D-Band Width Rationally Broadened by Configuring Nearest Coordination of Metal Site for Enhanced Active...

Area of Science:

• Heterogeneous catalysis
• Materials science
• Surface chemistry

Background:

• Metal active sites are crucial for redox and charge transfer in heterogeneous catalysis.
• Modulating metal valence states can control intermediate adsorption but is limited by local atomic configurations.
• Unpredictable catalytic failures arise from limitations in valence state modulation.

Purpose of the Study:

• To investigate the relationship between platinum's d-band width and intermediate adsorption strength.
• To develop a strategy for tuning catalytic activity by engineering the electronic structure of metal active sites.
• To enhance the hydrogen evolution reaction (HER) activity through d-band width modulation.

Main Methods:

• Correlating platinum's d-band width (Wd-Pt) with intermediate adsorption strength.
• Modulating the nearest-neighbor coordination environment of platinum sites by incorporating transition metals.
• Evaluating catalytic activity for the hydrogen evolution reaction (HER).

Main Results:

• A linear relationship was established between platinum's d-band width and intermediate adsorption strength.
• Adjusting the coordination environment of platinum sites effectively modulated Wd-Pt.
• This strategy resulted in high HER activity (η10 = 14 mV) due to elevated Pt-H anti-bonding states.
• Wd-Pt broadening strengthens active site-absorbate interactions, tuning catalytic activity.

Conclusions:

• The d-band width engineering strategy offers a method to boost metal active site activity in heterogeneous catalysis.
• This approach transcends limitations of valence state modulation and provides deeper insights into d-band structure.
• The strategy is potentially applicable to other metal-based catalysts.