Porous porphyrin-based photocatalysts: recent progress and applications in environmental remediation

Abstract

Environmental pollution from organic contaminants poses a significant threat to ecosystems and human health, which require innovative and efficient remediation strategies. Porphyrin-based materials, renowned for their excellent photochemical properties, have emerged as promising photocatalysts for degrading organic pollutants under light irradiation. Introducing porosity into these porphyrin systems further enhances their catalytic performance by improving pollutant adsorption, increasing surface area, and facilitating efficient light utilization. This review highlights recent progress in the design, synthesis, and functionalization of porous porphyrin-based photocatalysts, including metal–organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs) and porous organic polymers (POPs). Particular attention is given to their applications in environmental remediation, such as the degradation of pharmaceuticals, pesticides, dyes, and industrial wastes. The underlying photocatalytic mechanisms, performance metrics, and real-world applicability are discussed in detail. Finally, the prospects and challenges of porous porphyrin-based materials for photocatalysis are also discussed.

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Introduction

The rapid pace of industrialization and urbanization has led to the extensive discharge of organic pollutants into the environment.^1–5 These contaminants include pharmaceutical residues^6–8 (e.g., diclofenac sodium, ciprofloxacin, tetracycline and ranitidine), synthetic dyes^9–11 (such as rhodamine B, rose bengal, erythrosine B, and methylene blue), pesticides^12–14 (such as organophosphorus pesticides, nitenpyram, and 2,4-dichlorophenoxyacetic acid), and various industrial chemicals^15–17 (e.g., bisphenol A (BPA), bisphenol F and polychlorinated biphenyls) (Fig. 1). Their persistence and toxicity pose serious threats to ecosystems and human health.^17–24 Conventional remediation techniques—such as chemical oxidation,^25,26 physical adsorption,^27–29 and biological treatment^30–32—often fall short in effectively eliminating these complex pollutants. As a result, there is an urgent need for innovative, efficient, and sustainable technologies to address this escalating environmental challenge.^33,34

Fig. 1 Overview of major organic pollutants and their environmental and health impacts.

Photocatalysis, which utilizes solar or artificial light to drive chemical reactions for pollutant degradation, has emerged as a highly promising solution.^35–39 It enables the mineralization of harmful organic compounds into benign end-products such as CO₂ and H₂O under mild conditions.^40,41 Among the various photocatalytic materials investigated, porphyrin-based compounds have attracted considerable attention due to their exceptional photophysical and photochemical properties, which make them highly suitable for light-driven applications.^42–45 As naturally inspired macrocyclic molecules composed of four pyrrole rings linked via methine bridges, porphyrins possess a highly conjugated π-system that enables strong absorption in the visible region, particularly within the Soret and Q bands.^46–48 This extensive light-harvesting ability, combined with their high redox activity and photostability, allows porphyrins to undergo efficient photoinduced electron transfer processes and sustain multiple catalytic cycles without significant degradation. Moreover, their structural versatility permits easy modification through peripheral substitution or central metal coordination, enabling fine-tuning of their electronic properties and photocatalytic behaviour. These features collectively position porphyrins as promising candidates in the design of next-generation photocatalysts for environmental remediation and energy-related applications.^49–51 As shown in Fig. 2, building on the unique photophysical properties of porphyrins, their function as photocatalysts begins with the absorption of photons (hv) possessing energy greater than their band gap energy (E_g). This operation generates a charge separation due to the transfer of an electron from the VB (valence band) to the CB (conduction band), thus generating a pair of reactive species (h⁺ in the VB and e⁻ in the CB). A photocatalytic reaction proceeds if the recombination of hole pairs is delayed. This is because excited electrons react with the dye molecule to create a reduced product, and excited holes react with O₂ (the electron acceptor) dissolved in an aqueous solution and reduce it to a superoxide radical anion (O₂˙⁻). On the other hand, the excited holes can react with OH⁻ or water and oxidize them into hydroxyl radicals (˙OH).^52,53 Other highly oxidizing materials, such as peroxide radicals, may also be produced during photodecomposition.^54,55 The O₂˙⁻ is oxidized by the hole in the photocatalyst and partially becomes a singlet oxygen molecule (¹O₂). The resulting ROS are strong oxidizing agents that can mineralize pollutants into less toxic molecules.^56–58

Fig. 2 Schematic showing the photocatalytic mechanism of porous porphyrin-based materials.

Despite their inherent advantages, traditional porphyrin photocatalysts often suffer from limitations including low surface area, poor pollutant adsorption, and limited charge separation efficiency. To address these challenges, significant efforts have been devoted to integrating porphyrin moieties into porous materials, thereby enhancing their photocatalytic potential. In this context, porous architectures such as metal–organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and porous organic polymers (POPs) have emerged as highly promising platforms (Fig. 3). These materials not only provide large surface areas and tunable porosity but also facilitate efficient light harvesting, improved mass transport, and effective electron–hole separation.^59–61

Fig. 3 Schematic diagram of porphyrin-based porous materials.

The incorporation of porphyrins into these frameworks enables synergistic enhancements in photocatalytic performance. For instance, MOFs and COFs allow for the rational design of pore environments and active sites through modular synthesis.^62–64 Meanwhile, HOFs and POPs offer superior chemical and thermal stability, as well as ease of recyclability, which is crucial for sustainable environmental applications.^65,66 Through optimized structural design and functionalization, these hybrid materials exhibit remarkable activity in the degradation of diverse classes of pollutants, offering real-world potential for water purification and environmental remediation.^67,68

Recently, numerous reviews have documented the advancements in porphyrin-based materials, particularly in the context of energy-related applications such as photovoltaics, sensing, and photocatalytic hydrogen production.^56,69–76 However, a comprehensive understanding of the relationship between the structure of porphyrin-based porous materials and their photocatalytic performance in environmental applications—especially in water treatment—remains insufficiently explored. Furthermore, comparative analyses across different classes of porous architectures, including MOFs, COFs, HOFs, and POPs, are still limited, hindering the rational design of next generation photocatalysts.^77,78

The aim of this review is to evaluate the recent developments in porous porphyrin-based materials, elucidate the correlations between their structural features and photocatalytic activity, and assess their practical applicability in environmental remediation, particularly for the degradation of persistent organic pollutants. Special attention is given to the design principles, synthetic strategies, and functionalization approaches that enhance their light-harvesting capabilities, stability, and reactive species generation. By providing a unified perspective on both fundamental material design and application-driven performance, this review seeks to bridge the current gap between material innovation and real-world environmental challenges. It also highlights key bottlenecks and future directions to guide researchers in the development of more efficient, stable, and scalable porphyrin-based porous photocatalysts for water purification and related applications (Tables 1–3).

Table 1 Summary of porphyrin-based MOF photocatalysts for pollutant degradation, showing ligands, active species, and efficiencies

Target pollutant(s)	Photocatalyst	Porphyrin linkers	Metal nodes	Co-catalyst/sensitizer	Light source	Key active species	Efficiency (%) & time	Year	Ref.
BPA	PCN-222		Zr	—	300 W Xe	^1O2	99.9 in 20 min	2017	79
RND	TCPP@PCN-777		Zr	PCN-777	500 W Xe	^1O2	>99 in 1 h	2023	80
RhB, EB andRB	PCN-222(Fe)		Zr	Fe3O4@SiO2	500 W halogen	˙O2^−	RhB (92), EB (99), RB (98) in 1 h	2021	81
CIP	Fe-TCPP		Fe	—	500 W Xe	˙OH	100	2022	82
RhB	UiO-66 MOF		Zr	UiO-66	800 W Xe	˙OH	100 in 1 h	2019	83
RhB and TC	Cu-TCPP MOF		Cu	—	300 W Xe	˙O2^−	RhB (81.2), TC (86.3)	2020	84
BPF	PCN-223		Zr	—	500 W Xe	˙O2^−, ^1O2	78 in 30 mins	2022	85
NIT, THI, IPU, and ATZ	FMOF		Zr	—	Laser irradiation	h^+, ^1O2, ˙OH	NIT (95), THI (82.3), IPU (67.4), ATZ (76.2)	2020	86
CIP and TC	PCN-224		Zr	—	500 W Xe	^1O2	CIP (84), TC (92) in 1 h	2021	87
RhB and TC	PCN-222		Zr	Nitrogen-doped CDs	300 W UV lamp	^1O2, ˙OH, ˙O2^−, h^+	RhB (100), TC (90.93) in 20 mins	2021	88
MB	PCN-224		Zr	Polyvinyl dene fluoride	300 W Xe	^1O2	95.6 in 1 h	2021	89
MO, MB, CV, and RhB	2DZnTCPP		Zn	—	300 W Xe	ROS	MO (92), MB (99), RhB (98), CV (97)	2022	90
MO and MB	Fe–La		La	—	200 W Hg lamp	ROS	MO (55), MB (93)	2023	91
MB and RhB	AlPMOF(M)		Al	—	50 W white LED	˙OH, ˙O2^−	MB (98), RhB(96) in 1 h	2024	92
Atrazine	Fe-PCN-134		Zr	Zr-BTB	300 W xenon lamp	ROS	99.41 in 80 min	2024	93
Rh6G	UDS-2		Zn	—	520 nm LED	^1O2	61 in 3 h	2025	94

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Table 2 Summary of porphyrin-based COF, HOF and POP photocatalysts for pollutant degradation, showing ligands, active species, and efficiencies

Target pollution	Photocatalyst	Porphyrin	Linker	Light source	Active species	Efficiency (%) & time	Ref.	Year
CR	UPC-CMP-1			Visible light	˙OH, h^+, and ˙O^2−	88.3%	111	2016
RhB	CuPor-Ph- COF/g-C3N4			300 W Xe	ROS	86% in 15 min	108	2019
OPs	COF-366			LED-light	^1O2	>97% in 1 h	110	2023
RhB	CuTB-CO/CuTP-COF			Visible light	^1O2	98.70% in 1 h	112	2025
RhB	TAPP-TFPB-COF			Visible light	ROS	>95.6% in 3 h	113	2025
RhB	COF-H/HMTBD			300 W Xe	˙O2^−/˙OH	90% in 3 h	114	2022
9,10-Diphenylanthracene	TCPP-2		—	LED-light	Not mentioned	99% in 1.5 h	115	2019
SDZ	PFC-72/TiO2		—	Xe	^1O2	93.73% in 2 h	116	2025
MB	Por-CMPs			300 W Xe	˙O2^−/˙OH	98% in 1.5 h	117	2024
TC	Por-BT-1			300 W Xe	ROS	84% in 40 min	100	2025
BPA	Por-BT-2	Same as above	Same as above	300 W Xe	ROS	98% in 30 min	100	2025
MB	TCPP/TiO2 thin film		TCPP-sensitized TiO2 thin film	Visible light	ROS	49% for 5 h	118	2019
MB	Por-PD-COF			300 W Xe	˙O2^−/˙OH	MB (98%) for 3 h	119	2023
BPA 2,4-D	COPs			300 W Xe	ROS	99% for 30 min	120	2024
MB, MO, and TC	CuPT-CPP			Visible light	˙O2^−/˙OH/^1O2	100% in 3 h	121	2024

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Table 3 Comparison on the relative advantages and limitations of MOFs, COFs, HOFs, and POPs for photocatalytic applications

Material class	Key advantages	Limitations	Active species
MOFs	Highly crystalline; tunable metal nodes and organic linkers; well-defined active sites; good porphyrin incorporation	Hydrolytic instability in water; sometimes limited thermal stability; scale-up challenges	Mechanistic studies, tunable ROS generation, and selective degradation pathways
COFs	Robust covalent bonds; long-range order; efficient charge transport; high surface area	Harsh synthesis conditions; difficult scalability; some frameworks show poor water dispersibility	Visible-light-driven pollutant degradation with efficient charge separation
HOFs	Simple, mild synthesis; metal-free; structural flexibility; biocompatibility	Stability issues due to weak hydrogen-bonding; relatively young field with fewer examples	Emerging candidates for aqueous photocatalysis with tunable porosity
POPs	Exceptional thermal/chemical stability; scalable synthesis; modular design; versatile functionalization	Amorphous nature complicates structure–property analysis; sometimes less predictable porosity	Robust photocatalysts with high pollutant affinity and operational durability

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Through this effort, we hope to inspire further interdisciplinary research aimed at unlocking the full potential of these promising materials in sustainable pollution control technologies.

Porphyrin-based metal–organic frameworks

Since the pioneering work of Yaghi and his team in the 1990s, metal–organic frameworks (MOFs) have garnered considerable interest due to their unique structural features and broad applicability.^95–97 These porous crystalline materials are constructed from metal ions or clusters coordinated to organic ligands, offering exceptionally high surface areas, tunable pore sizes, and outstanding chemical versatility.^98,99 Among the various ligands explored for MOF construction, porphyrins and their derivatives stand out as particularly attractive building blocks for photocatalytic applications. Their strong light-harvesting capabilities, excellent photophysical and redox properties, and ease of structural modification make porphyrins ideally suited for integration into MOF architectures. When incorporated into MOFs, porphyrin units confer additional functionality, yielding porphyrin-based MOFs (P-MOFs) that combine the advantages of both components: the tunable, porous nature of MOFs and the efficient photoactivity of porphyrins. The resulting materials exhibit enhanced catalytic performance, particularly in light-driven degradation reactions. Thanks to their uniform open cavities and high surface accessibility, P-MOFs can act as multifunctional photocatalysts capable of generating reactive oxygen species under light irradiation, thereby enabling the efficient degradation of various organic pollutants.^85,90,93 Notably, P-MOFs have demonstrated excellent photocatalytic activity against common dye contaminants such as rhodamine B (RhB) methyl blue (MB), methyl orange (MO) etc., highlighting their potential in environmental remediation.^{80–91,100–102}

One of the earliest demonstrations of porphyrin-based MOFs for water treatment was reported by Meng et al., who employed PCN-222, a Zr-porphyrin framework, for the adsorption and visible-light-driven degradation of bisphenol A (BPA).⁷⁹ PCN-222 combined high adsorption capacity with remarkable photocatalytic activity, achieving complete BPA removal within 20 minutes under light irradiation. This pioneering work highlighted the dual roles of porphyrin MOFs as both adsorbents and photocatalysts, establishing a benchmark for environmental remediation applications. Building on such foundational studies, Tang and co-workers developed a porphyrin-based two-dimensional layered MOF, 2DZnTCPP, which was designed for efficient photo- and sono-catalytic water treatment, targeting both organic dyes and bacterial contaminants.⁹⁰ Constructed from Zn clusters and TCPP ligands, the MOF features a high surface area (854.4 m² g⁻¹), 55% porosity, and abundant exposed Zn sites that enhance catalytic activity. The Zn species promote intersystem crossing (ISC) via increased spin–orbit coupling, enabling efficient singlet oxygen (¹O₂) generation, while the 2D structure reduces self-quenching from π–π stacking (Fig. 4). Additionally, ligand-to-metal charge transfer (LMCT) modulates the energy band structure facilitating hydroxyl radical (˙OH) production through water splitting at Zn sites. As a result, 2DZnTCPP demonstrated excellent photocatalytic and sonocatalytic performance, completely degrading various organic dyes within 10 minutes and achieving over 99.99999% bactericidal efficiency within 30 minutes, all without the need for external oxidants like O₃ or H₂O₂. This study presents a strategy for designing and synthesizing MOF-based photocatalysts aimed at purifying and treating textile wastewater, with a focus on developing a more efficient, rapid, and environmentally friendly catalytic system.

Fig. 4 Schematic diagram of 2DZnTcpp for sono-/photo-catalytic water decontamination. Reprinted with permission.⁹⁰ Copyright (2022) of American Chemical Society.

Wang and co-workers developed a porphyrin-based MOF system demonstrating enhanced degradation of bisphenol F (BPF) under visible light, even under high salinity conditions in 2023.⁸⁵ The MOF exhibited excellent photocatalytic performance, attributed to its robust porphyrin ligand structure and porous framework, facilitating effective adsorption and activation of BPF molecules. Under visible light irradiation, the system rapidly generated singlet oxygen ¹O₂ and other reactive oxygen species responsible for efficient BPF degradation (Fig. 5). Remarkably, high salt concentrations typically inhibitory to photocatalysis instead enhanced degradation rates, highlighting the MOF's unique tolerance and adaptability to saline environments. Mechanistic investigations confirmed that ¹O₂ played a dominant role, supported by control experiments with scavengers. The material also showed good stability and recyclability, emphasizing its potential for practical water treatment applications in saline wastewater and marine environments.

Fig. 5 EPR spectra in the PCN-223/visible-light system with/without three coexisting anions (Cl⁻, SO₄²⁻ and NO₃⁻) using (a) DMPO for O₂⁻, (b) TEMP for ¹O₂, and (c) DMPO for ˙OH, (d) the concentrations of anions with/without catalysts, and (e) proposed mechanism of enhanced photo-induced ˙OH generation under high salinity conditions. Reprinted with permission.⁸⁵ (Copyright (2022) of Elsevier).

In 2025, Harvey and co-workers developed a porphyrin-based three-dimensional interpenetrated MOF, UDS-2 (3D-[Zn₂(TPyP)(NO₂)₂]_n) (Fig. 6), as a highly efficient photosensitizer for singlet oxygen (¹O₂) generation and photocatalytic water treatment.⁹⁴ Constructed from Zn(NO₂)₂ nodes and 5,10,15,20-tetrapyridylporphyrin zinc(II) (ZnTPyP) ligands, UDS-2 exhibits distinct zinc coordination environments—square pyramidal and quasi-octahedral—that contribute to its unique electronic structure. The MOF shows a low-energy charge transfer (CT) transition and enhanced energy transfer efficiency via singlet–singlet and triplet–triplet mechanisms, enabling strong ¹O₂ production in both solid and aqueous phases. Its structure supports rapid exciton migration, minimizing energy losses and surpassing benchmark porphyrin-based MOFs such as PCN-222 and PCN-224 in photosensitization performance. UDS-2 demonstrated remarkable photocatalytic degradation of rhodamine 6G under visible light. This work highlights a multifunctional MOF platform with superior photodynamic properties for sustainable water purification and environmental remediation.

Fig. 6 Schematic diagram of Zn–porphyrin MOFs for photocatalytic water decontamination. Reprinted with permission.⁹⁴ Copyright (2025) of the American Chemical Society.

Wu and researchers synthesized and characterized Fe-PCN-134, a mixed-linker metalloporphyrin metal–organic framework (MOF), designed for the efficient degradation of atrazine, a persistent herbicide, via a visible-light-driven photo-Fenton reaction in 2022.⁹³ The MOF incorporated both Fe centers and porphyrin ligands, enabling dual functionality as a photocatalyst and a Fenton reagent. Under visible light, Fe-PCN-134 generated hydroxyl radicals (˙OH) and singlet oxygen (¹O₂), leading to rapid and effective degradation of atrazine. The incorporation of mixed linkers enhanced light absorption and electronic transfer, improving catalytic efficiency (Fig. 7). Mechanistic studies, including radical scavenging experiments and spectroscopic analyses, confirmed the involvement of both ˙OH and ¹O₂ species. The material maintained high activity over multiple cycles and showed robust structural stability. Additionally, environmental evaluations demonstrated low Fe leaching and good performance across a wide pH range, highlighting Fe-PCN-134's potential for sustainable and practical application in the removal of organic micropollutants from contaminated water.

Fig. 7 Illustration of how the Zr-BTB/Fe-TCPP(Cl) photocatalyst uses sunlight to break down pollutants in water into harmless substances. The process is safe for plants and human cells. Reprinted with permission.⁹³ (Copyright (2024) of Elsevier).

Another work from Nguyen and co-workers in 2024 developed a series of porphyrinic aluminum-based metal–organic frameworks (AlPMOF(M)) metalated with Cu²⁺ and Co²⁺ ions for efficient photodegradation of organic dyes under visible light.⁹² Synthesized via a solvothermal method, these MOFs exhibited strong photoabsorption in the visible region, high stability, and suitable band gaps for photocatalysis (Fig. 8). Among them, the Cu-metallated AlPMOF showed outstanding performance, achieving 98% degradation of methylene blue and 96% of rhodamine B within 300 minutes at high dye concentrations (100 mg L⁻¹). This high activity was attributed to enhanced charge separation and reactive oxygen species generation, facilitated by the Cu-porphyrin centers. The material demonstrated excellent reusability over seven cycles without significant loss in performance. Mechanistic studies using UHPLC-MS and DFT calculations revealed detailed degradation pathways and confirmed the formation of oxidative intermediates, highlighting AlPMOF(Cu) as a promising and stable photocatalyst for wastewater treatment applications.

Fig. 8 The plausible photodegradation mechanism of organic dyes over AlPMOF(Cu). Reprinted with permission.⁹² (Copyright (2024) of Elsevier).

Porphyrin-based covalent organic frameworks

First reported by Yaghi and co-workers in 2005, COFs are a class of crystalline, porous materials constructed from light elements (C, H, N, O, and B) through strong covalent bonds.^103,104 Unlike MOFs, which incorporate metal nodes, COFs exhibit superior thermal and chemical stability, particularly in aqueous or harsh environments where many MOFs are prone to degradation.¹⁰⁵ Porphyrin-based COFs leverage the extended π-conjugation and strong light-harvesting capabilities of porphyrins, enabling efficient visible-light-driven photocatalysis and improved charge separation.^106–109 Their highly tunable structures allow for precise design of pore size and functionality, offering enhanced selectivity toward specific pollutants in complex mixtures. Although MOFs often display higher crystallinity and synthetic versatility due to the diversity of metal–ligand combinations, COFs—especially porphyrin-functionalized ones—provide a promising metal-free alternative for long-term, stable, and efficient environmental remediation.^{112–114,118}

The application of porphyrin COFs for the degradation of organic pollutants was first demonstrated in 2019. In this pioneering study, Hou et al. synthesized a g-C₃N₄-based 2D/2D heterojunction photocatalyst using a composite of the Cu-porphyrin COF (CuPor-Ph-COF) and g-C₃N₄ for RhB degradation under photocatalytic conditions at λ ≥ 420 nm.¹⁰⁸ The 2D COF/g-C₃N₄ heterojunction showed improved photodegradation of RhB (up to 86%), higher than parent components, g-C₃N₄ and CuPor-Ph-COP with percentage degradation of 23 and 36%, respectively. The improved catalytic activity of the heterojunction hybrid was aided by synergistic interaction between the COF and g-C₃N₄, facilitating photo-induced electron transfer from the porphyrinoid COF to g-C₃N₄ producing free superoxide radicals.

In 2023, Karimi and co-workers developed a sulfur-functionalized porphyrin-based covalent organic framework (COF), termed PS@COF, as a novel metal-free dual-functional photocatalyst for the degradation of organophosphorus pesticides under visible-LED light.¹¹⁰ Synthesized via post-modification of COF-366 with elemental sulfur under solvent-free conditions, the resulting material combined porphyrin's strong visible-light absorption with sulfur's nucleophilic catalytic activity. PS@COF achieved excellent degradation efficiency (>97%) of diazinon and parathion within 60 minutes at pH 5.5, even at concentrations up to 50 mg L⁻¹. Kinetic analysis followed a pseudo-second-order model, and mechanistic insights from GC–MS and TOC analysis revealed effective detoxification pathways. Importantly, PS@COF maintained its structural integrity and catalytic performance over six reuse cycles. This study presents a sustainable, metal-free strategy for pesticide degradation, leveraging visible-light energy and offering promising applications in water purification (Fig. 9).

Fig. 9 The suggested mechanism for the photocatalytic degradation process over PS@COF; and related photocatalytic equations. Reprinted with permission.¹¹⁰ (Copyright (2023) of Elsevier).

In 2023, Wu et al. reported the design and synthesis of a dual-functional porphyrin-based covalent organic framework (Por-PD-COF) with excellent selective adsorption and photocatalytic properties.¹¹⁹ Constructed through a condensation reaction between meso-tetrakis(p-carboxyphenyl)porphyrin (TCPP) and para-phenylenediamine (PD), the 2D COF featured amide linkages, high surface area, abundant active sites, and narrow bandgap (1.02 eV). Por-PD-COF demonstrated selective and high-capacity adsorption of methylene blue (MB) over other dyes like rhodamine B (RhB) and methyl orange (MO), attributed to its unique pore size and charge selectivity. Notably, in competitive systems, MB could replace pre-adsorbed MO, highlighting its superior affinity. Beyond adsorption, Por-PD-COF also showed excellent photocatalytic degradation of MB under visible light (99% removal in 180 minutes) and retained performance after four reuse cycles. This work presents Por-PD-COF as a promising, reusable material for targeted organic dye removal and environmental purification (Fig. 10).

Fig. 10 (a) Synthesis of Por-PD-COF by the condensation reaction between TCPP and PD; (b) dual functions of Por-PD-COF including MB selective absorption in the mixtures, and photocatalytic activity under visible light irradiation. Reprinted with permission.¹¹⁹ (Copyright (2023) of Elsevier).

Porphyrin-based hydrogen-bonded organic frameworks

Compared to covalent organic frameworks (COFs) and metal–organic frameworks (MOFs), hydrogen-bonded organic frameworks (HOFs) represent a newer and distinct class of porous crystalline materials that rely on reversible hydrogen bonding rather than covalent or coordination bonds for the framework assembly.^122–124 While HOFs typically offer lower thermal and chemical stability than COFs and MOFs due to the weaker nature of hydrogen bonds, they benefit from easier synthesis, solution processability, and recyclability. In environmental remediation, HOFs have shown promising potential in adsorbing pollutants and photocatalytic applications, owing to their tunable porosity, large surface areas, and modular design.¹²⁵ Their non-metallic and often biocompatible nature makes them attractive for green chemistry applications. However, HOFs still lag COFs and MOFs in terms of structural robustness and long-term durability, especially in aqueous or acidic environments. As research into HOFs continues to grow, integrating photoactive units such as porphyrins could enhance their functionality, bringing them closer to the performance of porphyrin-based COFs, which currently outperform HOFs in light-driven pollutant degradation due to their superior charge transport and visible-light absorption properties.^126–128 One such advancement is the work by He and colleagues, who developed TCPP-based HOFs using a “counterstrategy” that blocked strong hydrogen-bond donors with DMF, enabling tunable framework rigidity and enhanced photocatalytic performance for the degradation of 9,10-diphenylanthracene in 2019.¹¹⁵ This work demonstrates the structural dynamics and functional versatility of HOFs—particularly how weak van der Waals interactions, once thought to hinder framework stability, can be harnessed for porosity and catalytic efficiency. Compared to porphyrin-based MOFs and COFs, these HOFs offer easier synthesis, metal-free biocompatibility, and better recyclability, positioning them as attractive candidates for environmentally friendly photocatalytic applications (Fig. 11).

Fig. 11 Preparation conditions for the present three HOFs. Reprinted with permission.¹¹⁵ Copyright (2019) of the American Chemical Society.

Zhao and coworkers reported the development of a novel photocatalyst, PFC-72/TiO₂, combining porphyrinic hydrogen-bonded organic frameworks (porph-HOFs) with TiO₂ nanoparticles for efficient degradation of sulfadiazine (SDZ), a persistent antibiotic pollutant in wastewater. By integrating cobalt-based porphyrin ligands (TCPP-Co) with TiO₂ through 4-mercaptopyridine (4-PySH) as a bridging molecule, the resulting heterojunction exhibits enhanced visible-light absorption, improved charge separation, and high photocatalytic activity.¹¹⁶ The high surface area of PFC-72 facilitates better dispersion of TiO₂ and provides more active sites for SDZ adsorption and degradation. Density functional theory (DFT) analysis and characterization confirmed the system's improved light-harvesting and electron transfer properties. The optimized composite achieved a 93.73% SDZ removal rate within 120 minutes and retained high stability and reusability over multiple cycles, demonstrating its promise as a sustainable, high-performance material for environmental remediation (Fig. 12).

Fig. 12 Possible photocatalytic mechanism for PFC-72/TiO₂ (up). Possible degradation pathways of SDZ (below). Reprinted with permission.¹¹⁶ (Copyright (2025) of Elsevier).

Porphyrin-based porous organic polymers (POPs)

Porous organic polymers (POPs) are a distinct class of amorphous, covalently bonded porous materials known for their exceptional thermal and chemical stability.^129–131 Unlike metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), POPs are typically non-crystalline but benefit from high structural tunability, large surface areas, and the ability to incorporate a wide range of functional groups. Their all-organic composition and strong covalent linkages give them superior resistance to harsh environments, making them suitable for a variety of applications including gas storage, separation, catalysis, and environmental remediation.^114–117 POPs can be synthesized through diverse polymerization strategies, allowing for precise control over pore size and surface chemistry. Moreover, their modular design enables the integration of photoactive, redox-active, or catalytic units, expanding their potential in light-driven processes and green chemistry. While lacking long-range order, the durability and versatility of POPs position them as a valuable platform for developing advanced functional materials.^132–135

POPs have also shown promise in photocatalytic degradation of organic pollutants. A pioneering study by Xiao and co-workers reported the synthesis of an iron(III) porphyrin-based conjugated microporous polymer (UPC-CMP-1) via Sonogashira–Hagihara coupling between Fe(III) 5,10,15,20-tetrakis(4′-bromophenyl)porphine and 1,4-diethynylbenzene. This material exhibited a dendrite-like nanostructure and remarkable photocatalytic activity, achieving 88.3% degradation of Congo Red under visible light irradiation within only 120 seconds.¹¹¹ Moreover, UPC-CMP-1 demonstrated high selectivity toward Congo Red over other dyes, underscoring the advantages of porphyrin-based POPs in targeted pollutant degradation. Compared with traditional semiconductor catalysts such as TiO₂ and ZnO, which suffer from weak photostability and agglomeration issues, UPC-CMP-1 offers superior stability and reusability due to its fully covalent framework. This seminal contribution established POPs as a viable platform for efficient, selective, and stable photocatalytic remediation of organic contaminants, paving the way for subsequent innovations in post-synthetic modification and donor–acceptor engineering of porphyrin-based POPs.

The study by Zhang et al. introduces a strategic post-synthetic modification to enhance the hydrophilicity and photocatalytic performance of a porphyrin–perylene-based conjugated polymer.¹²⁰ By incorporating quaternary ammonium groups into the COP backbone (yielding PDIN-PyN⁺), the resulting material achieved not only improved water dispersibility but also a stronger electrostatic affinity for anionic pollutants like bisphenol A (BPA) and 2,4-dichlorophenoxyacetic acid. As shown in Fig. 13, this structural modification significantly enhanced charge separation and visible light utilization, enabling rapid degradation of both pollutants with removal efficiencies exceeding 99% within 30 minutes under visible light. The integration of electron donor–acceptor motifs and ionic functionalities underscores a rational design approach for POP-based photocatalysts with high reactivity and practical applicability in water purification. This work highlights the growing potential of post-modified POPs in environmental remediation, particularly in tackling persistent organic pollutants under mild and sustainable conditions.

Fig. 13 Schematic illustration of a porphyrin-based photocatalytic system for reactive oxygen species (ROS) generation and organic pollutant degradation. Reprinted with permission.¹²⁰ (Copyright (2024) of Elsevier).

Building upon the growing research into porphyrin-based porous organic polymers (POPs), recent studies have demonstrated innovative structural modifications and composite designs that significantly enhance photocatalytic activity for pollutant degradation. In particular, the work by Yu et al. introduces a new class of porphyrin-based conjugated microporous polymers (Por-CMPs-1–2), synthesized via Sonogashira–Hagihara coupling, and further functionalized by incorporating nanoscale zerovalent iron (nZVI) to form Por-CMPs-1–2@nZVI composites.¹¹⁷ This approach leverages the redox properties of nZVI and the extended conjugation and high surface area of CMPs to synergistically boost photocatalytic performance under visible light irradiation. The composite exhibits narrowed band gaps (1.45 and 1.32 eV), enabling efficient activation under visible light and facilitating the generation of reactive oxygen species (ROS), primarily superoxide anions and hydroxyl radicals, for effective degradation of organic dyes such as methylene blue (MB). Por-CMPs-2@nZVI achieved up to 98% degradation of 10 ppm MB in 150 minutes, outperforming its counterparts without nZVI. Moreover, this work addresses practical limitations of POP-based photocatalysts, such as recyclability and processability, by developing membrane materials (Por-CMPs@nZVI-m) through the immobilization of catalysts on copper nets. This not only enhances their reusability but also paves the way for industrial-scale applications. Collectively, the integration of porphyrinic light-harvesting units with redox-active metal nanoparticles into a robust CMP framework marks a significant step forward in designing multifunctional POP-based photocatalysts for environmental remediation (Fig. 14).

Fig. 14 Schematic diagram illustrating the mechanism of photocatalytic degradation of MB using Por-CMPs-2@nZVI (top). Synthesis route of Por-CMPs-1–2@nZVI and Por-CMPs-1@nZVI-membranes (below). Reprinted with permission.¹¹⁷ (Copyright (2024) of the American Chemical Society).

Xu et al. (2024) reported a significant advancement in the development of donor–acceptor (D–A) type conjugated porous polymers (CPPs) by synthesizing a three-dimensional CuPT-CPP using copper porphyrin (CuTAPP) as the donor and triazine (TFPT) as the acceptor.¹²¹ As shown in Fig. 15, this rational design integrates the strong visible-light absorption and catalytic capabilities of porphyrins with the electron-withdrawing nature of triazine, resulting in a material with enhanced intramolecular charge separation, broad light absorption (400–800 nm), and improved photocatalytic efficiency. The 3D architecture ensures high surface accessibility and spatial separation of active sites, promoting faster mass transfer and reducing charge recombination. CuPT-CPP exhibits outstanding visible-light-driven photodegradation performance against a range of organic pollutants, including rhodamine B, methylene blue, methyl orange, and tetracycline hydrochloride, achieving near-complete degradation in short timeframes. Its excellent chemical stability and reusability further highlight its potential for practical environmental remediation applications. Compared to other polymer-based photocatalysts, CuPT-CPP stands out due to its synergistic D–A framework and organometallic functionality, offering valuable insights for the future design of efficient, metal–organic photocatalysts for wastewater treatment.

Fig. 15 Schematic illustration of the photocatalytic mechanism of a porphyrin-based donor–acceptor porous polymer under visible light for the degradation of organic pollutants (RhB, MB, MO, and TC). Reprinted with permission.¹²¹ (Copyright (2024) of Elsevier).

Very recently, Fan et al. presented a facile and cost-effective approach for synthesizing porphyrin-based CMPs via Suzuki coupling, integrating electron donor–acceptor architectures by combining porphyrin and benzothiadiazole moieties.¹⁰⁰ This strategic molecular design enhances charge separation and light absorption, which are critical for efficient photocatalysis. Furthermore, through post-synthetic modifications such as quaternization, the authors successfully tailored the CMPs’ surface properties to improve their interaction with organic pollutants. The resulting materials, Por-BT-1 and Por-BT-2, exhibited excellent photocatalytic performance under visible light, achieving up to 98% removal efficiency of contaminants like tetracycline and bisphenol A within remarkably short irradiation times (Fig. 16). Notably, the study thoroughly investigated the influence of environmental parameters including pH, catalyst dosage, the presence of inorganic anions, and different water matrices, demonstrating the robustness and versatility of these CMPs in practical water treatment settings. This work not only highlights a scalable and efficient synthetic route but also underscores the potential of porphyrin-based CMPs as highly effective photocatalysts for the degradation of emerging organic contaminants, addressing an urgent need in environmental remediation.

Fig. 16 Porphyrin-based photocatalysts degrade tetracycline (TC) and bisphenol A (BPA) into CO₂ and H₂O by generating reactive oxygen species (¹O₂, ˙O₂⁻) under light irradiation. Reprinted with permission.¹⁰⁰ (Copyright (2025) of The Royal Society of Chemistry).

Discussion, conclusions and outlook

Porous porphyrin-based photocatalysts have emerged as a highly promising class of materials for the remediation of organic pollutants, offering unique advantages rooted in their intrinsic photophysical properties and engineered porous architectures. The integration of porphyrin units into metal–organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and porous organic polymers (POPs) has successfully addressed critical limitations such as low surface area and inefficient pollutant adsorption, thereby significantly enhancing photocatalytic performance under visible light irradiation. These systems facilitate improved light harvesting, accelerated charge separation, and enhanced generation of reactive oxygen species (ROS), leading to effective degradation of a wide range of emerging contaminants including pharmaceuticals, pesticides, dyes, and industrial chemicals.

The photocatalytic efficiency of porous porphyrin-based frameworks is governed by a delicate interplay between molecular-level porphyrin chemistry and framework-level design. At the molecular scale, metalation of the porphyrin core strongly influences light absorption and electron transfer, with Fe, Co, and Cu centers often enhancing redox activity and ROS generation relative to metal-free porphyrins. Substituent effects on the porphyrin ring further tune electronic properties, enabling selective activation pathways. At the framework level, pore size distribution and crystallinity dictate charge carrier mobility and pollutant accessibility; highly ordered COFs typically provide efficient charge transport, whereas flexible HOFs facilitate dynamic host–guest interactions. Incorporation of donor–acceptor motifs or ionic functional groups can improve charge separation, extend visible-light utilization, and enhance affinity toward specific pollutants, as exemplified in PDIN-PyN⁺ POPs for BPA degradation. Comparative studies reveal that MOFs excel in tunability of catalytic sites, COFs in directional charge transport, POPs in robustness and functional group diversity, and HOFs in mild synthesis and adaptability. These correlations underscore that deliberate molecular engineering combined with tailored framework design is essential for achieving high-performance photocatalysts.

This review has systematically summarized recent advances in the synthesis strategies and structural functionalization of porous porphyrin-based materials, underscoring their tunable porosity, chemical versatility, and the role of metal centers in modulating catalytic activity. Comprehensive discussions of photocatalytic mechanisms and performance evaluation metrics reveal that while substantial progress has been made, challenges such as photostability, catalyst recyclability, and operational robustness in complex aqueous environments persist. Moreover, discrepancies between laboratory-scale efficiencies and real-world applicability highlight the need for continued investigation into the influence of environmental variables such as pH, co-existing ions, and organic matter.

Looking forward, several critical research directions must be prioritized to propel porous porphyrin-based photocatalysts from conceptual frameworks to viable environmental technologies. Firstly, scalable and cost-effective synthetic routes that retain structural integrity and catalytic functionality are imperative for practical deployment. Advanced synthetic methodologies, including controlled post-synthetic modifications and hierarchical structure engineering, may enable fine-tuning of porosity and electronic properties to optimize photocatalytic activity. Secondly, mechanistic studies leveraging state-of-the-art spectroscopic and computational tools are essential to elucidate the complex charge transfer processes and ROS generation pathways at molecular and nanoscale levels. This knowledge will inform rational design principles for next-generation materials with enhanced quantum efficiencies.

Finally, rigorous assessment of environmental compatibility, toxicity, and recyclability must accompany the advancement of these materials to ensure sustainable application. Pilot-scale studies and field trials will be critical to validate performance under diverse and dynamic environmental conditions. The integration of porous porphyrin-based photocatalysts into existing water treatment infrastructure could offer transformative improvements in pollutant degradation efficiency and operational sustainability.

In conclusion, porous porphyrin-based photocatalysts represent a frontier in the development of sustainable, efficient, and versatile materials for environmental remediation. By bridging fundamental materials chemistry with applied environmental science, future research can unlock their full potential to mitigate pollution and safeguard ecological and human health on a global scale.

Conflicts of interest

There are no conflicts to declare.

Abbreviations

BET	Brunauer–Emmett–Teller (surface area analysis)
BPA	Bisphenol A
COF	Covalent organic framework
CMP	Conjugated microporous polymer
CPP	Conjugated porous polymer
CuPT-CPP	Copper porphyrin–triazine conjugated porous polymer
CuTCPP	Coppermeso-tetra(4-carboxyphenyl)porphyrin
CR	Congo red
D–A	Donor–acceptor
DAT	Diaminotriazine
DAT-porphyrin	5,10,15,20-tetra(4-(2,4-diaminotriazine)phenyl)porphyrin
DMPO	5,5-Dimethyl-1-pyrroline N-oxide
DFT	Density functional theory
EPR	Electron paramagnetic resonance
H6TZPP	5,10,15,20-Tetrakis[4-(2,3,4,5-tetrazolylphenyl)]porphyrin
HOF	Hydrogen-bonded organic framework
HR-TEM	High-resolution transmission electron microscopy
HSE	Heyd–Scuseria–Ernzerhof (hybrid functional used in DFT)
ISC	Intersystem crossing
k_obs	Observed Pseudo-first-order rate constant
LED	Light emitting diode
LMCT	Ligand-to-metal charge transfer
MB	Methylene blue
MO	Methyl orange
MOF	Metal–organic framework
nZVI	Nanoscale zerovalent iron
NIR	Near-infrared radiation
OPs	Organophosphorus pesticides
P-COF	Porphyrin-based covalent organic framework
P-CMP	Porphyrin-based conjugated microporous polymer
P-HOF	Porphyrin-based hydrogen-bonded organic framework
P-MOF	Porphyrin-based metal–organic framework
PD	para-Phenylenediamine
PDIN-PyN^+	Quaternized porphyrin–perylene POP
PFC-72	Porphyrin framework composite
POP	Porous organic polymer
Por-BT-1/2	Porphyrin-benzothiadiazole CMPs
Por-CMP	Porphyrin-based CMP
Por-CMPs@nZVI	Porphyrin CMPs with nanoscale zerovalent iron
Por-CMPs@nZVI-m	Membrane composite of porphyrin CMPs@nZVI
PS-mod	Post-synthetic modification
QY	Quantum yield
RND	Ranitidine
RhB	Rhodamine B
ROS	Reactive oxygen species
SDZ	Sulfadiazine
SIM	Simulated irradiation matrix
TCPP	meso-Tetrakis(4-carboxyphenyl)porphyrin
TC/TCH	Tetracycline/tetracycline hydrochloride
TEMP	2,2,6,6-Tetramethylpiperidine
TFPT	2,4,6-Tris(4-formylphenyl)-1,3,5-triazine
TGA	Thermogravimetric analysis
TOC	Total organic carbon
T 90	Time to reach 90% pollutant degradation
UHPLC-MS	Ultra high-performance liquid chromatography–mass spectrometry
UPC-H4a	Hydrogen-bonded porphyrin framework from DAT
VLP	Visible light photocatalysis
Xe lamp	Xenon Arc lamp (simulated solar light source)
^1O2	Singlet oxygen
˙OH	Hydroxyl radical
˙O2^−	Superoxide radical
h^+	Photogenerated hole
2,4-D	2,4-Dichlorophenoxyacetic acid

Data availability

The data that support the findings of this study are available from the corresponding author Ting Han, upon reasonable request.

Acknowledgements

This work was supported by the Welch Foundation (m-0200) and the start-up fund of T. Han provided by Texas Woman's University (TWU), the School of Sciences Project ACCESS grant and supported by the Texas Woman's University Small Grant Program.

Notes and references

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