Porphyrin-Cored H-Bonded Organic Polymer Hermetically Decorated MXene toward Broadband Optical Nonlinearities

Lulu Fu; Zihao Guan; Lu Chen; Zhenyi Yan; Zhipeng Huang; Mark G. Humphrey; Chi Zhang

doi:10.1021/acsami.5c04837

Porphyrin-Cored H-Bonded Organic Polymer Hermetically Decorated MXene toward Broadband Optical Nonlinearities

Lulu Fu^*
, Zihao Guan
, Lu Chen
, Zhenyi Yan
, Zhipeng Huang
, Mark G. Humphrey
, Chi Zhang^*

^*Corresponding author for this work

Research School of Chemistry

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

Two-dimensional MXene (Ti₃C₂T_x) nanosheets suffer from surface oxidation and limited optical tunability. Herein, we report an aqueous-phase functionalization strategy using porphyrin-cored dopamine-type hydrogen-bonded organic polymers (ppd-HOPs) to simultaneously etch, exfoliate, and encapsulate Ti₃C₂T_x. Inspired by mussel adhesion mechanisms, ppd-HOPs undergo spontaneous self-polymerization on MXene surfaces, effectively passivating terminal groups (−OH, ═O, -F) against ambient moisture/oxygen while expanding interlayer spacing. Comprehensive characterization (X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy) confirms the formation of hermetic ppd-HOP/Ti₃C₂T_x nanocomposites (Ti₃C₂T_x(Por₁)_y and Ti₃C₂T_x(Por₂)_y) with covalently anchored different porphyrin units (Por₁ and Por₂). The hybrids exhibit exceptional broadband nonlinear optical (NLO) responses spanning 400-1600 nm, attributed to synergistic effects between MXene’s plasmonic absorption and porphyrin’s excited-state dynamics. Structure-dependent NLO modulation is demonstrated: Ti₃C₂T_x(Por₁)_y functionalized with polymerizable ppd-HOP1 (Por₁-cored dopamine-type hydrogen-bonded organic polymer) achieves a record reverse saturable absorption (RSA) coefficient (β_eff = 587 ± 24.1 cm GW^-1 at 800 nm), outperforming Ti₃C₂T_x(Por₂)_y (β_eff = 396 ± 20.0 cm GW^-1 at 650 nm). Ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy indicates that significant red-shifted and broadened linear absorption induced by extended π-conjugation in ppd-HOP1 provides more ladders for two-photon absorption processes, enabling wavelength-selective RSA behavior. This bioinspired surface engineering approach not only improves MXene’s environmental stability but also pioneers a general paradigm for tailoring MXene-based optoelectronic materials through rational organic-inorganic hybridization.

Original language	English
Pages (from-to)	31295-31305
Number of pages	11
Journal	ACS Applied Materials and Interfaces
Volume	17
Issue number	21
DOIs	https://doi.org/10.1021/acsami.5c04837
Publication status	Published - May 2025

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10.1021/acsami.5c04837

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@article{437c593ce9ad4fbcb4b52ec18998d7d5,

title = "Porphyrin-Cored H-Bonded Organic Polymer Hermetically Decorated MXene toward Broadband Optical Nonlinearities",

abstract = "Two-dimensional MXene (Ti3C2Tx) nanosheets suffer from surface oxidation and limited optical tunability. Herein, we report an aqueous-phase functionalization strategy using porphyrin-cored dopamine-type hydrogen-bonded organic polymers (ppd-HOPs) to simultaneously etch, exfoliate, and encapsulate Ti3C2Tx. Inspired by mussel adhesion mechanisms, ppd-HOPs undergo spontaneous self-polymerization on MXene surfaces, effectively passivating terminal groups (−OH, ═O, -F) against ambient moisture/oxygen while expanding interlayer spacing. Comprehensive characterization (X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy) confirms the formation of hermetic ppd-HOP/Ti3C2Tx nanocomposites (Ti3C2Tx(Por1)y and Ti3C2Tx(Por2)y) with covalently anchored different porphyrin units (Por1 and Por2). The hybrids exhibit exceptional broadband nonlinear optical (NLO) responses spanning 400-1600 nm, attributed to synergistic effects between MXene{\textquoteright}s plasmonic absorption and porphyrin{\textquoteright}s excited-state dynamics. Structure-dependent NLO modulation is demonstrated: Ti3C2Tx(Por1)y functionalized with polymerizable ppd-HOP1 (Por1-cored dopamine-type hydrogen-bonded organic polymer) achieves a record reverse saturable absorption (RSA) coefficient (βeff = 587 ± 24.1 cm GW-1 at 800 nm), outperforming Ti3C2Tx(Por2)y (βeff = 396 ± 20.0 cm GW-1 at 650 nm). Ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy indicates that significant red-shifted and broadened linear absorption induced by extended π-conjugation in ppd-HOP1 provides more ladders for two-photon absorption processes, enabling wavelength-selective RSA behavior. This bioinspired surface engineering approach not only improves MXene{\textquoteright}s environmental stability but also pioneers a general paradigm for tailoring MXene-based optoelectronic materials through rational organic-inorganic hybridization.",

keywords = "hydrogen-bonded organic polymers, MXene nanosheets, nonlinear optical absorption, porphyrins, self-polymerization",

author = "Lulu Fu and Zihao Guan and Lu Chen and Zhenyi Yan and Zhipeng Huang and Humphrey, \{Mark G.\} and Chi Zhang",

note = "{\textcopyright} 2025 The Author(s) ",

year = "2025",

month = may,

doi = "10.1021/acsami.5c04837",

language = "English",

volume = "17",

pages = "31295--31305",

journal = "ACS Applied Materials and Interfaces",

issn = "1944-8244",

publisher = "American Chemical Society",

number = "21",

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TY - JOUR

T1 - Porphyrin-Cored H-Bonded Organic Polymer Hermetically Decorated MXene toward Broadband Optical Nonlinearities

AU - Fu, Lulu

AU - Guan, Zihao

AU - Chen, Lu

AU - Yan, Zhenyi

AU - Huang, Zhipeng

AU - Humphrey, Mark G.

AU - Zhang, Chi

PY - 2025/5

Y1 - 2025/5

N2 - Two-dimensional MXene (Ti3C2Tx) nanosheets suffer from surface oxidation and limited optical tunability. Herein, we report an aqueous-phase functionalization strategy using porphyrin-cored dopamine-type hydrogen-bonded organic polymers (ppd-HOPs) to simultaneously etch, exfoliate, and encapsulate Ti3C2Tx. Inspired by mussel adhesion mechanisms, ppd-HOPs undergo spontaneous self-polymerization on MXene surfaces, effectively passivating terminal groups (−OH, ═O, -F) against ambient moisture/oxygen while expanding interlayer spacing. Comprehensive characterization (X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy) confirms the formation of hermetic ppd-HOP/Ti3C2Tx nanocomposites (Ti3C2Tx(Por1)y and Ti3C2Tx(Por2)y) with covalently anchored different porphyrin units (Por1 and Por2). The hybrids exhibit exceptional broadband nonlinear optical (NLO) responses spanning 400-1600 nm, attributed to synergistic effects between MXene’s plasmonic absorption and porphyrin’s excited-state dynamics. Structure-dependent NLO modulation is demonstrated: Ti3C2Tx(Por1)y functionalized with polymerizable ppd-HOP1 (Por1-cored dopamine-type hydrogen-bonded organic polymer) achieves a record reverse saturable absorption (RSA) coefficient (βeff = 587 ± 24.1 cm GW-1 at 800 nm), outperforming Ti3C2Tx(Por2)y (βeff = 396 ± 20.0 cm GW-1 at 650 nm). Ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy indicates that significant red-shifted and broadened linear absorption induced by extended π-conjugation in ppd-HOP1 provides more ladders for two-photon absorption processes, enabling wavelength-selective RSA behavior. This bioinspired surface engineering approach not only improves MXene’s environmental stability but also pioneers a general paradigm for tailoring MXene-based optoelectronic materials through rational organic-inorganic hybridization.

AB - Two-dimensional MXene (Ti3C2Tx) nanosheets suffer from surface oxidation and limited optical tunability. Herein, we report an aqueous-phase functionalization strategy using porphyrin-cored dopamine-type hydrogen-bonded organic polymers (ppd-HOPs) to simultaneously etch, exfoliate, and encapsulate Ti3C2Tx. Inspired by mussel adhesion mechanisms, ppd-HOPs undergo spontaneous self-polymerization on MXene surfaces, effectively passivating terminal groups (−OH, ═O, -F) against ambient moisture/oxygen while expanding interlayer spacing. Comprehensive characterization (X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy) confirms the formation of hermetic ppd-HOP/Ti3C2Tx nanocomposites (Ti3C2Tx(Por1)y and Ti3C2Tx(Por2)y) with covalently anchored different porphyrin units (Por1 and Por2). The hybrids exhibit exceptional broadband nonlinear optical (NLO) responses spanning 400-1600 nm, attributed to synergistic effects between MXene’s plasmonic absorption and porphyrin’s excited-state dynamics. Structure-dependent NLO modulation is demonstrated: Ti3C2Tx(Por1)y functionalized with polymerizable ppd-HOP1 (Por1-cored dopamine-type hydrogen-bonded organic polymer) achieves a record reverse saturable absorption (RSA) coefficient (βeff = 587 ± 24.1 cm GW-1 at 800 nm), outperforming Ti3C2Tx(Por2)y (βeff = 396 ± 20.0 cm GW-1 at 650 nm). Ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy indicates that significant red-shifted and broadened linear absorption induced by extended π-conjugation in ppd-HOP1 provides more ladders for two-photon absorption processes, enabling wavelength-selective RSA behavior. This bioinspired surface engineering approach not only improves MXene’s environmental stability but also pioneers a general paradigm for tailoring MXene-based optoelectronic materials through rational organic-inorganic hybridization.

KW - hydrogen-bonded organic polymers

KW - MXene nanosheets

KW - nonlinear optical absorption

KW - porphyrins

KW - self-polymerization

UR - https://www.scopus.com/pages/publications/105005357549

U2 - 10.1021/acsami.5c04837

DO - 10.1021/acsami.5c04837

M3 - Article

C2 - 40371789

AN - SCOPUS:105005357549

SN - 1944-8244

VL - 17

SP - 31295

EP - 31305

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 21

ER -

Porphyrin-Cored H-Bonded Organic Polymer Hermetically Decorated MXene toward Broadband Optical Nonlinearities

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