The electrochemical carbon dioxide reduction reaction (CO2RR) offers a route to store renewable electricity as value-added chemicals. However, designing electrocatalysts with high selectivity and stability remains a significant challenge. Here, an elaborate catalyst, AuCu1 supported on polypyrrole (defined as AuCu1/PPy), synthesized via an electrodeposition-galvanic replacement reaction, featuring d-pi conjugation, demonstrates exceptional performance for CO2-to-CO conversion. With atomically isolated Cu sites confirmed by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption spectroscopy, the AuCu1/PPy catalyst modulates both electronic configuration and spatial immobilization of Au active sites, yielding 99.16% CO faradaic efficiency (FE) with sustained stability over 30 h at -0.6 V versus the reversible hydrogen electrode (RHE), representing 1.83-fold and 8.57-fold improvements in FE and stability compared to the control catalyst Au/PPy. In situ Raman experiments and density functional theory calculations reveal that isolated Cu promotes uniform Au growth, further modulating and stabilizing the *CO2 -/*COOH intermediate adsorption via d-pi conjugation. Concurrently, the delocalized electronic structure enhances charge transfer, lowering activation barriers for *CO formation by 58%. Critically, d-pi conjugation regulates electronic and geometric structures of Au nanoparticles, reducing the energy barrier to superior selectivity and durability. This work constructs a metal-coupled polymer electrocatalyst to decipher the mechanistic role of d-pi conjugation in the CO2RR, which may provide new insights for the rational design of advanced catalysts.

To address the challenges of Ag(I) recovery and sulfonamide antibiotics removal from water, we developed a water treatment system integrating selective Ag(I) adsorption with efficient degradation of sulfonamide antibiotics. In this system, an S,N-dual-adsorption-site MoS2/polypyrrole-methane carbon material (MC) was prepared, exhibiting selective Ag(I) capture with an adsorption capacity up to 674.1 mg/g. Subsequent in situ reduction at 80 °C yielded a composite catalyst (MCA) loaded with Ag nanoparticles (Ag NPs). The MCA/H2O2 system degrades sulfamethoxazole (SMX) through direct electron transfer (DET) from activated H2O2 synergized with a 1O2 non-radical pathway, achieving 98% removal in 60 min with a rate constant (k) 7.1 and 4.6 times that of MoS2 and MC, respectively, and exhibiting high efficacy for other sulfonamides degradation. Density functional theory (DFT) results reveal that Ag NPs incorporated into MCA facilitate interfacial charge transfer, lower the activation energy barrier for 1O2 generation, thus enabling direct activation of dissolved oxygen to 1O2. Continuous-flow experiments using sponge carriers validated the practical application potential of the MCA system. This work achieves a triple synergy of precious metal recovery, resource recycling, and efficient pollutant degradation, providing a new strategy for resource reclamation from Ag(I)-containing wastewater and advanced treatment of sulfonamide antibiotics in water.

Industrial wastewater containing mixed ionic dyes poses a significant treatment challenge. Herein, a conjugated microporous poly(pyrrole methylene) (Py-PPA-CMP) was synthesized using pyrrole and p-phthalaldehyde as monomers, and its adsorption performance was evaluated with the representative anionic dye Acid Red G (ARG) and cationic dye Methylene Blue (MB) as model pollutants. Under neutral conditions, the adsorption performance of Py-PPA-CMP in the dual-component system significantly surpassed that in single-component systems, with the equilibrium adsorption capacity for ARG increasing from 20 mg g(-1) to 109 mg g(-1) and for MB from 60 mg g(-1)to 147 mg g(-1). Remarkably, in the dual-component system, Py-PPA-CMP realized efficient simultaneous removal of ARG and MB across a wide pH range. ARG maintained high removal efficiencies (93-96%) under strongly acidic (pH 2), neutral (pH 7), and strongly alkaline (pH 11) conditions. Concurrently, MB removal was substantial (75%) at pH 2 and nearly reached completion (> 98%) at pH 7 and 11. This pH stability stands in stark contrast to that of single-pollutant systems, where adsorption is severely inhibited by pH-dependent electrostatic repulsion, resulting in a drastic decline in removal efficiency from 85% to 30%. This breakthrough overcomes the selective limitation of traditional adsorbents, highlighting its practical potential for complex wastewater treatment. Furthermore, this study establishes a design paradigm for the development of broad-spectrum dye adsorbents.

Over last decade, the superconducting transition temperature (Tc) has continuously refreshed new records at high pressure conditions. Among these superconductors, some systems show remarkably robust Tc after reaching the highest value for a quite broad pressure range, crossing metal elements, high/mid-entropy alloy, and metallic compounds. However, no known superconductor with robust Tc exceeding 20 K across a wide pressure range has been reported, and the underlying mechanism in known robust Tc superconductors is not well understood. Here, alpha-MoB2 maintains the robust Tc of 32 K up to 230 GPa, setting a new high record of robust Tc with a pressure range over 100 GPa, while the upper critical field mu 0Hc2 demonstrates a dome shape. Density Functional Theory (DFT) calculations reveal a pressure-induced compensatory effect, where the enhancement of superconductivity through an increase in the logarithmic average phonon frequency omega log is counterbalanced by a reduction in electron-phonon coupling (EPC) strength lambda, leading to the robust Tc behavior after reaching the record-high Tc over a broad pressure range. These exceptional high-pressure superconducting properties in MoB2 not only advance our understanding of this important metal diboride, but also offer valuable insights into the mechanisms driving robust superconductivity of other systems.

Despite years of development, electrochemical water softening continues to face challenges in achieving high softening efficiency and maintaining long-term cathode stability. To address these issues, this study builds upon the characteristics of membrane-free electrochemical water softening and prior research by employing a large-pore stainless steel filter as the cathode. During extended operation, a fluffy, porous scale layer gradually forms on the cathode surface, transforming the stainless-steel filter into a metal framework-scale composite (MF-S) cathode. This composite cathode enhances OH⁻ enrichment and extraction, improving water softening efficiency. Additionally, the soft scale deposited on the cathode's pores and surface can be partially removed through simple backflushing, extending system's operational lifespan. Experimental results indicate that using a stainless-steel cathode with 15×10 mm pore size, the effluent pH exceeds 11.0 after 18 h of operation, with a Ca2+ hardness removal rate of over 97 %. To prevent clogging of the cathode pores during extended operation, backflushing is conducted every 25 h to remove scale. Remarkably, after 700 h of continuous operation, there is no observed decline in hardness removal efficiency, and the cathode remains functional, allowing the water softening process to continue. Electrochemical tests and finite element simulations reveal that the composite cathode significantly outperforms the stainless-steel filter cathode in generating and enriching OH⁻. The proposed composite cathode demonstrates strong practical potential, offering a new perspective for applying membrane-free, high-efficiency electrochemical water softening processes.

Photocatalytic selective oxidation of alcohols to aldehydes coupled with H2 production is an eco-friendly strategy for generating both high value-added chemicals and clean energy. In this study, a novel titanium carbide-zinc indium sulfide/titanium dioxide (Ti3C2-ZnIn2S4/TiO2) heterostructure is assembled to photo-catalyze oxidation of benzyl alcohol (BA) into benzaldehyde (BAD) and coupled with H2 production. The introduction of Ti3C2 as a potential regulator and the TiO2 as the catalytic core of BA oxidation had a synergistic effect of H2 and BAD production. Thus, the Ti3C2-ZIS/TiO2 heterostructure exhibits an impressive BAD and H2 production rate of 6.59 and 7.71 mmol g−1 h−1, respectively. Additionally, this composite photocatalyst displays superior cyclic stability for simultaneous BA oxidation and H2 production. The dual charge transfer channels constructed in the Ti3C2-ZIS/TiO2 heterostructure have a crucial effect on enhancing the spatial separation and transport of carriers. This work supplies a promising strategy for constructing dual charge transfer channels to enhance the spatial isolation and gathering of charge carriers, aiming to achieve both high value-added chemical synthesis and clean H2 energy production.

Construction of an anion-rich solvation structure is crucial for the inorganic-rich interphase to stabilize the electrolyte under extreme potentials. While high-concentration electrolytes (HCEs) typically form an anion-rich solvated structure, this configuration has the drawback of significantly reducing ionic conductivity. This study introduces the design and synthesis of an ether-functionalized ionic liquid, tributyl(methoxymethyl)phosphonium hexafluorophosphate ([P4441O1][PF6]), which promotes the formation of an inorganic-rich interphase typically associated with HCEs while maintaining a favorable lithium-ion transport rate. The designed electrolyte can balance the anion-rich solvation structure with rapid ion transport, much like being at the "Golden Mean". [P4441O1][PF6] effectively controls the solvation structure of Li+ through electrostatic and weak interactions. Shielding effect of the cations in the ether-functionalized ionic liquid promotes the formation of PF6- anion- derived clusters, resulting in a thin and robust inorganic-rich interphase that mitigates lithium dendrite formation and enhances reversibility of batteries. Moreover, the ether groups reduced the viscosity of lithium salt/IL mixtures by facilitating interactions between Li+ and ether groups, which enhance lithium-ion transport rate. This approach represents a novel strategy for designing electrolytes for highly reversible lithium metal batteries.

Electrocatalytic nitrate reduction (eNitRR) has emerged as a carbon-free method for sustainable ammonia synthesis and wastewater treatment. However, the complex reaction intermediates and sluggish hydrogenation kinetics remain the key barriers of eNitRR. Herein, this work presented tandem catalysis strategy and developed a B-doped Cu2O nanowires decorated with CeOx to address the two critical issues. Our work presents a highperformance CeOx/B-Cu2O NWs catalyst for eNitRR, achieving an ammonia yield of 2.137 mmol h-1 cm-2 and a Faraday efficiency of 98.8 %, which are superior to those of most previously reported catalysts. At a voltage of-0.5 V vs. RHE, cyclic tests with 8 cycles verified the exceptional stability of the catalyst. In-depth in-situ characterization and density functional theory (DFT) computations demonstrated that doping with boron (B) enhances the adsorption of *NO3 due to the interactions between metallic and non-metallic components. Subsequently, the incorporation of CeOx modifies the electronic structure of Cu2O, thereby promoting hydrolysis and ensuring a sufficient supply of active hydrogen. Moreover, we report the successful development of an innovative Zn-NO3 battery, demonstrating remarkable performance characteristics with an open-circuit voltage of 1.182 V and an exceptional peak power density reaching 21.91 mW cm-2. Furthermore, by integrating eNitRR with an air stripping process, we successfully recovered high-purity NH4Cl products, providing a practical pathway for converting nitrate in wastewater into valuable ammonia-based products. This work provides comprehensive insights into the mechanism of tandem catalysis for eNitRR through the B doping and CeOx heterostructure.

The preparation and modification of porous electrodes are an important component of the new generation electrochemical oxidation technology. Rapid preparation of porous electrodes can be easily achieved by synchronous oxygen bubble electrodeposition. However, according to the reaction mechanism of lead dioxide anodic electrodeposition, there is bound to be a competitive reaction of adsorbed hydroxyl radicals in the oxygen bubble template method, which means that synchronous OER impacts both the surface morphology and potentially the crystalline structure of the metal oxides. Clarifying the comprehensive influence of synchronous OER on the morphology and microstructure of the coating is important. In this work, the electrodeposition process of porous lead dioxide coating is regulated by the way of linear potential increase and realized the rapid preparation of high-performance porous lead dioxide coating within 40 s. The morphology and microstructure, electrical, and electrochemical properties are characterized, combined with theoretical calculation and orthogonal analysis, to investigate the regulatory mechanism of the rapid growth of the porous lead dioxide by the electric potential. It is demonstrated that synchronous OER confers porous morphology and a large number of defects to the coating in situ, and enhancing the electrocatalytic oxidation performance of the electrode.

Ammonia is essential across industry, agriculture, and as a future carbon‐free energy carrier. Electrocatalytic nitrate reduction (NitRR) offers a sustainable path for removing nitrate contaminants from wastewater and groundwater while using abundant nitrate ions as nitrogen sources under eco‐friendly conditions. However, the NitRR pathway, which involves sequential reactions, poses challenges in synchronizing the rate of nitrate‐to‐nitrite conversion with the subsequent reduction of nitrite to ammonia, particularly as the initial reduction step is rate‐limiting. This study presents a CoNi layered double hydroxide (LDH) approach to finely control hydrogen radical (*H) supply, paired with Cu/Cu 2 O redox coupling, to achieve optimal rate matching. CoNi LDH is engineered with various anion intercalations (NO 3 − , Cl − , SO 4 2− , MoO 4 2− , WO 4 2− ) to regulate *H capacity. By integrating Cu/Cu 2 O and CoNi LDH, tandem kinetic descriptors, including a volcano curve, are employed to predict rate constants, facilitating ideal kinetic matching for efficient ammonia synthesis. The optimized MoO 4 ‐CoNi LDH/CuO NW/CF electrode demonstrated exceptional performance, achieving a 99.78% Faraday efficiency, a yield of 1.12 mmol cm −2 h −1 at −0.2 V vs. RHE, and robust 14‐h stability. The model descriptors effectively elucidated the kinetic pathway, linking reaction rates and factors impacting ammonia production.

Materials science exploits only properties that are available at ambience. Therefore, although high-pressure changes the physical state of all condensed matter, most of the extraordinary properties discovered vanish after decompression and cannot be utilized. Here, we demonstrate sublattice decoupling in a mixed-anion chalcohalide Rb6Re6S8I8 upon compression, in which the [Rb6I2]4+ framework is soft and plastic, while the [Re6S8I6]4- clusters are hard and elastic. This discrepancy in the rigidity allows the applied pressure to selectively amorphize the framework while maintaining the ordered state in the cluster, leading to intriguing photocurrent generation and enhancement upon compression. These high-pressure properties are retained at ambience, permitting scalable synthesis of the decompressed samples using a large-volume press, followed by further fabrication into self-powered broadband photodetectors with a response time of ~ 102 μs and a specific detectivity of ~ 1011 Jones. This study subverts the stereotype that pressure engineering is hardly to be employed for device applications.

The regulation of product selectivity in electrochemical CO2 reduction (ECO2R) remains fundamentally constrained by the dynamic equilibrium between intermediate transport and surface coverage. In this study, we report a progress in catalytic architecture through precision-engineered Au@Cu2O yolk-shell tandem nanoreactors featuring dual-tunable parameters: cavity confinement dimensions and shell thickness gradients. This structural modulation enables dynamic control over both *CO intermediate enrichment and reaction pathway bifurcation. ECO2R performance evaluations demonstrate significant product selectivity switching at -1.31 V (vs. reversible hydrogen electrode (RHE)). The Faradaic efficiency (FE) for CH4 exhibits significant architectural dependence, increasing from 43.02% (thick-shell/large-cavity) to 65.54% (medium-dimension) and then decreasing to 23.26% (thin-shell/small-cavity). Conversely, the FE for C2H4 demonstrates an inverse structural correlation, improving from 6.68% (medium-dimension) to 38.73% (thin-shell/small-cavity). The spatial domain-limiting mechanism of the yolk-shell structure directly controls the transition between protonation-dominated CH4 formation and coupling-driven C2H4 production. This work establishes a pioneering paradigm for dynamically steering catalytic selectivity through purely geometrical modulation, bypassing traditional compositional tuning limitations, thereby opening avenues for precision design of advanced electrocatalytic systems.

In this study, chlorine anchored pyrrole-based conjugated porous polymers (CPPs) with distinct pore properties were synthesized using the Knoevenagel reaction and the double chain condensation method. The partially crosslinked and partially oxidized structures of the materials exhibit a unique microstructure integrating interconnected nets and molecular hooks. This architecture utilizes pore channels for physical interception of Hg(II), while synergistic chemical immobilization at N, O, and Cl active sites enables multifunctional enhancement of Hg(II) capture efficiency. Among these materials, the maximum adsorption capacity reached 1183 mg center dot g(-1), demonstrating ultrahigh selectivity. Moreover, the adsorbents maintained > 90 % removal efficiency over 10 adsorption-desorption cycles, confirming excellent reusability. Mechanistic studies revealed that Hg(II) adsorption primarily whin material pores through hydrogen bonding and coordination interactions, and their synergistic interactions. This work highlights the efficiency of the double chain condensation design strategy in advancing conjugated porous polymers for the removal of heavy metals, particularly Hg(II), from wastewater.

The present study successfully synthesized a novel functionalized poly(pyrrole methane) adsorbent with superior hydrophilicity, which effectively combines polypyrrole and polyphenols for the efficient removal of Cr(VI) through adsorption-reduction-sequestration in water. The removal of Cr(VI) by polyphenol-functionalized poly (pyrrole methane) (PhPPm) is pH-dependent, with the optimum value of pH 1.5. For the high hydrophilicity, PhPPm demonstrates rapid Cr(VI) removal from water, reducing the Cr(VI) from 10 and 50 mg center dot L-1 center dot L- 1 to less than 0.1 mg center dot L-1 center dot L- 1 within 3 and 30 min, respectively. The maximum Langmuir theoretical adsorption capacity of PhPPm for Cr(VI) is estimated as 648 mg center dot g- center dot g- 1 at 318 K. And the thermodynamic parameters show that the adsorption process of Cr(VI) is endothermic, entropy-increasing and spontaneous. Co-existing ions such as K+, + , Na+, + , Mg2+, 2+ , Ca2+, 2+ , Cl-and- and NO3-do 3- do not interfere with the Cr(VI) removal, while only SO42-exhibits 4 2- exhibits a slight inhibitory effect due to its more negative charge and similar molecular structure to Cr(VI). Characterization techniques (FT-IR, XPS) combined with DFT calculations confirm that the removal mechanism of Cr(VI) involves electrostatic interactions, adsorption-reduction and chelation, among which strong chelation is the main contributor to the effective sequestration of Cr(III). This study demonstrated that PhPPm is an effective adsorbent for the purification of Cr(VI)-contaminated wastewater.

The report of superconductivity (SC) with Tc 80 K in bilayer Ruddlesden-Popper (RP) nickelate La3Ni2O7-delta have sparked considerable investigations on its normal state properties and SC mechanism under pressure and at low temperature. It is believed that the density wave (DW) at 150 K plays an important role in SC emergence, but its nature remains largely underexplored. Here, we utilized temperature-dependent in-situ Ni K-edge X-ray Absorption Near-edge Spectroscopy (XANES) to probe the Ni-3d/4p electronic states of La3Ni2O7-delta and La2PrNi2O7-delta samples down to 4.8 K, enabling us to witness the evolution of both in-plane d_(x^2-y^2)/p_x (p_y) and out-of-plane d_(3z^2-r^2)/p_z orbitals of NiO6 octahedron across the DW transition. Main edge energy associated with Ni 4p orbital shows an anomalous decline near DW transition, signifying the occurrence of lattice distortions as a hallmark of charge density wave. Below DW transition, the enlarged crystal field splitting (CFS) indicates an enhanced NiO6 octahedral distortion. Intriguingly, magnetic Pr substituents could activate the mutual interplay of d_(x^2-y^2) and d_(3z^2-r^2) orbitals. We discussed its relevance to the favored bulk SC in the pressurized polycrystalline La2PrNi2O7-delta than pristine.

The removal of non-steroidal anti-inflammatory drugs (NSAIDs) via adsorption necessitates the development of advanced adsorbents that harmonize efficiency with cost-effectiveness. Herein, a circular and economic approach is proposed by repurposing Fe-saturated polyaniline (Fe-PANI) waste into a high-performance adsorbent for carboxylic acid drug removal. The Fe-PANI exhibited high equilibrium adsorption capacities of 196.8 mg/g (diclofenac, DCF), 75.2 mg/g (naproxen, NPX), and 40.5 mg/g (ibuprofen, IBP) under neutral conditions (pH 6.0), outperforming the performance of pristine PANI material. Adsorption experiments revealed pseudosecond-order kinetics and Langmuir monolayer adsorption behavior. The pH values and the presence of carbonate species (CO32- and HCO3-) were identified as critical factors affecting adsorption process. Experimental evidence and density functional theory (DFT) calculations confirmed that the incorporation of Fe2+/Fe3+ into PANI significantly altered its electronic structure, facilitating synergistic adsorption via Fe-carboxylate coordination, pi-pi stacking, and proton-enhanced electrostatic interactions. The used adsorbent was successfully regenerated via a Fe-mediated heterogeneous Fenton reaction (0.025 mol/L H2O2, pH 6.0), retaining 82% of its adsorption capacity after three cycles. This dual-functional strategy effectively utilizes hazardous metal-loading waste and addresses drug pollution through adsorption and oxidative regeneration, providing a sustainable approach for water remediation technologies.

Mercury pollution is becoming an increasingly serious issue in the ecological environment. Herein, two aminefunctionalized poly(pyrrole methane)s materials were synthesized from hydrazine for the efficient and selective removal of mercury ions in water. PPDHA and PPD12HA exhibit exceptional adsorption capacities of 1124 and 1080 mg center dot g-1 at 298 K, respectively, and achieve rapid adsorption equilibrium within 20 and 45 min, demonstrating their superior performance. Meanwhile, the two amine-functionalized poly(pyrrole methane)s have excellent adsorption selectivity, for distribution coefficient (Kd) values of Hg(II) greater than 5 x 105 mL center dot g-1, which is 103 (alpha s) times that of other divalent metal ions. Even after 10 adsorption-desorption cycles, the removal efficiency for 10 mg center dot L-1 of Hg(II) remained above 98 %. Additionally, the adsorption mechanism research reveals that amine groups serve as the primary adsorption sites for Hg(II) through infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. This study demonstrates the potential of amine-functionalized poly(pyrrole methane)s synthesized from hydrazine as highly efficient adsorbents for Hg(II) in water, providing a viable approach for further remediation of heavy metal-contaminated wastewater.

Photocatalytic technology has great potential in environmental remediation due to the advantages of being green and cost-effective. Still, drawbacks such as high carrier recombination and poor photo-utilization efficiency hinder its large-scale application. Fortunately, defect modulation has been proven to be an effective tactic for solving the above problems. In this study, cationic vacancies were introduced in layered bismuth molybdate (Bi2MoO6) by controlled alkali etching. The results showed that the optimized Mo vacancy concentration increased the degradation efficiency of tetracycline hydrochloride to 82 % with a kinetic constant 2.4 times higher than that of bulk Bi2MoO6, which is superior to most reported Bi-based catalysts. In-situ KPFM, PL, and photoelectrochemical measurements confirm that the boosted activity is attributed to photo-excited charge carriers' excellent separation and migration ability. This work supplies a feasible strategy to enhance the photocatalytic performance of Bi2MoO6 and provides a novel insight into designing other advanced materials for photocatalytic applications.

Rational design of high-performance catalysts for CO2 electroreduction is crucial for achieving carbon neutrality, yet effective modification strategies remain scarce. In this study, we present the microwave heating approach to incorporate La3+ ions into Sn-based perovskite oxides, significantly enhancing their electrocatalytic performance for the reduction of CO2 to formate. Through comprehensive characterization techniques, including X-ray photoelectron spectroscopy, synchrotron radiation X-ray absorption spectroscopy, electrochemical measurements (Tafel analysis and impedance spectroscopy), and density functional theory calculations, we demonstrate that La3+ substitution effectively modulates the Sn-O bond distance in BaSnO3. This structural modification induces local charge density enrichment, facilitates CO2 adsorption, and enhances electron transfer kinetics, resulting in a substantial improvement in the formate Faradaic efficiency. In situ Raman spectroscopic analysis and postreaction XPS characterization confirmed the structural integrity of the perovskite framework and the preservation of Sn valence states under negative potentials. This work provides fundamental insights into the CO2 reduction reaction mechanism on perovskite electrocatalysts and establishes a framework for the design of advanced tin-based electrocatalysts.