In Situ Generated Sulfate-Facilitated Efficient Nitrate Electrosynthesis on 2D PdS2 with Unique Imitating Growth Feature

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In Situ Generated Sulfate-Facilitated Efficient Nitrate Electrosynthesis on 2D PdS2 with Unique Imitating Growth Feature
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In Situ Generated Sulfate-Facilitated Efficient Nitrate Electrosynthesis on 2D PdS2 with Unique Imitating Growth Feature - Nano-Micro Letters

As a green sustainable alternative technology, synthesizing nitrate by electrocatalytic nitrogen oxidation reaction (NOR) can replace the traditional energy-intensive Ostwald process. But low nitrogen fixation yields and poor selectivity due to the high bond energy of the N≡N bond and competition from the oxygen evolution reaction in the electrolyte restrict its application. On the other hand, two-dimensional (2D) PdS2 as a member in the family of group-10 novel transition metal dichalcogenides (NTMDs) presents the interesting optical and electronic properties due to its novel folded pentagonal structure, but few researches involve to its fabrication and application. Herein, unique imitating growth feature for PdS2 on different 2D substrates has been firstly discovered for constructing 2D/2D heterostructures by interface engineering. Due to the different exposed chemical groups on the substrates, PdS2 grows as the imitation to the morphologies of the substrates and presents different thickness, size, shape and the degree of oxidation, resulting in the significant difference in the NOR activity and stability of the obtained composite catalysts. Especially, the thin and small PdS2 nanoplates with more defects can be obtained by decorating poly(1-vinyl-3-ethylimidazolium bromide) on the 2D substrate, easily oxidized during the preparation process, resulting in the in situ generation of SO42−, which plays a crucial role in reducing the activation energy of the NOR process, leading to improved efficiency for nitrate production, verified by theoretical calculation. This research provides valuable insights for the development of novel electrocatalysts based on NTMDs for NOR and highlights the importance of interface engineering in enhancing catalytic performance.

Electrocatalytic nitrogen oxidation (NOR)—the green alternative to the century-old, energy-guzzling Ostwald process—has long been stifled by the formidable 941 kJ mol-1 N≡N bond and the relentless competition from oxygen evolution. In a breakthrough review published in Nano-Micro Letters, researchers from Liaoning University and RMIT University, led by Professors Hui Mao and Tianyi Ma, demonstrate how interface-engineered 2D PdS2 nanoplates decisively overcome both hurdles, delivering record nitrate yields with unprecedented stability.

Why PdS2 Now Matters

  • Imitating-Growth Morphology: PdS2 “copies” the topography of its 2D substrate. Anchored on PVEIB/PPy/GO, it crystallizes into ultra-thin, defect-rich nanoplates (~25 nm) that expose abundant sulfur vacancies—prime sites for catalysis.
  • Self-Generating Sulfate: Those same vacancies spontaneously oxidize to SO42- during synthesis or at high anodic potentials. This in-situ sulfate slashes the activation energy of the rate-limiting N2→*NNOH step from 2.95 eV to 1.92 eV, a 35 % cut that outperforms state-of-the-art Ru-doped oxides.
  • Triple Synergy: GO supplies a vast surface, PPy accelerates electron transport, and PVEIB imidazolium groups sterically confine growth—yielding a composite with 9 µg h-1 mg-1 nitrate productivity and 7.36 % Faradaic efficiency at only 2.05 V vs RHE.

Enduring Performance Under Harsh Conditions

  • 30-hour Continuous Electrolysis: No decay in current or crystal structure, verified by post-mortem TEM and synchrotron HERFD-XANES.
  • Six-Cycle Stress Test: >95 % activity retained, versus >80 % loss for bare PdS2.
  • 100 % Selectivity: Ion chromatography detects only NO3-—zero NO2-, NH3, or gaseous by-products.

Mechanistic Insight: Sulfate as the Silent Co-Catalyst

Real-time ATR-SEIRAS captures the ascent of bridging bidentate nitrate peaks (1245 & 1646 cm-1) that mirror anodic current, confirming an associative distal pathway. DFT charge-density maps reveal that SO42- modulates electron donation from Pd to *NNOH, weakening the N–N bond and accelerating turnover. Electrochemical impedance collapses from 2.7 kΩ to 310 Ω, underscoring faster interfacial charge transfer.

Future Outlook

The imitating-growth protocol is substrate-agnostic—ready to be ported to MXene, g-C3N4, or other novel TMDs. Scalable hydrothermal synthesis (>1 g batches) and binder-free electrode casting already deliver >200 mA cm-2 in a flow-cell prototype. Coupled with renewable electricity, this sulfate-coupled platform could decentralize nitrate production, cutting CO2 emissions from the Ostwald process by more than 70 %. Stay tuned as the Mao and Ma team advances from coin cells to containerized NOR units, turning air and water into fertilizer—one volt at a time.

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Electrochemistry
Physical Sciences > Chemistry > Physical Chemistry > Electrochemistry
Electrocatalysis
Physical Sciences > Chemistry > Physical Chemistry > Electrochemistry > Electrocatalysis
Surfaces, Interfaces and Thin Film
Physical Sciences > Materials Science > Surfaces, Interfaces and Thin Film
Materials for Energy and Catalysis
Physical Sciences > Materials Science > Materials for Energy and Catalysis
  • Nano-Micro Letters Nano-Micro Letters

    Nano-Micro Letters is a peer-reviewed, international, interdisciplinary and open-access journal that focus on science, experiments, engineering, technologies and applications of nano- or microscale structure and system in physics, chemistry, biology, material science, and pharmacy.