Work

Experimentally Validated Design Principles of D‐Block Transition Metal Single‐Atom Non‐Dissociative Chemisorption Solid‐State Hydrogen Storage Materials

Year: 2025

Type: article

Abstract: D‐block transition metal (TM) single‐atom non‐dissociative chemisorption solid‐state H 2 storage materials (MSA‐NC‐SHSMs) hold great promise for simultaneously achieving high capacity and fast H 2 adsorption/desorption rates. This potential essentially originates from the abundant d‐orbital electronic states and suitable d‐band centers of d‐block elements, which enable the tuning of H 2 adsorption strength to an appropriate level. However, a lack of guiding principles and fundamental insights has hindered the rational design of these d‐block TM MSA‐NC‐SHSMs. Here in, we introduce various TM single atoms into porphyrin‐based covalent organic frameworks (COFs) to design and prepare d‐block TM MSA‐NC‐SHSMs. A novel descriptor Φ is proposed and validatedthrough integrated theoretical calculations and experimental investigation on a series of TM‐porphyrin‐based MSA‐NC‐SHSMs synthesized by a facile hydrothermal method. A well‐defined volcano relationship based on descriptor Φ effectively quantifies the complicated interaction between H 2 molecules and the surface of host materials, and serves as a reliable tool for guiding the rational design of such materials. Importantly, this study offers in‐depth insight into the origin of the descriptor, and establiahes a systematic, bottom‐up three‐step design principle. This framework enables the development of the materials with hydrogen storage capacities surpassing those of the current best carbon‐based solid‐state hydrogen storage materials.

Source: Advanced Functional Materials

DOI: 10.1002/adfm.202509275