Electronic Band Research Articles

Constructing Metal-Organic Framework Films with Adjustable Electronic Properties on Hematite Photoanode for Boosting Photogenerated Carrier Transport.

Hematite (α-Fe2O3) has become a research hotspot in the field of photoelectrochemical water splitting (PEC-WS), but the low photogenerated carrier separation efficiency limits further application. The electronic structure regulation, such as element doping and organic functional groups with different electrical properties, is applied to alleviate the problems of poor electrical conductivity, interface defects, and band mismatch. Herein, α-Fe2O3 photoanodes are modified to regulate their electric structures and improve photogenerated carrier transport by the bimetallic metal-organic frameworks (MOFs), which are constructed with Fe/Ni and terephthalate (BDC) with 2-substitution of different organic functional groups (─H, ─Br, ─NO2 and ─NH2). The α-Fe2O3 photoanode loaded with FeNi-NH2BDC MOF catalyst exhibits the optimal photocurrent density (2mAcm-2) at 1.23VRHE, which is 2.33 times that of the pure α-Fe2O3 photoanode. The detailed PEC analyses demonstrate that the bimetallic synergistic effect between Fe and Ni can improve the conductivity and inhibit the photogenerated carrier recombination of α-Fe2O3 photoanodes. The ─NH2 group as an electron-donor group can effectively regulate the electron distribution and band structure of α-Fe2O3 photoanodes to prolong the lifetime of photogenerated holes, which facilitates photogenerated carrier transport and further enhances the PEC-WS performance of α-Fe2O3 photoanode.

Modulation of magnetic properties of trilayer MoS2/ZnO/VS2 van der Waals heterostructure via strain engineering for spintronics application

MoS2/ZnO/VS2 trilayer van der Waals (vdW) heterostructure is reported for its electronic and magnetic properties for the first time. Heyd-Scuseria-Ernzerhof (HSE) hybrid functional is used to compute the electronic band structure and it is observed that the heterojunction exhibits an indirect transition. The trilayer showed type II band alignment. This along with the Charge Density Difference (CDD) isosurface and plot showed the charge transfer in both the spin channels from ZnO to both MoS2 and VS2 monolayer. Monte Carlo (MC) simulation revealed a low Curie temperature (TC) value of 65 K. Effect of compressive and tensile biaxial strain on the trilayer was studied where all the strained system turned metallic. Under both biaxial tensile and compressive strain, the TC at first increased and then gradually decreased which hints at tuning the TC with strain engineering. Thus, the metallic strained MoS2/ZnO/VS2 trilayer has potential application in the spintronics devices.

Computational study of the structural, mechanical, electronic, optical and thermal properties of BaLiX (X =P, As, Sb) perovskites

This study explores the structural, optical, mechanical, electronic, and thermal characteristics of ionic semiconductor compounds BaLiX (X = P, As, Sb) using Density Functional Theory (DFT). A comprehensive analysis of BaLiX (X = P, As, Sb) is conducted, proving that the estimated and observed lattice parameters coincide well and confirming mechanical stability through elastic stiffness constants. Electronic band structures reveal direct bandgap semiconductor properties with values of 0.70 eV, 0.30 eV, and 0.95 eV for BaLiP, BaLiAs, and BaLiSb, respectively, suggesting specific applications such as mid-infrared photodetectors, terahertz devices, and near-infrared sensors. Optical property analyses, including energy loss function, reflectivity, refractive index, and absorption coefficient, highlight the potential of these materials for optoelectronic and photovoltaic applications. Despite elastic anisotropy, optical anisotropy remains minimal. The materials exhibit potential for use as thermal barrier coatings (TBC) due to their comparatively lower Debye temperature (D), minimum thermal conductivity (Kmin) and lattice thermal conductivity (kph). Moreover, heat capacity calculations and thermal coefficient of expansion are also calculated.

Lifshitz Transition in a Single-Atom-Thick GdxYb1-xPb3 Kagome Compound on Si(111).

Lanthanide (Ln) elements Gd and Yb alloyed with a Pb monolayer on the Si(111) substrate form LnPb3 compounds having the same crystal structure. They comprise a single-atom-thick Pb layer arranged in a slightly distorted kagome lattice with Ln atoms filling the hexagonal voids. They have similar electronic band structures except for the Fermi level position, which varies between the divalent Yb- and trivalent Gd-containing compounds by ∼0.47 eV. The ability to create a 2D solid solution with the unified continuous Pb layer and hexagonal voids randomly filled with either Gd or Yb atoms allows precise control of the Fermi level position. Small alteration of the Fermi level triggers drastic changes in the Fermi surface topology due to the Lifshitz transition, hence in the physical properties. In particular, the sheet resistance of the GdxYb1-xPb3/Si(111) system can be controllably varied over an order of magnitude range.

Crystal structure and microwave dielectric properties of BaZn(1-x)CoxP2O7 ceramics

BaZn(1-x)CoxP2O7 (0 ≤x≤ 0.125) ceramics were synthesized using the solid-state reaction method, with sintering temperatures ranging from 875 °C to 975 °C. The study systematically investigated the phase composition, crystal structure, and microstructure of the ceramics, and correlated these characteristics with their dielectric properties. Additionally, density functional theory (DFT) was employed to examine the energy band structure, electron density, and density of states of the materials. The dielectric constant εr values were primarily influenced by polarizability, while the Q × f values of BaZn(1-x)CoxP2O7 ceramics were predominantly affected by the packing fraction and full width at half maximum (FWHM). The temperature coefficient of resonant frequency was influenced by a decrease in bond valence and an increase in PO4 tetrahedral distortion. Notably, the BaZn0.975Co0.025P2O7 ceramic demonstrated promising microwave dielectric properties, with εr = 8.15, Q × f = 42,431 GHz, and τf = −27.5 ppm/°C, when sintered at 950 °C for 4 h.

Spin-orbit coupling effects in single-layer phosphorene

The electronic band structure of monolayer phosphorene is thoroughly studied by considering the presence of spin-orbit interaction. We employ a multiorbital Slater-Koster tight-binding approach to derive effective k·p-type Hamiltonians that describes the dominant spin-orbit coupling (SOC) effects of the Rashba and intrinsic origin at the high Γ and S high symmetry points in phosphorene. In the absence of SOC effects a minimal admixture of pz and py atomic orbitals suffices to reproduce the well-known anisotropy of highest valence and the lowest conduction bands at the Γ point, consistent with density functional theory (DFT) and k·p methods. In contrast, the inclusion of the px and s atomic orbitals are rather crucial for an adequate description of the SOC effects in phosphorene at low energies, particularly at the S point. We introduce useful analytical expressions for the Rashba and intrinsic SOC parameters in terms of the relevant Slater-Koster integrals. In addition, we report simple formulas for the interband dipole strengths, revealing the nature of the strong anisotropic behavior of its lower bands. Our findings can be useful for further studies of electronic and spin transport properties in monolayer phosphorene and its nanoribbons. Published by the American Physical Society 2024

Revealing Roles of High-Electronegativity Fluorine Atoms in Boosting Redox Potential of Layered Sodium Cathodes.

The development of high-energy-density cathode materials is regarded as the ultimate goal of alkali metal-ion batteries energy storage. However, the strategy of regulating specific capacity is limited by the theoretical capacity, and meanwhile focusing on improving capacity will lead to structural destructions. Herein, a novel perspective is proposed that tuning the electronic band structure by introducing highly electronegative fluoride atoms in NaxTMO2-yFy (0 < x < 1, 0 < y < 2) model compounds to improve redox potential for developing high-energy-density layered oxides. Highly electronegative fluoride atoms is introduced into P2-type Na0.67Fe0.5Mn0.5O2 (NFM), and the thus fluoride NFM (F-NFM) cathode achieved high redox potential (3.0V) and high energy density (446Whkg-1). Proved by structural characterizations, fluorine atoms are successfully incorporated into oxygen sites in NFM lattice. Ultraviolet photoelectron spectroscopy is applied to quantitatively analyze the improved redox potential of F-NFM, which is achieved by the decreased valence band energy in electronic band structure due to the strongly electrophilic fluoride ions. Moreover, fluoride atoms can stabilize the local environment of NFM and improve its redox potential. The work provides a perspective to improve redox potential by tuning the electronic band structure in layered oxides and developing high-energy-density alkali metal-ion batteries.

Possible gapless helical edge states in hydrogenated graphene

Electronic band structures in hydrogenated graphene are theoretically investigated by means of first-principle calculations and an effective tight-binding model. It is shown that regularly designed hydrogenation to graphene gives rise to a large band gap about 1 eV. Remarkably, by changing the spatial pattern of the hydrogenation, topologically distinct states can be realized, where the topological nontriviality is detected by C2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$C_2$$\\end{document} parity indices in bulk and confirmed by the existence of gapless edge/interface states as protected by the mirror and sublattice symmetries. The analysis of the wave functions reveals that the helical edge states in hydrogenated graphene with the appropriate design carry pseudospin currents that are reminiscent of the quantum spin Hall effect. Our work shows the potential of hydrogenated graphene in pseudospin-based device applications.

Effect of precursors on the structure and photocatalytic performance of g-C3N4 for NO oxidation and CO2 reduction

Graphitic carbon nitride (g-C3N4, CN) is recognized as the most extensively studied organic polymeric photocatalyst for pollution control and energy conversion due to its facile synthesis and suitable electronic band structure. The aim of the present work is to explore the effect of precursors, such as urea (U, (NH2)2CO), dicyandiamide (D, C2H4N4) and melamine (M, C3H6N6), on the structure and photocatalytic activity of the obtained CN samples, denoted as UCN, DCN and MCN, respectively. The sheet-like UCN sample shows significantly enhanced photoreactivity in both NO oxidation and CO2 reduction compared to the bulk DCN and MCN materials. In addition, UCN demonstrates the ability to suppress the formation of toxic NO2 intermediate during the photocatalytic oxidation of NO. The improved photocatalytic activity of UCN can be attributed to a dual effect: first, its increased specific surface area provides more active sites for the photocatalytic reaction; second, it exhibits a stronger affinity for substrates like NO and CO2, which facilitates charge migration at the interface.

Computational Prediction of Structural, Optoelectronic, Thermodynamic, and Thermoelectric Response of the Cubic Perovskite RbTmCl3 via DFT‐mBJ + SOC Studies

Perovskite halides, owing to their environmental stability, non‐toxicity, and remarkable efficiency, are emerging as potential candidates for photovoltaic, solar cell, and thermodynamic applications. The electronic, optical, thermoelectric, and thermodynamic properties of cubic perovskite RbTmCl3 are studied using density functional theory (DFT). The electronic, optical, and thermoelectric properties are calculated both with and without spin‐orbit coupling (SOC) using the Tran and Blaha functional in the structure of the modified Becke Johnson (mBJ) exchange potential, while structural and mechanical properties are assessed using the exchange‐correlation functional calculated using the Perdew Burke Ernzerhof Generalized Gradient Approximation (PBE‐GGA). The negative formation energy (−592.39 KJ mol−1) and tolerance factor (1.17) for structural stability and current their existences in the cubic phase are found. Evaluation of the obtained data with and without SOC shows that the SOC effect causes the Tm‐d states to be shifted toward the level of Fermi, thereby decreasing the energy band gaps from 1.42 to 1.32 eV. Nevertheless, only the shift of the third variable peak to lower energies indicates the impact of SOC on optical properties. The effectiveness of RbTmCl3 in optical devices operating in the visible and ultraviolet regions is demonstrated by the exceptional absorption of light in these ranges. Using TB‐mBJ + SOC functional, the electronic band structure research reveals a direct semiconducting band gap of 1.32 eV in comparison to earlier calculations like LDA, PBE‐GGA, and TB‐mBJ. The absorption spectrum, reflectivity, extinction coefficient, refractive index, and dielectric function are displayed in addition to the electrical properties. Additionally, the quasi‐harmonic Debye model, which accounts for lattice vibrations, was used to study the corresponding volume, heat capacity, expansion of the heat coefficient, and Debye temperature of the RbTmCl3 crystal. We have calculated the thermoelectric parameters such as the Seebeck coefficient, thermal conductivity, electrical conductivity, and power factor as a function of temperature (100–900 K).

The A-Ni chemical bond in AIIINiSb (AIII=Sc, Y, Er) half-Heusler materials triggers the formation of anomalous vacancy defects

Defects exert a profound influence on thermoelectric materials by altering electronic band structures and significantly impacting their performance. Despite being a potentially promising thermoelectric material, the mechanism behind defect formation in half-Heusler (HH) compounds ABX remains unclear, impeding the enhancement of their thermoelectric properties. In this study, we investigated the intrinsic defect formation energies for AⅢNiSb (AⅢ = Sc, Y, Er) and other 9 HH compounds, namely AⅣNiSn (AⅣ = Ti, Zr, Hf), AⅤFeSb (AⅤ = V, Nb, Ta), and AⅣCoSb (AⅣ = Ti, Zr, Hf), using first-principles calculations and thermodynamics. The results reveal that AⅢNiSb (AⅢ = Sc, Y, Er) exhibits anomalous B (Ni) vacancy defects, with their formation energies being significantly lower than those of the corresponding B vacancy defects in the other 9 HH compounds. This anomaly can be attributed to the strength of the A-B bonds, where a decrease in bond strength leads to a decrease in the formation energy of B vacancies. This approach of exploring the influence of interatomic bond strength on defect formation is not only insightful for HH compounds but also holds potential applications in defect studies across various materials, offering a broader perspective on the fundamental mechanisms governing defect formation and stability.

Temperature dependent electrical resistance and mesoscopic electronic transport mechanisms on aerographite and single-walled carbon nanotube aerogel

We investigate temperature dependent electrical resistance properties of aerographite and single-walled carbon nanotube (SWCNT) aerogel in the temperature range of 2–300 K by employing the four-probe method with magnetic field effects (in the range 0–9 T, in steps of 2 T). The current–voltage (I–V) curves were taken for several temperatures varying from 5 to 300 K, and the electrical resistance values of aerographite and SWCNT aerogel were decreased from 7.30 Ω (5 K, 0 T) to 4.88 Ω (300 K, 0 T) and 22.56 Ω (5 K, 0 T) to 0.99 Ω (300 K, 0 T) with temperature increases, respectively. Experimental results show that the electrical resistance falls exponentially as the temperature increases. Such temperature dependence of R(T) points to a form of tunneling conduction or hopping. Two mesoscopic mechanisms for electronic transport, fluctuation-induced tunneling conduction (FITC) and variable range hopping (VRH), are employed to explicate possible electrical conduction mechanisms occurring in aerographite and SWCNT aerogel, respectively. These mainly result in disorder-induced symmetry-breaking, which are modified by their structural symmetries and electronic band structures, both play important roles in temperature dependent electrical resistance properties of aerographite and SWCNT aerogel. Characteristic parameters (T0, T1, and R0) have been estimated using the morphology and the uncertainty principle for aerographite and the percolation theory for SWCNT aerogel. While the FITC mechanism captures a wide temperature range of data for aerographite, the VRH model provides an explanation for SWCNT aerogel. This study provides groundwork for further development of carbon aerogel systems with high conductivity in large-scale preparation.

Tuning of Band Gap of Cathode Li2NiPO4F by Replacing P to Nb and Forming Li2NiNbO4F for Application as 5 V Cathode in Lithium Ion Battery: A Density Functional Theory Study

Electrochemical properties of Li2NiPO4F were studied using density functional theory. The obtained voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density are achieved as 5.33 V, 4.0 eV, 287.3 mAh g−1 and 1531.31 Wh kg−1, respectively. Although, the electrochemical properties of Li2NiPO4F are promising, large electronic band gap would certainly pose a limitation for its commercial application. Nb is a transition metal and its electronegativity is 1.6 which is less than the electronegativity of 2.19 for P. This implies, less operating voltage would be obtained if we replace P in Li2NiPO4F by Nb to form Li2NiNbO4F. However, electronic configuration of Nb is [Kr] 4d45 s1 and the valance state of Nb in Li2NiNbO4F is +5, which in turn specify that, localized Nb d states will reside in conduction band of Li2NiNbO4F and hence the electronic band-gap would be less owing to this localized Nb-d states. Our speculation gets verified by the calculated properties of Li2NiNbO4F obtained through DFT as follows; Voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density achieved, respectively, are 5.01 V, 3.64 eV (less than LiFePO4), 215.71 mAh g−1, 1080.71 Wh kg−1. Lower electronic band gap of Li2NiNbO4F makes it an alternative to Li2NiPO4F.

A first principles study of stability, electronic and thermoelectric characteristics of novel high temperature half- heusler alloys ScAgX (X=Si,Ge,Sn)

To meet the ever-increasing renewable energy demand Half- Heusler (HH) materials can be a potential candidate. Heusler materials are seeking popularity as efficient high-temperature thermoelectric materials. Here we systematically investigated the structural, electronic, mechanical and thermoelectric properties of novel HH compounds ScAgX (X = Si,Ge,Sn) in the framework of the first principles approach. These materials are found to be chemically, mechanically and dynamically stable. Born-Oppenheimer molecular dynamics simulations (BOMD) verify the thermal stability of these materials from 300 K to 1100 K. The semiconducting nature of these materials is confirmed by the electronic band structure. ScAgX (X = Si,Ge,Sn) have an indirect band gap of 0.37 eV, 0.42 eV and 0.38 eV respectively. A high value of Seebeck coefficient of 6351 μV/K, 6955 μV/K and 6558 μV/K has been obtained at room temperature. ScAgSi shows a high value of electrical conductivity (∼106 S/m) among these compounds at room temperature. The calculated value of the figure of merit (ZT) of ScAgX (X = Si,Ge,Sn) is 0.12, 0.08 and 0.16 at 1100 K respectively. Our present investigation shows that these materials can be a potential candidate for high-temperature thermoelectric power generation.

Investigating the effects of hydrostatic pressure on the physical properties of cubic Sr3BCl3 (B = As, Sb) for improved optoelectronic applications: A DFT study

This article explores changes in the structural, electronic, elastic, and optical properties of the novel cubic Sr3BCl3 (B = As, Sb) with increasing pressure. This research aims to decrease the electronic band gap of Sr3BCl3 (B = As, Sb) by applying pressure, with the objective of enhancing the optical properties and evaluating the potential of these compounds for use in optoelectronic applications. It has been revealed that both the lattice parameter and cell volume exhibit a declining pattern as pressure increases. At ambient pressure, analysis of the band structure revealed that both Sr3AsCl3 and Sr3SbCl3 are direct band gap semiconductors. With increasing pressure up to 25 GPa the electronic band gap of Sr3AsCl3 (Sr3SbCl3) reduces from 1.70 (1.72) eV to 0.35 (0.10) eV. However, applying hydrostatic pressure enables the attainment of optimal bandgaps for Sr3AsCl3 and Sr3SbCl3, offering theoretical backing for the adjustment of Sr3BCl3 (B = As, Sb) perovskite's bandgaps. The electron and hole effective masses in this perovskite exhibit a gradual decrease as pressure rises from 0 to 25 GPa, promoting the conductivity of both electrons and holes. The elastic properties are calculated using the Thermo-PW tool, revealing that they are anisotropic, ductile, mechanically stable, and resistant to plastic deformation. Importantly, these mechanical properties of both compounds are significantly enhanced under pressure. Optical properties, including the absorption and extinction coefficients, dielectric function, refractive index, reflectivity, and loss function, were calculated within the 0–20 eV range under different pressure conditions. The calculated optical properties highlight the versatility and suitability of Sr3AsCl3 and Sr3SbCl3 perovskites for pressure-tunable optoelectronic devices.

Electronic Band Offset in a Diamond|cBN|Diamond System for Modulation Doping

AbstractDiamond is a material with promising electronics applications but with challenges in effective doping. Cubic boron nitride (cBN), due to its similar lattice structure, is ideal for forming heterostructures with diamond, to modify electronic properties and especially shift the band positions. Here it is demonstrated how integrating cBN layers of finite thickness in diamond can induce an electronic band offset near the polarized diamond‐cBN interface. Beyond the direct density functional theory computations, an analytical model is developed for rapid examination of the band offset, for a broad number of crystallographic orientations, in excellent agreement with ab initio calculations. Results show that near [100] and [111] crystal directions, the diamond|cBN|diamond heterostructure displays a 3–4 eV band offset which is expected to facilitate effective modulation doping of diamond.

Superconductive Sodalite‐Like Clathrate Hydrides MXH12$\left(\text{MXH}\right)_{12}$ with Critical Temperatures of near 300 K under Pressures

Herein, a series of ternary hydride compounds crystallizing in the cubic structure as potential rare‐earth and alkaline‐earth superconductors are designed and investigated. First‐principles calculations are performed on these prospective superconductors across the pressure range of 50–200 GPa, revealing their electronic band structures, phonon dispersions, electron–phonon (e–) interactions, and superconducting properties. Several compounds are identified as dynamically stable, with ScYbH and LuYbH remaining stable at 70 GPa and at 100 GPa. Notably, Eliashberg theory and e– coupling calculations predict CaLuH to exhibit a remarkable of up to 294 K at 180 GPa. In these findings, ternary hydrides are unveiled as a promising class of high‐temperature superconductors and insights are provided for achieving superconductivity at lower or ambient pressures through material design and exploration.

Constructing Slip Stacking Diversity in Van der Waals Homobilayers.

The van der Waals (vdW) interface provides two important degrees of freedom-twist and slip-to tune interlayer structures and inspire unique physics. However, constructing diversified high-quality slip stackings (i.e., lattice orientations between layers are parallel with only interlayer sliding) is more challenging than twisted stackings due to angstrom-scale structural discrepancies between different slip stackings, sparsity of thermodynamically stable candidates and insufficient mechanism understanding. Here, using transition metal dichalcogenide (TMD) homobilayers as a model system, this work theoretically elucidates that vdW materials with low lattice symmetry and weak interlayer coupling allow the creation of multifarious thermodynamically advantageous slip stackings, and experimentally achieves13 and 9 slip stackings in 1T″-ReS2 and 1T″-ReSe2 bilayers via direct growth, which are systematically revealed by atomic-resolution scanning transmission electron microscopy (STEM), angle-resolved polarization Raman spectroscopy, and second harmonic generation (SHG) measurements. This work also develops modulation strategies to switch the stacking via grain boundaries (GBs) and to expand the slip stacking library from thermodynamic to kinetically favored structures via in situ thermal treatment. Finally, density functional theory (DFT) calculations suggest a prominent dependence of the pressure-induced electronic band structure transition on stacking configurations. These studies unveil a unique vdW epitaxy and offer a viable means for manipulating interlayer atomic registries.

Exploring Structural, Electronic, Vibrational, and Thermophysical Properties of Fe–Pt, Fe3–Pt, and Fe–Pt3 Alloys: A Density Functional Theory Study

Utilizing density functional theory, the structural, electronic, vibrational, and thermophysical properties of L10 FePt, L12 Fe3Pt, and L12 FePt3 alloys are meticulously analyzed. Employing projected augmented wave pseudopotentials alongside the Perdew–Burke–Ernzerhof exchange‐correlation function, equilibrium lattice constants are computed, aligning closely with existing data, thus validating our approach. To ascertain the dynamical stability of these alloys, phonon frequencies and density of states across high symmetry directions of the Brillouin zone are computed, affirming their stability with positive phonon frequencies throughout. Furthermore, the electronic band structure, the total and projected density of states, electronic charge density, and Fermi surfaces of the alloys are delved. The thorough analysis of phonon dispersion curves, electronic band structures, and the density of states, charge densities, and Fermi surfaces provides conclusive insights into the properties and behavior of the alloys. In essence, comprehensive investigation offers valuable insights into the thermophysical properties of L10 FePt, L12 Fe3Pt, and L12 FePt3 alloys, spanning equilibrium lattice constants, phonon characteristics, and electronic properties. These findings significantly augment the understanding of the structural stability, phonon dynamics, and electronic behavior exhibited by these alloys.

Macrocyclic porphyrin photocatalysts without metal chelation: A novel pathway for complete degradation of tough halophenols with longwave visible LED light source

Halophenols are toxic and persistent pollutants in water environments which poses harm to various organisms. Due to their high stability and long residence time, ultraviolet radiation, heavy metals and oxidizing agents have been largely adopted on treating these compounds. However, these treatment methods could pose toxicity or hazardous risks to the marine environment and plant operators. In this study, a water-soluble porphyrin photocatalyst was synthesized and introduced for halophenol treatment using UV-free LED white light. The porphyrin catalyst is a macrocyclic ring consisting of pyrroles linked with methine bridges, the highly conjugated ring provided the superior functionality of visible light absorption. Surprisingly, over 99 % degradation of halophenols and over 90 % dehalogenation have been achieved without metal chelation, even higher than those of transition metal porphyrins with inclusion of Fe3+, Zn2+, Cu2+, Co2+, Ni2+, and Mn2+. Ring-opening reactions were confirmed with the formation of carboxylic acids; dicarboxylic acids like acrylic acid, and malonic acid; while fumaric acid was the main product. Total organic carbon results indicated no CO2 produced during the reaction. Triplet absorbance and scavenger studies also indicated that singlet oxygen and conduction band electrons are the main radical species for halophenol degradation. The 100-fold singlet emission quenching over triplet absorption quenching indicated that the excited electrons tend to be transferred via singlet state. This concept brings along new approaches detoxifying halophenol-related wastewater without UV, metals and other additives, which is more environmentally-friendly and sheds light to the conversion of toxic materials into useful chemical precursors.