Deciphering in-situ surface reconstruction in two-dimensional CdPS₃ nanosheets for efficient biomass hydrogenation

Area of Science:

• Electrochemistry
• Materials Science
• Catalysis

Background:

• Efficient electrochemical biomass upgrading requires precise control over electrode active sites.
• Developing selective catalysts for converting biomass-derived platform molecules like 5-hydroxymethylfurfural (HMF) is crucial for sustainable chemical synthesis.

Purpose of the Study:

• To investigate the in-situ surface reconstruction of a CdPS₃ nanosheet electrocatalyst for enhanced HMF hydrogenation.
• To develop a CdPS₃/CdS heterostructure for efficient and selective conversion of HMF to 2,5-bis(hydroxymethyl)furan (BHMF).

Main Methods:

• In-situ Raman spectroscopy and post-mortem catalyst characterizations were employed to study the catalyst's structural evolution.
• Electrochemical hydrogenation of HMF was performed using the reconstructed catalyst.
• Density functional theory (DFT) calculations were utilized to understand the reaction mechanism at the interface.

Main Results:

• An in-situ surface reconstruction formed a CdPS₃/CdS heterostructure from the CdPS₃ nanosheet electrocatalyst.
• The CdPS₃/CdS heterostructure achieved a high Faradaic efficiency of 91.3% for BHMF and a yield of 4.96 mg/h at -0.7 V vs RHE.
• DFT calculations confirmed the pivotal role of the CdPS₃/CdS interface in optimizing intermediate adsorption for HMF hydrogenation.

Conclusions:

• The electrolyte-triggered in-situ reconstruction of CdPS₃ nanosheets into a CdPS₃/CdS heterostructure is an effective strategy for electrocatalytic HMF upgrading.
• The developed electrocatalyst demonstrates high activity and selectivity for BHMF production.
• The CdPS₃/CdS heterostructure cathode, coupled with a MnCo₂O_4.5 anode, enables efficient simultaneous synthesis of BHMF and formate from HMF and glycerol.