Nickel Tetraphenylporphyrin Research Articles

Homomolecular Triplet-Triplet Annihilation in Metalloporphyrin Photosensitizers.

Metalloporphyrins are ubiquitous in their applications as triplet photosensitizers, particularly for promoting sensitized photochemical upconversion processes. In this study, bimolecular excited state triplet-triplet quenching kinetics, termed homomolecular triplet-triplet annihilation (HTTA), exhibited by the traditional triplet photosensitizers-zinc(II) tetraphenylporphyrin (ZnTPP), palladium(II) octaethylporphyrin (PdOEP), platinum(II) octaethylporphyrin (PtOEP), and platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP)─were revealed using conventional transient absorption spectroscopy. Nickel(II) tetraphenylporphyrin was used as a control sample as it is known to be rapidly quenched intramolecularly through ligand-field state deactivation and, therefore, cannot result in triplet-triplet annihilation (TTA). The single wavelength transients associated with the metalloporphyrin triplet excited state decay─measured as a function of incident laser pulse energy in toluene─were well modeled using parallel first- and second-order kinetics, consistent with HTTA being operable. The combined transient kinetic data enabled the determination of the first-order rate constants (kT) for excited triplet decay in ZnTPP (4.0 × 103 s-1), PdOEP (3.6 × 103 s-1), PtOEP (1.2 × 104 s-1), and PtTPBP (2.1 × 104 s-1) as well as the second-order rate constant (kTT) for HTTA in ZnTPP (5.5 × 109 M-1 s-1), PdOEP (1.1 × 1010 M-1 s-1), PtOEP (7.1 × 109 M-1 s-1), and PtTPBP (1.6 × 1010 M-1 s-1). In most instances, triplet excited state extinction coefficients are either reported for the first time or have been revised using ultrafast transient absorption spectroscopy and singlet depletion: ZnTPP (78,000 M-1 cm-1) at 470 nm, PdOEP (67,000 M-1 cm-1) at 430 nm, PtOEP (51,000 M-1 cm-1) at 418 nm, and PtTPBP (100,000 M-1 cm-1) at 460 nm. The combined experimental results establish competitive time scales for homo- and heteromolecular TTA rate constants, implying the significance of considering HTTA processes in future research endeavors harnessing TTA photochemistry using common metalloporphyrin photosensitizers.

Adsorption of metal porphyrins using chitosan/zeolite-X composite as an efficient demetallization agent for crude oil: Isotherm, kinetic, and thermodynamic studies

Chitosan/zeolite-X (CHS/ZX) was synthesized to serve as an effective adsorbent for metal porphyrins through adsorption processes as an alternative to traditional separation methods from crude oil. The adsorption-desorption mechanisms of vanadyl and nickel tetraphenyl porphyrin (VO-TPP and Ni-TPP) were conducted on the model solution. Compared to individual components CHS and ZX, the CHS/ZX composite exhibited a doubled capacity for metal porphyrin removal. The synthesized composite was systematically characterized using FESEM, BET, XRD, FTIR, TGA, XPS, and CHN analyses. The study investigated the impact of many factors, including temperature, initial metal-porphyrin concentration, CHS/ZX dose, and contact time, on the adsorption efficiency of metal-porphyrin using CHS/ZX adsorbents. The adsorption processes of VO-TPP and Ni-TPP on CHS/ZX were effectively assessed through various equilibrium models, such as Langmuir, Freundlich, and Dubinin-Radushkevich (D-R). The pseudo-second-order model accurately depicted the adsorption processes of both VO-TPP and Ni-TPP. Determining the point of zero charge (pHPZC) highlighted the composite's surface charge distribution. Furthermore, considering the ΔG° and ΔH° values, the adsorption processes at different temperatures are exothermic, and VO-TPP exhibits a greater adsorption capacity than Ni-TPP under similar conditions. Notably, 73.7 % of VO-TPP and 83.8 % of Ni-TPP that were adsorbed were successfully recovered.

Tuning Transition Metal‐Containing Molecular Magnets by On‐Surface Polymerization

AbstractPorphyrins are promising multifunctional units particularly interesting for the realization of molecular nanodevices. Their structural variety allows to create precursors suitable for the on‐surface polymerization of porphyrin blocks. The corresponding increased stability and improved transport properties of the formed polymerized molecular nanostructures make them practically worthwhile. For the case of 2D porphyrin materials, the effect of polymerization on the magnetic properties of transition metal ions has not been reported yet. Therefore, details on the properties of an extended covalent nickel tetraphenylporphyrin network formed via Ullmann coupling on the Cu(111) surface are reported. By using photoelectron and absorption spectroscopies together with density functional theory calculations, it is systematically evolving how the functional properties of the Ni centers are changed within a polymerized molecular structure in comparison to single‐molecule nickel tetraphenylporphyrin derivatives that build the 2D molecular network. A model that explains the differences in the electronic and magnetic properties observed for the Ni centers in both structures based on the additional rigidity characteristic of the molecular layer after polymerization is drawn.

Computational study on the adsorption of small molecules to surface-supported Ni-porphyrins

With their flexible oxidation and spin states, surface-supported metalloporphyrins are attractive building blocks for tuneable, periodic spin interfaces. A technique to manipulate the spin in such systems is based on the adsorption of external gas ligands to the chelated metal center. In the search for promising interfaces, computational studies allow for a convenient scan through potential ligand candidates. In this contribution, we perform density functional theory calculations to investigate the coordination of six exemplary gases (CH4, H2O, NH3, CO, NO and NO2) to nickel tetraphenylporphyrin interfaces. Analyzing the formed complexes, we distinguish four major interaction mechanisms between metal center and ligand: non-interacting, weak field d-splitting, competing surface trans-effect and redox reaction. We find that a surface-mediated redox reaction between a strong π-acceptor (e.g.: NO2) and an unusually reduced metal (e.g.: Ni d9) has the strongest potential to induce spin changes at ambient conditions. Furthermore, we demonstrate how commonly chosen theoretical approximations may influence the interpretation of DFT calculations for metalloporphyrins and their complexes. By highlighting the limitations and possibilities of theoretical approaches, we hope to contribute to a better understanding and more selective harnessing of the special properties of surface-supported metalloporphyrins.

Extraction of Metalloporphyrins Using Subcritical Toluene-Assisted Thermally Stable Ionic Liquid

Due to the depleting production of conventional petroleum, heavy oil is turned to as an alternative. However, the presence of trace nickel and vanadium in heavy oil poses problems for the refining process in producing lighter-end products. Such problems are its tendency to poison the catalyst, accumulate during distillation, and corrode the equipment. The objective of this work is to remove the metal porphyrins from model oil using the thermally stable ionic liquid 1-butyl-3-methylimidazolium octylsulfate, [BMIM][OS] assisted by subcritical toluene (above boiling point, 110.6°C and below a critical point, 318.6°C at 41.264 bar) in a novel attempt. The experiments were conducted at 150ºC to 210ºC under a mixing time of 30 to 90 minutes while the pressure was monitored. Four metal porphyrins are used: nickel etioporphyrin, nickel tetraphenylporphyrin, vanadium oxide etioporphyrin, and vanadium oxide tetraphenylporphyrin. The results show that more than 40% of removal is achieved for all metal porphyrins, which shows great potential for further technological improvement. The Nuclear Magnetic Resonance (NMR) shows that the ionic liquid did not decompose at the process temperature, which proves great stability. The extraction of metal porphyrins follows the second-order extraction model with an R2 of more than 0.98.

Post-Growth Dynamics and Growth Modeling of Organic Semiconductor Thin Films.

The ability to control the properties of organic thin films is crucial for obtaining highly performant thin-film devices. However, thin films may experience post-growth processes, even when the most sophisticated and controlled growth techniques such as organic molecular beam epitaxy (OMBE) are used. Such processes can modify the film structure and morphology and, thus, the film properties ultimately affecting device performances. For this reason, probing the occurrence of post-growth evolution is essential. Equally importantly, the processes responsible for this evolution should be addressed in view of finding a strategy to control and, possibly, leverage them for driving film properties. Here, nickel-tetraphenylporphyrin (NiTPP) thin films grown by OMBE on highly oriented pyrolytic graphite (HOPG) are selected as an exemplary system exhibiting a remarkable post-growth morphology evolution consistent with Ostwald-like ripening. To quantitatively describe the growth, the height-height correlation function (HHCF) analysis of the atomic force microscopy (AFM) images is carried out, clarifying the role of the post-growth evolution as an integral part of the whole growth process. The set of scaling exponents obtained confirms that the growth is mainly driven by diffusion combined with the presence of step-edge barriers, in agreement with the observed ripening phenomenon. Finally, the results together with the overall approach adopted demonstrate the reliability of the HHCF analysis in systems displaying post-growth evolution.

Conservation of Nickel Ion Single‐Active Site Character in a Bottom‐Up Constructed π‐Conjugated Molecular Network

AbstractOn‐surface chemistry holds the potential for ultimate miniaturization of functional devices. Porphyrins are promising building‐blocks in exploring advanced nanoarchitecture concepts. More stable molecular materials of practical interest with improved charge transfer properties can be achieved by covalently interconnecting molecular units. On‐surface synthesis allows to construct extended covalent nanostructures at interfaces not conventionally available. Here, we address the synthesis and properties of covalent molecular network composed of interconnected constituents derived from halogenated nickel tetraphenylporphyrin on Au(111). We report that the π‐extended two‐dimensional material exhibits dispersive electronic features. Concomitantly, the functional Ni cores retain the same single‐active site character of their single‐molecule counterparts. This opens new pathways when exploiting the high robustness of transition metal cores provided by bottom‐up constructed covalent nanomeshes.

Conservation of Nickel Ion Single-Active Site Character in a Bottom-Up Constructed π-Conjugated Molecular Network.

On-surface chemistry holds the potential for ultimate miniaturization of functional devices. Porphyrins are promising building-blocks in exploring advanced nanoarchitecture concepts. More stable molecular materials of practical interest with improved charge transfer properties can be achieved by covalently interconnecting molecular units. On-surface synthesis allows to construct extended covalent nanostructures at interfaces not conventionally available. Here, we address the synthesis and properties of covalent molecular network composed of interconnected constituents derived from halogenated nickel tetraphenylporphyrin on Au(111). We report that the π-extended two-dimensional material exhibits dispersive electronic features. Concomitantly, the functional Ni cores retain the same single-active site character of their single-molecule counterparts. This opens new pathways when exploiting the high robustness of transition metal cores provided by bottom-up constructed covalent nanomeshes.

Chemical Structure and Distribution in Nickel-Nitrogen-Carbon Catalysts for CO2 Electroreduction Identified by Scanning Transmission X-ray Microscopy.

Atomically dispersed metal-nitrogen-carbon (M-N-C) materials are a class of electrocatalysts for fuel cell and electrochemical CO2 reduction (CO2R) applications. However, it is challenging to characterize the identity and concentration of catalytically active species owing to the structural heterogeneity of M-N-C materials. We utilize scanning transmission X-ray microscopy (STXM) as a correlative spectromicroscopy approach for spatially resolved imaging, identification, and quantification of structures and chemical species in mesoscale regions of nickel-nitrogen-carbon (Ni-N-C) catalysts, thereby elucidating the relationship between Ni content/speciation and CO2R activity/selectivity. STXM results are correlated with conventional characterization approaches relying on either bulk average (X-ray absorption spectroscopy) or spatially localized (scanning transmission electron microscopy with electron energy loss spectroscopy) measurements. This comparison illustrates the advantages of soft X-ray STXM to provide spatially resolved identification and quantification of active structures in Ni-N-C catalysts. The active site structures in these catalysts are identified to be atomically dispersed NiN x /C sites distributed throughout entire catalyst particles. The NiN x /C sites were notably demonstrated by spectroscopy to possess a variety of chemical structures with a spectroscopic signature that most closely resembles nickel(II) tetraphenylporphyrin molecules. The quantification and spatial distribution mapping of atomically dispersed Ni active sites achieved by STXM address a target that was elusive to the scientific community despite its importance in guiding advanced material designs.

Coverage-dependent study of nickel tetraphenyl-porphyrin on Au(332) and Au(788)

The coverage-dependent self-assembly of Nickel-tetraphenyl porphyins on Gold vicinal surfaces was studied by scanning tunneling microscopy. On Au(788) the molecular self-assembly is square-shaped, following the molecular symmetry. On Au(332) the molecules nucleate in a parallelogram lattice for monolayer coverage and in a squared lattice for multilayer coverage. Depending on the vicinal surface the molecules adopt either a saddle shaped or a more planar conformation. The experiments demonstrate that crystallographic direction, terrace sizes and coverage are important in establishing different assembly geometries.

Solubility and Activation of Hydrogen in the Non-Catalytic Upgrading of Venezuela Orinoco, China Liaohe, and China Fengcheng Atmospheric Residues

The solubility of hydrogen in the Venezuela Orinoco, China Liaohe, and China Fengcheng atmospheric residues under reaction conditions of 400 °C, 4 MPa for 20 min was analyzed by determining the composition and structure changes of the products. Activation of hydrogen during the upgrading process was also determined and discussed by the probe method. The results show that lighter components produced in the reaction can increase the hydrogen solubility as the reaction proceeds, and the lighter components present at the liquid level have positive effects on the transfer of hydrogen from the gas phase to the liquid phase. Naphthenic aromatic structures, sulphur and metals have a positive effect on hydrogen activation in the trend of naphthenic aromatic structures > sulphur > metals. Moreover, when sulphur is present, nickel tetraphenylporphyrin has a better effect on hydrogen activation than Vanadium tetraphenylporphyrin. During upgrading, the Venezuela Orinoco atmospheric residue with more sulphur, metals and naphthenic aromatic structures can activate more hydrogen. Both the hydrogen solubility and residue composition have significant effect on the upgrading process.

Evaluation of molecular orbital symmetry via oxygen-induced charge transfer quenching at a metal-organic interface

Thin molecular films under model conditions are often exploited as benchmarks and case studies to investigate the electronic and structural changes occurring on the surface of metallic electrodes. Here we show that the modification of a metallic surface induced by oxygen adsorption allows the preservation of the geometry of a molecular adlayer, giving access to the determination of molecular orbital symmetries by means of near-edge X-ray absorption fine structure spectroscopy, NEXAFS. As a prototypical example, we exploited nickel tetraphenylporphyrin molecules deposited on a bare and on an oxygen pre-covered Cu(1 0 0) surface. We find that adsorbed atomic oxygen quenches the charge transfer at the metal-organic interface but, in contrast to a thin film sample, maintains the ordered adsorption geometry of the organic molecules. In this way, it is possible to disentangle π* and σ* symmetry orbitals, hence estimate the relative oscillator strength of core level transitions directly from the experimental data, as well as to evaluate and localize the degree of charge transfer in a coupled system. In particular, we neatly single out the σ* contribution associated with the N 1s transition to the mixed N 2px,y-Ni 3dx2-y2 orbital, which falls close to the leading π*-symmetry LUMO resonance.

Synthesis, Electrochemistry, and Reversible Interconversion among Perhalogenated Hydroxyphenyl Ni(II) Porphyrins, Porphodimethenes, and Porpho-5,15-bis-paraquinone Methide.

Two octahalogenated nickel(II) hydroxyphenylporphyrins were synthesized and characterized as to their electrochemical and spectroscopic properties as well as their reactivity in neutral, acidic, and basic nonaqueous media. The newly synthesized complexes are represented as NiPorCl8 and NiPorBr8, where Por is the dianion of meso-tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin. The UV-vis spectra of NiPorCl8 and NiPorBr8 vary with the solvent and degree of axial coordination but are almost identical to each other in a given solvent. These spectra are also substantially different from that of the unhalogenated NiPor parent porphyrin (which resembles nickel tetraphenylporphyrin, NiTPP), and they also differ from the spectra of β-octahalogenated NiTPPCl8 and NiTPPBr8 under the same solution conditions. The NiPorX8 spectra are stable with time and interpreted in terms of 4- or 6-coordinate derivatives in 13 different nonaqueous solvents. This is not the case, however, in DMF or DMSO, where a transient six-coordinate complex is initially formed upon dissolving the NiPorCl8, followed by the formation of an air-oxidized porphodimethene-like product called porpho-5,15-bis-paraquinone methide, with the time of this chemical transformation depending upon the concentration of the porphyrin in solution. The initial species formed from NiPorCl8 and NiPorBr8 after the first one-electron addition in CH2Cl2 is stable for short times at -60 °C, but this is not the case at room temperature, where a rapid homogeneous chemical reaction occurs. Four additional redox reactions are also observed in CH2Cl2, and the UV-visible spectra of several in-situ-generated electroreduction products are compared with that of chemically synthesized porphodimethenes formed in neutral, acidic, and basic solutions of CH2Cl2 containing acid in the form of TFA or base in the form of TBA+X, where X = OAc-, CN-, and OH-. Finally, a reversible electrochemically driven conversion between the Ni(II) hydroxyphenylporphyrin and a reduced porphodimethene or oxidized porphyrin-like product, porpho-5,15-bis-paraquinone methide, is described.

Nickel(II) Tetraphenylporphyrin as an Efficient Photocatalyst Featuring Visible Light Promoted Dual Redox Activities

AbstractNickel(II) tetraphenylporphyrin (NiTPP) is presented as a robust, cost‐effective and efficient visible light induced photoredox catalyst. The ground state electrochemical data (CV) and electronic absorption (UV‐Vis) spectra reveal the excited state redox potentials for [NiTPP]*/[NiTPP].− and NiTPP].+/[NiTPP]* couples as +1.17 V and −1.57 V vs SCE respectively. The potential values represent NiTPP as a more potent photocatalyst compare to the well‐explored [Ru(bpy)3]2+. The non‐precious photocatalyst exhibits excited state redox reactions in dual fashions, i. e., it is capable of undergoing both oxidative as well as reductive quenching pathways. Such versatility of a photocatalyst based on first‐row transition metals is very scarce. This unique phenomenon allows one to perform diverse types of redox reactions by employing a single catalyst. Two different sets of chemical reactions have been performed to represent the synthetic utility. The catalyst showed superior efficiency in both carbon‐carbon and carbon‐heteroatom bond‐forming reactions. Thus, we believe that NiTPP is a valuable addition to the photocatalyst library and this study will lead to more practical synthetic applications of earth‐abundant‐metal‐based photoredox catalysts.magnified image

Comparative X-Ray Absorption Analysis of the Spectrum of Vacant Electronic States in Cobalt and Nickel Tetraphenylporphyrin Complexes

The energy distributions and the properties of the lower vacant electronic states in cobalt and nickel tetraphenylporphyrin complexes CoTPP and NiTPP are studied by X-ray absorption spectroscopy. Q ...

Сравнительное рентгеноабсорбционное исследование спектра свободных электронных состояний в комплексах тетрафенилпорфиринов кобальта и никеля

AbstractThe energy distributions and the properties of the lower vacant electronic states in cobalt and nickel tetraphenylporphyrin complexes CoTPP and NiTPP are studied by X-ray absorption spectroscopy. Quasimolecular analysis of the experimental absorption spectra measured in the region of the 2 p and 1 s ionization thresholds of complexing metal atoms, as well as the 1 s thresholds of ligand atoms (nitrogen and carbon), is based on the comparison of the corresponding spectra with each other and with the spectra of the simplest nickel porphyrin NiP. It has been established that, despite a general similarity of the spectra of nitrogen and carbon in CoTPP and NiTPP, the fine structure of the 2 p and 1 s absorption spectra of cobalt and nickel atoms are radically different. The observed differences in the spectra of cobalt and nickel are associated with the features of the energy distribution of vacant 3 d electron states. The presence in CoTPP of the partially filled valence 3 db _2 g molecular orbital (MO) results in the appearance in the cobalt spectra of a low-energy band, which is absent in the spectrum of nickel in NiTPP and leads to a doublet structure of transitions to b _1 g and e _ g MOs due to the exchange interaction between 3 d electrons in partially filled 3 db _2 g and 3 db _1 g or 3 de _ g MOs. The spectrum of vacant states in CoTPP differs from that in NiTPP also due to the smaller energy distance between 3 db _1 g and e _ g MOs and the different positions of nonbonding MOs with the C2 p character of the porphine ligand.

Reductive Functionalization of Graphenides With Nickel(II) Porphyrin Diazonium Compounds

A novel type of a graphene‐porphyrin hybrid with a direct covalent linker between graphene and a nickel(II) tetraphenylporphyrin unit has successfully been synthesized by the reductive exfoliation/functionalization of potassium intercalated graphite as starting material. Moreover, we directly compared the reactivity of two structurally different porphyrin derivatives, namely, meso‐NiTPP‐N2+, with the diazonium group in 4′‐position of a peripheral phenyl ring and a novel β‐NiTPP‐N2+ diazonium cation, where the diazonium group is directly attached to the β‐pyrrolic position of the 18 π electron core. Due to sterical restraints, this intermediately generated porphyrin radical cannot attack the extended π surface of graphene and only a functionalization of present dangling bonds at the flake edges may be obtained in this case. All reaction products have been analyzed in detail be means of Raman and UV/Vis spectroscopy as well as thermogravimetric analysis.

Multi-orbital charge transfer at highly oriented organic/metal interfaces

The molecule–substrate interaction plays a key role in charge injection organic-based devices. Charge transfer at molecule–metal interfaces strongly affects the overall physical and magnetic properties of the system, and ultimately the device performance. Here, we report theoretical and experimental evidence of a pronounced charge transfer involving nickel tetraphenyl porphyrin molecules adsorbed on Cu(100). The exceptional charge transfer leads to filling of the higher unoccupied orbitals up to LUMO+3. As a consequence of this strong interaction with the substrate, the porphyrin’s macrocycle sits very close to the surface, forcing the phenyl ligands to bend upwards. Due to this adsorption configuration, scanning tunneling microscopy cannot reliably probe the states related to the macrocycle. We demonstrate that photoemission tomography can instead access the Ni-TPP macrocycle electronic states and determine the reordering and filling of the LUMOs upon adsorption, thereby confirming the remarkable charge transfer predicted by density functional theory calculations.

Green reduction of reduced graphene oxide with nickel tetraphenyl porphyrin nanocomposite modified electrode for enhanced electrochemical determination of environmentally pollutant nitrobenzene.

Nitrobenzene (NB) is widely used in the manufacturing of different types of products and other aromatic chemicals. Moreover, it is highly toxic and environmental pollutant compound. Therefore, the detection of nitro aromatic compounds (NACs) has gained more attention in the field of sensor. This article describes the green reduction utilized to preparation of green reduced graphene oxide/nickel tetraphenyl porphyrin (GRGO/Ni-TPP) nanocomposite modified electrode for the determination of nitrobenzene (NB). The GRGO was prepared by environmentally friendly method and using caffeic acid (CA) as a reducing agent. Moreover, the GRGO/Ni-TPP nanocomposite was prepared via the π-π stacking interaction between the RGO and Ni-TPP. In addition, the prepared material was confirmed by the UV-Visible spectroscopy (UV), nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FTIR). The structural morphology and elemental composition of the prepared nanocomposite was confirmed by the scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX). Besides, the electrochemical studies of the prepared nanocomposite was characterized by the CV and DPV technique. The DPV studies displayed the linearity response of the proposed sensor about 0.5-878µM with the sensitivity of 1.277µAµM-1cm-2 and the limit of detection (LOD) is 0.14µM. Furthermore, the GRGO/Ni-TPP nanocomposite modified electrode shows good selectivity towards the detection of NB. In addition, the real sample analysis exhibited appreciable recovery towards the determination of NB using various types of water samples.

Nickel tetraphenylporphyrin doping into ZnO nanoparticles for flexible dye-sensitized solar cell application

In this study, we report on ZnO-based flexible dye-sensitized solar cells (DSCs) doped with different concentrations of 5,10,15,20-tetraphenyl-21H,23H-porphyrin nickel(II) (NiTPP). The photoelectrodes were prepared by blade coating, followed by a hot-compression technique. The effects of NiTPP doping on the surface morphology, structural, optical, and photovoltaic properties were studied. The surface morphology was observed by scanning electron microscopy (SEM), which confirmed the presence of NiTPP particles and also some aggregated particles visible at higher doping concentrations. The structural properties were examined by X-ray diffraction analysis and Raman spectroscopy, which confirmed the hexagonal wurtzite ZnO structure. The crystallite size of the ZnO nanoparticles (NPs) increased while the lattice strain decreased with increasing NiTPP doping concentration. The increment in the crystallite size might have induced light scattering inside the film to some extent. Optical absorption spectra showed the broadening of the spectrum in the lower-wavelength region, and a new absorption peak appeared (at 422 nm) as an effect of NiTPP doping. The red and blue shifts were observed for that peak as an effect of various doping concentrations. The Raman study of the films showed that there is no significant changes in the ZnO or NiTPP crystallite structure because of the NiTPP doping at different concentrations. Photocurrent–voltage (I–V) analysis showed that the 0.7%-NiTPP-doped cell attained the highest light-to-electric conversion efficiency of 2.7% in this investigation, which was about 42% higher than that of a non-NiTPP-doped cell.