Specific Sn–O–Fe Active Sites from Atomically Sn-Doping Porous Fe2O3 for Ultrasensitive NO2 Detection

Published in Chemistry and Materials

Specific Sn–O–Fe Active Sites from Atomically Sn-Doping Porous Fe2O3 for Ultrasensitive NO2 Detection
Like

Share this post

Choose a social network to share with, or copy the URL to share elsewhere

This is a representation of how your post may appear on social media. The actual post will vary between social networks

Explore the Research

SpringerLink
SpringerLink SpringerLink

Specific Sn–O–Fe Active Sites from Atomically Sn-Doping Porous Fe2O3 for Ultrasensitive NO2 Detection - Nano-Micro Letters

Conventional gas sensing materials (e.g., metal oxides) suffer from deficient sensitivity and serve cross-sensitivity issues due to the lack of efficient adsorption sites. Herein, the heteroatom atomically doping strategy is demonstrated to significantly enhance the sensing performance of metal oxides-based gas sensing materials. Specifically, the Sn atoms were incorporated into porous Fe2O3 in the form of atomically dispersed sites. As revealed by X-ray absorption spectroscopy and atomic-resolution scanning transmission electron microscopy, these Sn atoms successfully occupy the Fe sites in the Fe2O3 lattice, forming the unique Sn–O–Fe sites. Compared to Fe–O–Fe sites (from bare Fe2O3) and Sn–O–Sn sites (from SnO2/Fe2O3 with high Sn loading), the Sn–O–Fe sites on porous Fe2O3 exhibit a superior sensitivity (Rg/Ra = 2646.6) to 1 ppm NO2, along with dramatically increased selectivity and ultra-low limits of detection (10 ppb). Further theoretical calculations suggest that the strong adsorption of NO2 on Sn–O–Fe sites (N atom on Sn site, O atom on Fe site) contributes a more efficient gas response, compared to NO2 on Fe–O–Fe sites and other gases on Sn–O–Fe sites. Moreover, the incorporated Sn atoms reduce the bandgap of Fe2O3, not only facilitating the electron release but also increasing the NO2 adsorption at a low working temperature (150 °C). This work introduces an effective strategy to construct effective adsorption sites that show a unique response to specific gas molecules, potentially promoting the rational design of atomically modified gas sensing materials with high sensitivity and high selectivity.

Led by Prof. Xuhui Sun at Soochow University’s Institute of Functional Nano & Soft Materials (FUNSOM), a team has devised a metal–organic-framework (MOF)-derived α-Fe2O3 scaffold in which single Sn atoms occupy Fe lattice positions, forging Sn–O–Fe bridges. This first-of-its-kind single-atom architecture, reported in Nano-Micro Letters, delivers record-breaking NO2 sensitivity (Rg/Ra = 2,646 at 1 ppm, 10 ppb limit of detection) at only 150 °C, while a MEMS implementation sips 8 mW—five-fold lower than commercial MOS sensors.

Why This Work Matters

  • Health & Regulation: WHO sets 82 ppb as the 1-hour NO2 exposure limit. The new sensor reliably quantifies 10 ppb—an order of magnitude lower—enabling early indoor/outdoor pollution alerts.
  • Energy Footprint: 150 °C operating temperature plus 8 mW power budget (0.7 V micro-hotplate) unlock battery-driven wearables, IoT nodes and drone-mounted grids.
  • Selectivity: Sn–O–Fe sites suppress cross-responses to SO2, NH3, H2S, acetone and CO (<5 % relative signal), eliminating false alarms in complex exhaust streams.
  • Stability: >60 days continuous operation and humidity immunity (0–90 % RH) meet industrial-grade reliability.

Innovative Design & Mechanisms

  • MOF-to-SAC Synthesis

      – Fe-MIL-88B-NH2 MOF “molecular fences” pre-isolate Sn4+ ions (2–8 at %).

      – One-step 500 °C air anneal converts MOF into porous α-Fe2O3 while locking Sn atoms into exact Fe sites (HAADF-STEM shows bright single dots; no SnO2 clusters until 8 at %).

  • Electronic Structure Engineering

      – XANES + DFT: Sn donation narrows bandgap from 2.24 eV (pristine) to 1.67 eV, increasing electron density at 150 °C.

      – Oxygen-vacancy-rich lattice (EPR g = 2.005) further accelerates O₂⁻ formation and NO₂ charge transfer.

  • Adsorption & Kinetics

      – DFT shows NO2 binds at −2.20 eV on Sn–O–Fe vs −0.48 eV on Fe–O–Fe, cutting response/recovery times to 16 s / 148 s.

      – Linear calibration (R2 = 0.996) spans 0.2–1 ppm for alumina substrates and 10–50 ppb for MEMS chips.

Applications & Future Outlook

  • Smart Cities: Wafer-level MEMS arrays (3 × 3 × 1.3 mm3) integrate into streetlights and HVAC ducts for distributed NO2 mapping.
  • Wearable Health: Flexible PET patches (demonstrated in lab) provide personal exposure analytics with BLE transmission to smartphones.
  • Industrial Safety: Explosion-proof probes for petrochemical stacks (150 °C operation eliminates need for flame-proof heaters).
  • Roadmap: Roll-to-roll coating of Sn-Fe2O3 inks on polyimide foils, AI-driven drift compensation, and extension to SO2 and VOC single-atom sensors.

Conclusions

By merging single-atom catalysis with semiconductor gas sensing, Prof. Sun’s group achieves the first ppb-level NO2 detector that marries high sensitivity, low power and scalable fabrication. The MOF-derived Sn–O–Fe platform not only redefines NO2 monitoring but also sets a universal blueprint for atomically engineered MOS sensors across toxic and greenhouse gases.

Please sign in or register for FREE

If you are a registered user on Research Communities by Springer Nature, please sign in

Follow the Topic

Sensors and Biosensors
Physical Sciences > Materials Science > Materials for Devices > Sensors and Biosensors
Materials for Devices
Physical Sciences > Materials Science > Materials for Devices
Metal-organic Frameworks
Physical Sciences > Chemistry > Organic Chemistry > Metal-organic Frameworks
Nanoscale Design, Synthesis and Processing
Physical Sciences > Materials Science > Nanotechnology > Nanoscale Design, Synthesis and Processing
Porous Materials
Physical Sciences > Chemistry > Materials Chemistry > Porous Materials
  • 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.