Ferrielectric Dipolar Ordering in a Donor-Acceptor Based Covalent-Organic Framework for Piezocatalytic Water Splitting

被引：1

作者：

Ghosh, Adrija ^{[1
]}

Menon, Surabhi ^{[2
]}

Biswas, Sandip ^{[3
]}

Sahoo, Supriya ^{[4
,5
]}

Dey, Anupam ^{[3
]}

Boomishankar, Ramamoorthy ^{[4
,5
]}

Zareba, Jan K. ^{[6
]}

Waghmare, Umesh V. ^{[2
]}

Maji, Tapas Kumar ^{[1
,3
]}

机构：

[1] Jawaharlal Nehru Ctr Adv Sci Res JNCASR, Sch Adv Mat SAMat, New Chem Unit, Jakkur PO, Bangalore 560064, India

[2] Jawaharlal Nehru Ctr Adv Sci Res JNCASR, Theoret Sci Unit, Jakkur PO, Bangalore 560064, India

[3] Jawaharlal Nehru Ctr Adv Sci Res JNCASR, Sch Adv Mat SAMat, Chem & Phys Mat Unit, Jakkur PO, Bangalore 560064, India

[4] Indian Inst Sci Educ & Res IISER, Dept Chem, Dr Homi Bhabha Rd, Pune 411008, India

[5] Indian Inst Sci Educ & Res IISER, Ctr Energy Sci, Dr Homi Bhabha Rd, Pune 411008, India

[6] Wroclaw Univ Sci & Technol, Inst Adv Mat, PL-50370 Wroclaw, Poland

来源：

ADVANCED FUNCTIONAL MATERIALS | 2025年

关键词：

covalent-organic Frameworks (COF); ferrielectrics; green H-2 production; metal-free catalysis; piezocatalysis; REDOX REACTIONS; CO2; REDUCTION; CRYSTALLINE; FERROELECTRICITY; POLARIZATION; HYDROGEN;

D O I：

10.1002/adfm.202502787

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Piezocatalysis has emerged as a promising technique for the production of green H-2 fuel by harvesting mechanical energy. A metal-free, highly porous covalent-organic framework (COF) as a piezocatalyst that produces H2 at an ultra-high rate of 6.6 mmol g(-1) h(-1 )under ultrasonication is reported. This activity originates from the electron-hole carriers generated in "nested" nearly degenerate conduction and valence bands driving ferrielectric ordering of dipoles whose coupling with soft torsional phonons facilitates absorption of energy from the mechanical stress fields. Conformationally flexible donor tris(4-aminophenyl)amine (TAPA) moiety in COF introduces soft torsional lattice modes that interact with pyromellitic dianhydride (PDA) acceptor to generate stress tunable dipoles and surface charges. As electron-hole pairs generated throughout the bulk ferrielectric are available at the pore surfaces of the COF, they are readily accessible to the water molecules to be split. The work provides a design concept based on donor-acceptor based frameworks showing conformational flexibility-driven symmetry breaking for piezocatalysis.

引用

页数：11