The products distributions of OS pyrolysis was fully explored by combining the pyrolysis experiments and molecular simulation, to help to deeply understand this complicated reaction process. The results of products analysis indicated that the main reactions include chain-breaking reactions, dehydrogenation reactions, aromatization reactions, alkylation reactions, and dehydrogenation condensation reactions. Microwave pyrolysis of model OS comprised of n-dodecane and OS sediment were conducted to further explore the specific reaction during the pyrolysis process, and the results showed that the pyrolysis of saturated alkanes begins at 350℃, and dehydrogenation condensation begins at 500℃. Specifically, saturated alkanes first dehydrogenated to form large molecules of α-alkene, then α-alkenes broke chains to form smaller molecules of alkanes. Furthermore, the pyrolysis process of n-dodecane was simulated by Reactive force field molecular dynamics (ReaxFF MD), and the molecular pyrolysis products distribution obtained by simulation was in good agreement with the experimental result. GRAPHICAL ABSTRACT

Aqueous zinc–iodine batteries (AZIBs) are emerging as highly promising candidates for next-generation, grid-scale energy storage due to the intrinsic safety of water-based electrolytes, the high theoretical capacity of the zinc anode, and the rapid conversion kinetics of the iodine cathode. However, the practical commercialization of AZIBs is severely impeded by formidable interfacial instabilities, including the uncontrollable growth of zinc dendrites, parasitic hydrogen evolution reactions (HER), and the notorious polyiodide (I₃⁻, I₅⁻) shuttle effect. These macroscopic degradation modes are fundamentally rooted in the robust [Zn(H₂O)₆]²⁺ primary solvation sheath and the immense thermodynamic driving force for polyiodide dissolution in highly polar aqueous media. To address these interconnected challenges, electrolyte engineering has evolved into the most potent, holistic strategy. This comprehensive review systematically evaluates the latest advancements in electrolyte engineering for AZIBs. We first deeply decipher the fundamental thermodynamic mechanisms governing Zn²⁺ desolvation and iodine multiphase conversion. Subsequently, we critically analyze cutting-edge regulation paradigms, including water-in-salt (WIS) and localized high-concentration electrolytes (LHCE), cosolvent networks, functional molecular additives, deep eutectic solvents (DES), and quasi-solid-state hydrogels. By integrating in situ/operando spectroscopic characterizations with multiscale theoretical computations (such as MD and DFT), we elucidate the structure–activity relationships at the atomic level. Finally, we provide strategic perspectives on the future trajectories of the field, emphasizing the stabilization of multi-electron (I⁻/I⁰/I⁺) halogen chemistry, AI-driven high-throughput screening, and the rigorous standardization of Ah-level pouch cell engineering for extreme-environment applications.

Due to a positive standard reaction Gibbs free energy (Δ _r G _m ^θ ) of 237.1 kJ mol ⁻¹ , electric energy input is indispensable for hydrogen production by conventional electrochemical water splitting. This energy requirement can be reduced by replacing the anodic oxygen evolution reaction to thermodynamic favorable small‐molecules oxidation reactions. In this work, anodic formaldehyde oxidation reaction (FOR) in alkaline media was paired with cathodic hydrogen evolution reaction (HER) in acidic media to establish a thermodynamically downhill system. The utilization of electrochemical neutralization energy in a hybrid alkaline‐acidic electrolyte configuration enables a further decrease in Δ _r G _m ^θ . Therefore, the resulting hybrid alkaline‐acidic formaldehyde‐proton fuel cell (FPFC) exhibits a significantly reduced Δ _r G _m ^θ of −101.5 kJ mol ⁻¹ . A bifunctional Ru‐doped Cu catalyst (Ru─Cu NTs@CM) was designed and synthesized to simultaneously promote the kinetics of acidic HER and alkaline FOR, demonstrating superior catalytic activity and durability to pristine Cu and Ru catalysts. This catalyst enabled concurrent bipolar H ₂ production and electricity generation from the assembled FPFC, reaching a peak power density of 18.3 mW cm ⁻² at 53.4 mA cm ⁻² . A combination of (quasi) in situ characterizations and theoretical calculations unveiled the important mechanistic role of Ru‐doping in enhancing the Cu catalyst's activity and stability.

As the primary renewable reservoir of aromatic carbon, lignin motivates the development of efficient catalysts as a promising route to depolymerization under mild conditions. To address this challenge, layered double hydroxide (LDH) derived Ni-Al catalysts with varying Ni/Al ratios, engineering Ni(0)/Ni(II) interfaces, were developed. Beyond achieving complete β-O-4 conversion of the 2-phenethyl phenyl ether at 125 °C and 25 bar, outperforming previously reported noble- and non-noble-metal catalysts for this model compound, the catalyst also effectively depolymerizes organosolv lignin under 150 °C. A suite of characterizations, including in situ XAFS, confirmed the coexistence of Ni(0) and Ni(II) and the formation of Ni(0)/Ni(II) interfacial sites. Additionally, DFT calculations employing a Ni(1 1 1)/NiO(1 0 0) nanowire model showed that Ni(II) modulates the electronic structure of Ni(0), significantly enhancing its catalytic activity. Reaction pathways identified at the Ni(1 1 1)/NiO(1 0 0) interface exhibit superior thermodynamic and kinetic profiles relative to conventional Ni(1 1 1) surfaces. Combined experimental evidence and DFT analyses establish the Ni(0)/Ni(II) interface as the decisive active site enabling hydrogenolysis under mild conditions. This work provides an efficient platform for mild lignin depolymerization and elucidates the synergistic catalysis at the Ni(0)/Ni(II) interface, paving the way for sustainable biomass conversion.