Revealing the structure–activity relationship of two Cu-porphyrin-based metal–organic frameworks for the electrochemical CO<sub>2</sub>-to-HCOOH transformation

Liu, Mengjie; Cao, Si-Min; Feng, Bo; Dong, Bao‐Xia; Ding, Yuhao; Zheng, Qiu-Hui; Teng, Yun‐Lei; Li, Zongwei; Liu, Wenlong; Feng, Ligang

doi:10.1039/d0dt02683b

Cited by 35 publications

(10 citation statements)

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“…In contrast, higher CO 2 uptake for PCN‐222(M) (M = Fe, Co, Ni, and Cu) was observed (37, 35, 39, and 36 cm 3 g −1 ), respectively (Figure 4). According to the previous literature reports, [ 26,33–36 ] the values of the heat of adsorption ( Q st ) for CO 2 were estimated, implying that PCN‐222 and PCN‐222(M) have a high affinity for CO 2 which can improve the photocatalytic reaction.…”

Section: Resultsmentioning

confidence: 99%

Effective visible‐light CO₂ photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Hariri

Dehghanpour

2021

Applied Organom Chemis

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Metal–organic frameworks (MOFs) have proved to be particularly appropriate for CO2 conversion. In the present work, we report metalloporphyrin‐based MOFs, PCN‐222(M) (M = Fe, Co, Ni, and Cu), which promote photocatalytic CO2 conversion to valuable chemicals. These ultra‐highly stable frameworks are constructed from Zr6 clusters and metalloporphyrin linkers. Metalloporphyrinic MOF has been synthesized and employed as a visible‐light photocatalyst for carbon dioxide to form formate. The effect of metalloporphyrinic PCN‐222(M) on CO2 reduction has been studied. Remarkably, PCN‐222(M) is highly efficient in visible light‐driven CO2 reduction into formate ion compared with the nonmetal porphyrinic PCN‐222. Metal ions of porphyrinic linkers play a great role in CO2 sorption, light harvesting, bandgap, photoluminescence (pL) intensity, and charge transfer, which influence CO2 reduction. CO2 adsorption and activation over metal ions of porphyrinic linkers play a significant part in the improvement of the conversion efficiency; the product obtained was characterized by gas chromatography/mass spectrometry (GC/MS) and ion mobility spectrometry (IMS) analyses. The reaction mechanism has been discussed in detail.

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Section: Resultsmentioning

confidence: 99%

Effective visible‐light CO₂ photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Hariri

Dehghanpour

2021

Applied Organom Chemis

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“…Currently, CPs are being used in the electrochemical fields, including fuel cells, supercapacitors, − and batteries, , due to their electrochemical activity. Especially, some redox-active pristine CPs exhibited excellent electrocatalytic activity − and attracted new attentions in nonenzymatic electrochemical sensing for some analytes. ,, For example, two novel CPs with anthracene derivatives, 1D {[Zn(L)(DMF) 2 ]} n and 3D {[Cd(L)(DMF)]·DMF} n [H 2 L = 4,4′-(9,10-anthracenediyl)dicinnamic acid], show electrochemical sensing toward H 2 O 2 (linear range: 0.2–1.4 mM) . The introduction of melamine (Mel) into CPs has been proved to be an efficient approach to realize nonenzymatic glucose sensing because Mel-based CPs can accumulate glucose on the CP-modified electrode through hydrogen bonding.…”

Section: Introductionmentioning

confidence: 99%

Proton-Conductive and Electrochemical-Sensitive Sensing Behavior of a New Mn(II) Chain Coordination Polymer

Yang

Zhang

2023

Crystal Growth & Design

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In this work, a novel Mn(II) chain coordination polymer (Mn-CP), {[Mn(iip)(2bbpum) 0.5 (H 2 O) 3 ]•2H 2 O} n [H 2 iip = 5-iodoisophthalic acid, 2bbpum = N,N′-bis(2-pyridinemethyl)oxamide] was synthesized under ambient conditions. Mn-CP further assembles into a 3D supramolecular architecture through hydrogen bonds, halogen bonds, and ππ stacking interactions. The composite Mn-CP/nafion membrane has low activation energy for proton transfer, which results in its temperature-insensitive proton conductivity. The cyclic voltammetry demonstrates that the Mn-CP electrode (Mn-CP/GCE) shows quite different redox properties in 0.1 M H 2 SO 4 and 0.1 M PBS aqueous solutions. The Mn-CP/GCE exhibits a couple of irreversible redox peaks with an oxidation peak potential suitable for the nitrite oxidation in 0.1 M H 2 SO 4 . Quite differently, in the PBS aqueous buffer solution, the Mn-CP electrode has a couple of irreversible redox peaks. The reduction peak potential is appropriate for the H 2 O 2 reduction. So, the Mn-CP/GCE can be used not only in the electrocatalytic oxidation of NO 2 − but also in the electrocatalytic reduction of H 2 O 2 . The amperometric response reveals that the Mn-CP/GCE exhibits high-selective and extremely sensitive oxidation sensing of NO 2 − and reduction sensing of H 2 O 2 . The exponential detection range is 0.01−20 mM for NO 2 − and 0.01−10.5 mM for H 2 O 2 . The linear detection range for both H 2 O 2 and NO 2 − is 0.01−0.10 mM. The detection limit is 1.865 μM for NO 2 − and 8.57 μM for H 2 O 2 . The Mn-CP/GCE exhibits high electrochemical stability and fine reproducibility. Moreover, the strategy can be translated to a portable screen-printed electrode (SPE). The Mn-CP/SPE shows more sensitive sensing to NO 2 − and H 2 O 2 than Mn-CP/GCE. Moreover, it can detect NO 2 − and H 2 O 2 efficiently in the real-world samples. So, Mn-CP may be a potential dual nonenzymatic electrochemical sensory material for NO 2 − via oxidation sensing and H 2 O 2 via reduction sensing.

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“…Porphyrins are widely used as building blocks for the assembly of covalent organic frameworks because of their high stability, easy chelation with metal ions, and ease of modification [ 19 ]. Several porphyrin-based COFs (Por-COFs) have been constructed for use in electro chemiluminescence, heterogeneous catalysis, and photooxidization reactivity [ 20 , 21 , 22 ]. In addition, metalloporphyrin COFs (MPor-COFs) possess a unique N-C framework, which offers a novel platform for the preparation of self-supporting M-N-C sites with intrinsic metal coordination for use as porous electrocatalysts [ 23 ].…”

Section: Introductionmentioning

confidence: 99%

Ultrasensitive Electrochemical Detection of Butylated Hydroxy Anisole via Metalloporphyrin Covalent Organic Frameworks Possessing Variable Catalytic Active Sites

et al. 2022

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Three novel two-dimensional metalloporphyrin COFs (MPor−COF−366, M = Fe, Mn, Cu) were fabricated by changing the metal atoms in the center of the porphyrin framework. The physicochemical characteristics of MPor−COF−366 (M = Fe, Mn, Cu) composites were fully analyzed by diverse electron microscopy and spectroscopy. Under optimal conditions, experiments on determining butylated hydroxy anisole (BHA) at FePor−COF−366/GCE were conducted using differential pulse voltammetry (DPV). It is noted that the FePor−COF−366/GCE sensor showed excellent electrocatalytic performance in the electrochemical detection of BHA, compared with MnPor−COF−366/GCE and CuPor−COF−366/GCE. A linear relationship was obtained for 0.04–1000 μM concentration of BHA, with a low detection limit of 0.015 μM. Additionally, the designed sensor was successfully employed to detect BHA in practical samples, expanding the development of COF-based composites in electrochemical applications.

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Revealing the structure–activity relationship of two Cu-porphyrin-based metal–organic frameworks for the electrochemical CO₂-to-HCOOH transformation

Abstract: The eCO2RR activity is correlated to the internal structural character of the catalyst. We employ two types of structural models of porphyrin-based MOFs of PCN-222(Cu) and PCN-224(Cu), featured with the...

Cited by 35 publications

References 49 publications

Effective visible‐light CO₂ photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Effective visible‐light CO₂ photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Proton-Conductive and Electrochemical-Sensitive Sensing Behavior of a New Mn(II) Chain Coordination Polymer

Ultrasensitive Electrochemical Detection of Butylated Hydroxy Anisole via Metalloporphyrin Covalent Organic Frameworks Possessing Variable Catalytic Active Sites

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Revealing the structure–activity relationship of two Cu-porphyrin-based metal–organic frameworks for the electrochemical CO2-to-HCOOH transformation

Abstract: The eCO2RR activity is correlated to the internal structural character of the catalyst. We employ two types of structural models of porphyrin-based MOFs of PCN-222(Cu) and PCN-224(Cu), featured with the...

Cited by 35 publications

References 49 publications

Effective visible‐light CO2 photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Effective visible‐light CO2 photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Proton-Conductive and Electrochemical-Sensitive Sensing Behavior of a New Mn(II) Chain Coordination Polymer

Ultrasensitive Electrochemical Detection of Butylated Hydroxy Anisole via Metalloporphyrin Covalent Organic Frameworks Possessing Variable Catalytic Active Sites

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Revealing the structure–activity relationship of two Cu-porphyrin-based metal–organic frameworks for the electrochemical CO₂-to-HCOOH transformation

Effective visible‐light CO₂ photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons

Effective visible‐light CO₂ photoreduction over (metallo)porphyrin‐based metal–organic frameworks to achieve useful hydrocarbons