Amino-Acid-Functionalized Metal–Organic Frameworks as Excellent Precursors toward Bifunctional Metal-Free Electrocatalysts

Abstract

Metal–organic frameworks (MOFs) are promising precursors for synthesizing functional carbon materials, and their atomic-scale designs have recently been studied for improving their performance. Herein, we synthesized an alanine-decorated MOF-5 via a solvothermal method using a mixture of dimethylformamide and water as the solvent. Experimental and computational investigations revealed that alanine residues were located in the micropores of MOF-5 due to interactions between the MOF Zn clusters and the carboxylic acid groups of the alanine moieties. In addition, the alanine-decorated MOF-5 was carbonized at 1100 °C for application as an electrocatalyst. It was found that the resulting N-doped carbonized sample exhibited excellent catalytic activities in the oxygen reduction and hydrogen evolution reactions and afforded superior results to those reported for other metal-free carbon catalysts. This high activity originated from the single nitrogen configuration (pyrrolic N) in the hierarchical pores. This article presents a facile strategy for the syntheses of both functionalized MOFs and N-doped carbon materials.

Metal‐Organic Framework (MOF)‐Based Clean Energy Conversion: Recent Advances in Unlocking its Underlying Mechanisms

“…used alanine modified MOF‐5 carbonized at 1100 °C as an electrocatalyst for ORR and HER, showing good activity using a single nitrogen configuration in the lamellar pores. [ 81 ] In this work, the authors found by grand‐canonical Monte Carlo simulations that the uniform micropores of pristine MOF‐5 disappeared the sharp peak at 0.78 nm compared to the precursor, and that A/MOF/x (alanine‐treated MOF‐5) exhibited a wider peak than that of pristine MOF‐5. It reveals that the chemical interaction between alanine and the structural units of MOF‐5 affects the ordered pore structure.…”

“…The application of Monte Carlo molecular simulation methods to simulate chemical reactions, especially in pores, is one of the more cutting-edge and emerging research directions in the field of molecular simulation. [80][81][82] This method is able to observe the pore size, shape, surface non-uniformity and other properties of catalytic materials, as well as the effects of temperature, pressure and other variables on the equilibrium and kinetics of chemical reactions from the molecular microscopic level, so as to better grasp the essential characteristics of chemical reactions. For instance, Shu et al used alanine modified MOF-5 carbonized at 1100 °C as an electrocatalyst for ORR and HER, showing good activity using a single nitrogen configuration in the lamellar pores.…”

Biological Metal–Organic Framework-Embedded MXene Nanocomposite as a Wearable Transducer Patch for Real-Time Monitoring of the Sleep Hormone

“…Additionally, a N peak was not observed on the as-synthesized Nb 2 CT x MXene. Figure e shows the HR scan of N1 s, which consists of a peak at 399.5 eV that could be attributed to amine groups, while the other peak at 401.5 eV can be assigned to protonated amines …”

“…Figure 2e shows the HR scan of N1 s, which consists of a peak at 399.5 eV that could be attributed to amine groups, while the other peak at 401.5 eV can be assigned to protonated amines. 56 Electrochemical Analysis. The electrochemical performance of the CY electrode modified with Zn-MOF, Nb Ultimately, the optimal pH for the electrocatalytic oxidation of MEL was determined to be 7.2.…”

Zn(ii)-MOF derived N-doped carbons achieve marked ORR activity in alkaline and acidic media

“…However, the nitrogen-heteroatoms need to be incorporated exteriorly in a controllable manner. 16,17 To this end, we envision that Zn-MOFs with mixed azolate and terephthalate ligands (herein denoted as Zn-MOF-mix) might be a better option since they perfectly merge the merits of the abovementioned two types of Zn-MOFs. Nonetheless, it remains scarce to apply Zn-MOF-mix to prepare metal-free carbon materials.…”