The emergence of bio-essential nitrogenous molecules like ammonia and urea on early Earth is crucial for the origins of life. Herein, we propose a prebiotic molecular synthesis process involving ammonia and urea on rhodochrosite via a geo-electrochemical mechanism, offering another similar inorganic pathway that produces simple molecules like methane and carbon monoxide in primordial environments. Though long overlooked, Mn element is an essential cofactor in redox enzymes and linked to organic-rich mineral deposits, indicating its role in early biological processes. In this context, the potential of rhodochrosite (the most abundant sedimentary manganese-bearing mineral with naturally doping) to catalyze the conversion of NO_x^- and CO₂ into NH₃ and/or urea within a geo-electrochemical system was explore. In situ experiments and theoretical modeling show that dopant modulation of Mn sites optimizes the d-band center, strengthening adsorption of NO_x⁻ and CO₂ and enabling efficient NH₃ and urea production. This finding provides an abiotic pathway for the accumulation of key nitrogenous compounds under prebiotic oceanic conditions, without enzymes or extreme processes, suggesting a compelling mineral-mediated origin for prebiotic nitrogenous molecules.

The universality and atomic-level structure of solid-liquid interfaces critically govern functionality across chemical, biological, and geological systems. In electrocatalysis, this interfacial structure dictates reaction thermodynamics and kinetics. However, fundamental understanding of structure-property relationships and their correlation with preferential reaction pathways remains incomplete. While conventional models emphasize adsorbate-surface covalent bonding and long-range electrode-electrolyte electrostatic interactions, emerging evidence highlights the significant impact of non-covalent adsorbate-electrolyte interactions on the electrical double layer (EDL) structure and electrocatalytic kinetics. Critically, both electrode and electrolyte co-determine catalytic performance. Despite advances in catalyst design, the electrolyte's role in modulating the local interfacial environment is inadequately understood, hindering optimization of activity, selectivity, and stability. Elucidating interfacial electrolyte effects is thus paramount, equaling the importance of intrinsic catalyst properties. This review commences by evaluating established and emerging theoretical frameworks describing the electrochemical solid-liquid interphase. Progressing to mechanistic insights, we decipher the role of electrolyte composition—specifically cation/anion speciation, concentration, and pH—in modulating the activity and selectivity of core electrocatalytic reactions. Critical assessment follows of state-of-the-art operando spectroscopic and scattering methodologies for resolving the dynamic evolution of buried interfaces. We conclude by delineating fundamental knowledge gaps and strategic research trajectories for electrolyte engineering to advance electrocatalytic microenvironments.

Advances in research and development of carbon-based metal-free electrocatalysts (C-MFECs) have provided potential alternatives to precious metal catalysts for various reactions important to renewable energy and environmental remediation. This timely but critical review provides an overview of recent breakthroughs (within the past 5 years or so) on C-MFECs in all aspects, including the design and regulation of intrinsic catalytic active sites, design and synthesis of carbon composite and hybrid carbon catalysts, mechanism understanding, and potential applications in clean energy storage and energy/chemical conversion. Current challenges and future opportunities in the field of metal-free carbon electrocatalysis are also discussed to provide forward-looking opportunities for their potential applications in various catalytic processes of practical significance.

Atomically dispersed metals stabilized by nitrogen elements in carbon skeleton hold great promise as alternatives for Pt-based catalysts towards oxygen reduction reaction in proton exchange membrane fuel cells. However, their widespread commercial applications are limited by complicated synthetic procedures for mass production. Herein, we are proposing a simple, green mechanochemical approach to synthesize zeolitic imidazolate frameworks precursors for the production of atomically dispersed “Fe-N₄” sites in holey carbon nanosheets on a large scale. The thin porous carbon nanosheets (PCNs) with atomically dispersed “Fe-N₄” moieties can be prepared in hectogram scale by directly pyrolysis of salt-sealed Fe-based zeolitic imidazolate framework-8 (Fe-ZIF-8@NaCl) precursors. The PCNs possess large specific surface area, abundant lamellar edges and rich “Fe-N₄” active sites, and show superior catalytic activity towards oxygen reduction reaction in an acid electrolyte. This work provides a promising approach to cost-effective production of atomically dispersed transition metal catalysts on large scale for practical applications.