Synthesis and investigation of tetraphenyltetrabenzoporphyrins for electrocatalytic reduction of carbon dioxide

Apaydın, Doğukan Hazar; Portenkirchner, Engelbert; Jintanalert, Pichayada; Strauss, Maurice B.; Luangchaiyaporn, Jirapong; Sariciftci, Niyazi Serdar; Thamyongkit, Patchanita

doi:10.1039/c8se00422f

Cited by 8 publications

(4 citation statements)

References 40 publications

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“…Over the past decade, tremendous effort has been dedicated to developing an efficient catalyst for achieving efficient CO2 reduction [16][17][18][19][20][21][22][23][24] . Although progress has certainly been made, the CO2 photocatalytic efficiency is still far from satisfactory, primarily because of the huge CO2 activation energy and the slow kinetics of the complicated multiple electron transfer and reaction processes involved [25][26][27][28] . Hence, it is necessary to design a new artificial material based on proper architectures, high selectivities and high activities by using inexpensive materials for solar-driven CO2 reduction.…”

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confidence: 99%

Photocatalytic CO2 Reduction Using Ni2P Nanosheets

Pan¹,

Liu²,

Niu³

et al. 2020

Acta Physico-Chimica Sinica

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Artificial photosynthesis is an ideal method for solar-to-chemical energy conversion, wherein solar energy is stored in the form of chemical bonds of solar fuels. In particular, the photocatalytic reduction of CO2 has attracted considerable attention due to its dual benefits of fossil fuel production and CO2 pollution reduction. However, CO2 is a comparatively stable molecule and its photoreduction is thermodynamically and kinetically challenging. Thus, the photocatalytic efficiency of CO2 reduction is far below the level of industrial applications. Therefore, development of low-cost cocatalysts is crucial for significantly decreasing the activation energy of CO2 to achieving efficient photocatalytic CO2 reduction. Herein, we have reported the use of a Ni2P material that can serve as a robust cocatalyst by cooperating with a photosensitizer for the photoconversion of CO2. An effective strategy for engineering Ni2P in an ultrathin layered structure has been proposed to improve the CO2 adsorption capability and decrease the CO2 activation energy, resulting in efficient CO2 reduction. A series of physicochemical characterizations including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and atomic force microscopy (AFM) were used to demonstrate the successful preparation of ultrathin Ni2P nanosheets. The XRD and XPS results confirm the successful synthesis of Ni2P from Ni(OH)2 by a low temperature phosphidation process. According to the TEM images, the prepared Ni2P nanosheets exhibit a 2D and near-transparent sheet-like structure, suggesting their ultrathin thickness. The AFM images further demonstrated this result and also showed that the height of the Ni2P nanosheets is ca 1.5 nm. The photoluminescence (PL) spectroscopy results revealed that the Ni2P material could efficiently promote the separation of the photogenerated electrons and holes in [Ru(bpy)3]Cl2·6H2O. More importantly, the Ni2P nanosheets could more efficiently promote the charge transfer and charge separation rate of [Ru(bpy)3]Cl2·6H2O compared with the Ni2P particles. In addition, the electrochemical experiments revealed that the Ni2P nanosheets, with their high active surface area and charge conductivity, can provide more active centers for CO2 conversion and accelerate the interfacial reaction dynamics. These results strongly suggest that the Ni2P nanosheets are a promising material for photocatalytic CO2 reduction, and can achieve a CO generation rate of 64.8 μmol·h −1 , which is 4.4 times higher than that of the Ni2P particles. In addition, the XRD and XPS measurements of the used Ni2P nanosheets after the six cycles of the photocatalytic CO2 reduction reaction demonstrated their high stability. Overall, this study offers a new function for the 2D transition-metal phosphide catalysts in photocatalytic CO2 reduction.

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confidence: 99%

Photocatalytic CO2 Reduction Using Ni2P Nanosheets

Pan¹,

Liu²,

Niu³

et al. 2020

Acta Physico-Chimica Sinica

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“…NHE and the second ones at around −1.30 V vs . NHE, corresponding to the reduction of the benzoporphyrinic cores [36] …”

Section: Resultsmentioning

confidence: 99%

“…[32a] On a reduction side, the TBPs exhibited the first reduction at reduction peak potentials (E red,peak ) of À 0.90 to À 0.93 V vs. NHE and the second ones at around À 1.30 V vs. NHE, corresponding to the reduction of the benzoporphyrinic cores. [36] Following previous studies, [37] highest occupied molecular orbital (HOMO) levels of the target TBPs could be represented by the E ox,peak values of their first oxidation, while lowest unoccupied molecular orbital (LUMO) levels of the photoexcited molecule can be estimated from their excited state oxidation potentials (E * 0-0 ) by the following equation:…”

Section: Compoundmentioning

confidence: 99%

Benzoporphyrin‐Based Nanocomposites for Photoelectrochemical O₂ Reduction

Keawsongsaeng

Seelajareon

Namuangruk

et al. 2021

Israel Journal of Chemistry

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This research presents a new series of tetrabenzoporphyrins (TBPs) bearing p-diphenylaminophenylethynyl and p-carboxylphenylethynyl groups or two p-carboxylphenylethynyl groups in a trans-fashion on a TBP core for photoelectrochemical O 2 reduction. Impact of electron-donating diphenylamino and electron-withdrawing surface-anchoring carboxyl groups on photophysical and electrochemical properties of the target TBPs was experimentally and theoretically investigated in comparison with those of their benchmark analog. The results show that while the p-carboxylphenylethynyl group give an electronic contribution to the molecules by lowering energy gap, the role of the p-diphenylaminophenylethynyl group is found to be trivial. Preliminary inves-tigation on electrochemical O 2 reduction indicates significant catalytic activities of TBP-modified TiO 2 /fluorene-doped tin oxide electrodes at potentials of À 0.2 V and À 0.3 V vs. normal hydrogen electrode (NHE) in a pH-neutral and ambient aqueous condition, leading to H 2 O 2 formation. Upon photoirradiation, catalytic performance of such TBPbased electrodes is further enhanced with the optimum yield obtained when the dicarboxyl derivatives and the potential of À 0.3 V vs. NHE are applied. Proposed photoinjection mechanism of the dye/TiO 2 simulated by time-dependent density functional theory calculations supported the experimental results indicating the favorable role of the target TBPs as photoelectrocatalysts in the O 2 reduction.

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“…Electrochemical impedance spectroscopy (EIS) is one of the most utilized electrochemical methods to characterize electrode materials relevant to energy conversion and storage technologies, including heterojunction and dye-sensitized solar cells, [83][84][85][86] rechargeable batteries, [37,[87][88][89][90][91] and electrocatalysts/ photocatalysts for water splitting and CO 2 reduction. [92][93][94][95] EIS is a non-destructive tool that allows to investigate and differentiate several interfaces like solid/electrolyte or solid/ solid, within a devices on the basis of their frequency response under potential control and the subsequent decoupling of resistive and capacitive circuit components. [96] Therefore, EIS allows to study these components independently based on the frequency dependent current response of the electrode.…”

Section: Electrochemical Impedance Spectroscopymentioning

confidence: 99%

Substrate Dependent Charge Transfer Kinetics at the Solid/Liquid Interface of Carbon‐Based Electrodes with Potential Application for Organic Na‐Ion Batteries

Werner

Alexander

Winkler

et al. 2021

Israel Journal of Chemistry

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Electroactive organic semiconducting pigments represent a group of very promising electrode materials for the next generation of energy conversion and storage technologies. However, most pigments suffer from high solubility in organic electrolytes and poor electrical conductivity, which have severely impeded their practical applications. Among different strategies to improve their electrochemical performance, using conductive carbon substrates to form composite electrodes is one of the most used methods to solve these problems. In this work we investigate the role of conductive carbon substrates towards their charge transfer kinetics at the solid/liquid interface with potential application for organic sodium (Na)‐ion batteries. This study reveals that the role of conductive carbon is related not only to the optimal electronic path but also to the ionic path towards the electrode active material. Perylentetracarboxylicdiimide is used as the electrode active material coated on graphite/copper and carbon paper substrates. The morphology, structure, and chemical composition of our electrodes are investigated via scanning electron microscopy, X‐ray photoelectron and Raman spectroscopy. A thorough kinetic analysis is systematically implemented by cyclic voltammetry and electrochemical impedance spectroscopy. We performed a quantitative analysis of the resistance and capacitive components of the composite electrodes using the theory of the transmission line model and electrochemical impedance spectroscopy with symmetric cells. Our results indicate that a decrease in pore resistance is key to achieve high charge transfer kinetics in electrochemical systems. This work will therefore contribute towards future, efficient electrode design with low pore resistance and high charge transfer kinetics. This may prove of great importance for the development of energy conversion and storage technologies, including heterojunction solar cells, electrocatalysts/photocatalysts for water splitting, carbon dioxide (CO2) reduction and lithium (Li)‐ and Na‐ion batteries.

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Synthesis and investigation of tetraphenyltetrabenzoporphyrins for electrocatalytic reduction of carbon dioxide

Abstract: Benzoporphyrins with varying non-noble metal centers can reduce carbon dioxide to carbon monoxide with faradaic efficiencies changing between 33 and 48%.

Cited by 8 publications

References 40 publications

Photocatalytic CO<sub>2</sub> Reduction Using Ni<sub>2</sub>P Nanosheets

Photocatalytic CO<sub>2</sub> Reduction Using Ni<sub>2</sub>P Nanosheets

Benzoporphyrin‐Based Nanocomposites for Photoelectrochemical O₂ Reduction

Substrate Dependent Charge Transfer Kinetics at the Solid/Liquid Interface of Carbon‐Based Electrodes with Potential Application for Organic Na‐Ion Batteries

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Synthesis and investigation of tetraphenyltetrabenzoporphyrins for electrocatalytic reduction of carbon dioxide

Abstract: Benzoporphyrins with varying non-noble metal centers can reduce carbon dioxide to carbon monoxide with faradaic efficiencies changing between 33 and 48%.

Cited by 8 publications

References 40 publications

Photocatalytic CO<sub>2</sub> Reduction Using Ni<sub>2</sub>P Nanosheets

Photocatalytic CO<sub>2</sub> Reduction Using Ni<sub>2</sub>P Nanosheets

Benzoporphyrin‐Based Nanocomposites for Photoelectrochemical O2 Reduction

Substrate Dependent Charge Transfer Kinetics at the Solid/Liquid Interface of Carbon‐Based Electrodes with Potential Application for Organic Na‐Ion Batteries

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Benzoporphyrin‐Based Nanocomposites for Photoelectrochemical O₂ Reduction