA, the interfaces with the NF substrate are found to promote the formation of crystalline/amorphous interfaces within the nanosheets. This study offers appealing opportunities for tailoring the electrocatalytic performance of self-supported electrodes via dual interface engineering.

The prevailing paradigm in piezo-photocatalysis primarily focuses on leveraging piezoelectric polarization fields to enhance the separation of photogenerated charges. Herein, we transcend this conventional approach by demonstrating that piezoelectric polarization can synergize with precisely engineered molecular structures to regulate both the reaction kinetics and thermodynamics for hydrogen peroxide (H2O2) production by using the cyano-functionalized and K+-intercalated carbon nitride (MCN) with enhanced intrinsic dipole moment and piezoelectric response as model catalyst. Combined experimental characterizations and DFT calculations unveil that the piezoelectric field not only facilitates charge separation but, more importantly, cooperates with the electron-withdrawing cyano groups to boost O2 adsorption, elongate the O=O bond, and lower the energy barrier of the rate-determining step. Consequently, MCN achieves an exceptional piezo-photocatalytic H2O2 production rate of 8.03mmol/g/h. Furthermore, the as-formed flexible MCN/PVDF-HFP film demonstrates practical potential under outdoor sunlight with mechanical agitation, enabling efficient H2O2 accumulation, which is successfully utilized for the rapid degradation of organic pollutants. This work introduces a novel concept of synergistic polarization and molecular engineering, paving the way for advanced catalyst design in sustainable chemical synthesis.

Although photocatalytic CO2 reduction holds promise for producing high-value chemicals, its efficiency is constrained by bottlenecks such as narrow light absorption, inefficient carrier separation, and slow interfacial reactions. Herein, a tightly coupled p-n heterojunction (MoO2-x/Cu2-xS) was constructed to regulate interfacial charge dynamics and extend the photo-response toward the near-infrared (NIR) region. Owing to the band alignment and Fermi-level equilibration between the p-type and n-type components, a built-in electric field is established at the interface, which enables efficient spatial separation of photogenerated electrons and holes and suppresses bulk/interfacial recombination. Importantly, the enhanced charge separation not only improves carrier utilization under visible light but also translates into markedly boosted catalytic activity under NIR irradiation, highlighting the decisive role of junction-driven carrier management in activating the low-energy photons. It is noteworthy that the CO yield of the MoO2-x/Cu2-xS heterojunction photocatalyst under fullspectrum and near-infrared light are 61.76 and 34.07 mu mol gcatalyst respectively, and the AQY of 30% CS/MO reaches a maximum of 0.096% (lambda = 420 nm). Meanwhile, the interfacial electronic coupling generates electron-enriched states that facilitate adsorption/activation of key intermediates (*COOH-*CO) and lower the kinetic barrier along the reaction pathway, thereby improving both reaction rate and product selectivity. This work provides a general p-n junction engineering strategy to couple charge separation with NIR-responsive catalysis, offering mechanistic insights for designing high-performance photocatalysts with broadened solar-spectrum utilization.

The electrochemical CO2 reduction reaction (CO2RR) to formic acid (HCOOH) is constrained by slow kinetics and limited selectivity due to inefficient proton-coupled electron transfer (PCET). Herein, we synthesized Cu-doped BiO2u2212x (CuBiO) nanosheets to facilitate proton transfer through reconstruction of the hydrogen-bond (HB) network, thereby accelerating the PCET process. The in-situ measurements reveal that part of the 4-coordinated hydrogen-bonded water (4-HBu00B7H2O) transforms into 2-coordinated hydrogen-bonded water (2-HBu00B7H2O) over CuBiO during CO2RR. This reconstruction forms a linear proton transport pathway which efficiently promotes proton transport during PCET steps and concurrently inhibits the competing hydrogen evolution reaction. Density functional theory (DFT) calculations further elucidate that the Cu doping not only facilitates water dissociation into protons while inhibiting proton dimerization, but also enhances CO2 activation and reduces the energy barrier for of *CO2 u2192 *OCHO. Ultimately, the CuBiO-6 displays highly efficient conversion of CO2 to HCOOH with a Faradaic efficiency (FE) of 92.4% and maintains stable operation for over 22 h. These findings provide a novel strategy to accelerate the PCET through regulation of interfacial HB network towards efficient CO2RR to HCOOH.

Developing photocatalysts capable of efficient in situ H2O2 generation and pollutant degradation remains a major challenge for advanced water treatment. Herein, a one-step thermal polymerization strategy is proposed to construct K, O co-doped graphitic carbon nitride with simultaneously introduced nitrogen vacancies and cyano groups. This multi-active-site architecture induces local structural disorder while preserving long-range layered stacking, enabling enhanced light harvesting, accelerated charge separation, and selective two-electron oxygen reduction. The optimized catalyst exhibits an exceptionally high H2O2 production rate (3878 mu mol g- 1 h- 1) and apparent quantum yield (71.5%), suppressed H2O2 decomposition, and broad pH adaptability. Benefiting from the efficient in situ generation of reactive oxygen species, rapid degradation (92% in 60 min) and partial mineralization of tetracycline (42.1%) are achieved under visible light. Mechanistic evidence shows K+, -OH, -C---N and N-vacancy synergy in modulating O2 adsorption, electron transfer and ROS generation, offering quantitative, mechanism-based guidance for multi-site photocatalyst design and photocatalytic water purification.

Converting CO2 into solar fuels via photocatalysis represents a promising strategy for advancing toward carbon neutrality. Nevertheless, the efficiency of this process is frequently hindered by the rapid recombination of photoexcited charge carriers. Herein, we fabricated a Cu2-xS/g-C3N4 (CS/CN) p-n heterojunction with closely-contacted heterojunction interface for CO2 photoreduction. The results of photoelectrochemical tests and transient absorption spectra indicated the p-n heterojunction between CS and CN generated a robust built-in electric field, which promoted unidirectional transport of electrons from CS to CN and holes from CN to CS, thereby accelerating the spatial separation of photogenerated carriers. Both theoretical and experimental studies demonstrated that the addition of Cu2-xS not only intensified the interaction between CN and CO2, but also significantly promoted the adsorption and subsequent activation of CO2 molecules, and reduced the formation energy barrier of intermediate *COOH from 1.09 to 0.42 eV during CO2 reduction. As a result, the CS/CN p-n heterojunction exhibited an average CO yield of 67.4 μmol g-1. This work reveals the dual roles of p-n heterojunctions in simultaneously addressing the limitations of bulk charge transport and tailoring the surface catalytic environment, establishing a general framework for the design of p-n heterojunctions.

Artificial photosynthesis is considered an ideal technology to achieve the "dual-carbon" goals. However, sluggish H2O/CO2 activation and carriers' severe recombination impede photocatalytic CO2 reduction reaction. Herein, this work innovatively proposes an "interfacial H2O dissociation" strategy on a MoN/Mo2N (MN) dual-plasmon heterojunction for achieving interface structure-dependent active *H generation in the CO2 photoreduction process. The formation of MN heterojunctions with a low lattice mismatch diminished interfacial mass transfer obstruction and promoted charge carriers' separation efficiency, triggering a fast H2O dissociation reaction for proton *H generation with a decreased longitudinal relaxation time of 342.40 ms from more than 600 ms and prolonging the average carriers' lifetime to 410 ps. Theoretical calculations reveal that the strong interface coupling effect greatly decreases the energy barrier of *H generation and rate-limiting intermediate formation steps of CO2 reduction. Without cocatalysts and sacrificial reagents, the MN metallic heterojunctions exhibit an efficient CO2 photoreduction activity with a CH4 evolution rate of 8.2 mu mol h(-1). This work offers an atomic-level insight into H2O dissociation and the design of metallic heterojunction for CO2 reduction.

Photocatalytic low concentration CO2 (LC-CO2) reduction is a key issue in the field of solar-to-fuel conversion. The main problem affecting the efficient conversion is the poor adsorption and activation efficiency of LC-CO2 molecules at the interface. Herein, a heterojunction of Bi2MoO6/MoSxSey (BMO/MSS) composite with oxygen vacancies (VOs) is successfully constructed via a facile method. Various experiments and density-functional theory (DFT) calculations show that the composite possesses the S-scheme charge transfer pathways which can facilitate the photogenerated carrier separation efficiency. Electron accumulation (1.1886 |e|) of VOs-BMO/ MSS is much higher than that of BMO (0.0371 |e|) and MSS (0.0633 |e|), and CO2 adsorption model changes from linear (180 degrees in BMO and MSS) to bend (127 degrees in VOs-BMO/MSS), demonstrating that VOs serve as crucial electron traps and CO2 activation centers. Gibbs free energy also show that the VOs effectively lower the reaction barriers for the sequential formation of key intermediates such as *CO, *CH2O, and *OCH3, ultimately yielding reduction products like CH4 and CO. As a result, under the simulated flue gas concentration of 15 % CO2/Ar, the yields of CH4 and CO reached to 8.65 and 60.58 mu mol g- 1 h- 1 respectively. This work provides an effective strategy for the resource utilization of LC-CO2.