Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction

Zhang, Xiao; Yang, Wang; Gu, Meng; Wang, Maoyu; Zhang, Zisheng; Pan, Wei-Ying; Zhan, Jing; Zheng, Hongzhi; Lucero, Marcos; Wang, Hailiang; Sterbinsky, George E.; Ma, Qing; Feng, Zhenxing; Li, Jun; Dai, Hongjie; Liang, Yongye

doi:10.1038/s41560-020-0667-9

Cited by 465 publications

(427 citation statements)

References 62 publications

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“…According to the above experimental results, we can see that NiPc‐TFPN COF's CO 2 to CO selectivity and current density are higher than CoPc‐TFPN COF in a wide potential range, which leads us to the conclusion that NiPc‐TFPN COF shows optimal performance for ECR among these COFs materials. This result is consistent with the results previously reported for NiPc or Ni‐N 4 based catalysts [7a,d, 8c] . Besides, the turnover frequency (TOF) of NiPc‐TFPN COF was calculated to be 490 h −1 at −0.9 V, large than CoPc‐TFPN COF(369 h −1 at −0.9 V).…”

Section: Resultssupporting

confidence: 92%

Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO₂Reduction

Zhang

Liu

et al. 2021

Angewandte Chemie

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In this work, we rationally designed a series of crystalline and stable dioxin‐linked metallophthalocyanine covalent organic frameworks (COFs; MPc‐TFPN COF, M=Ni, Co, Zn) under the guidance of reticular chemistry. As a novel single‐site catalysts (SSCs), NiPc/CoPc‐TFPN COF exhibited outstanding activity and selectivity for electrocatalytic CO2 reduction (ECR; Faradaic efficiency of CO (FECO)=99.8(±1.24) %/ 96.1(±1.25) % for NiPc/CoPc‐TFPN COF). More importantly, when coupled with light, the FECO and current density (jCO) were further improved across the applied potential range (−0.6 to −1.2 V vs. RHE) compared to the dark environment for NiPc‐TFPN COF (jCO increased from 14.1 to 17.5 A g−1 at −0.9 V; FECO reached up to ca. 100 % at −0.8 to −0.9 V). Furthermore, an in‐depth mechanism study was established by density functional theory (DFT) simulation and experimental characterization. For the first time, this work explored the application of COFs as photo‐coupled electrocatalysts to improve ECR efficiency, which showed the potential of using light‐sensitive COFs in the field of electrocatalysis.

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Section: Resultssupporting

confidence: 92%

Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO₂Reduction

Zhang

Liu

et al. 2021

Angewandte Chemie

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“…Such durability was much better than Ni@NC/NCNT, Ni@NC and NCNT (Figure S7c and d). More importantly, our catalyst surpassed most state‐of‐the‐art CO‐selective catalysts in terms of long‐term durability in CO 2 RR (Figure 4f and Table S7) [16,17,19,26,33–35,37,60,66,67,69,72,76–94] . These unambiguously demonstrated the advantage of the dual chainmail structure in reinforcing the catalyst and boosting the CO 2 RR performance.…”

Section: Resultsmentioning

confidence: 60%

Confining Chainmail‐Bearing Ni Nanoparticles in N‐doped Carbon Nanotubes for Robust and Efficient Electroreduction of CO₂

et al. 2021

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It still remains challenging to simultaneously achieve high stability, selectivity, and activity in CO2 reduction. Herein, a dual chainmail‐bearing nickel‐based catalyst (Ni@NC@NCNT) was fabricated via a solvothermal‐evaporation‐calcination approach. In situ encapsulated N‐doped carbon layers (NCs) and nanotubes (NCNTs) gave a dual protection to the metallic core. The confined space well maintained the local alkaline pH value and suppressed hydrogen evolution. Large surface area and abundant pyridinic N and Niδ+ sites ensured high CO2 adsorption capacity and strength. Benefitting from these, it delivered a CO faradaic efficiency of 94.1 % and current density of 48.0 mA cm−2 at −0.75 and −1.10 V, respectively. Moreover, the performance remained unchanged after continuous electrolysis for 43 h, far exceeding Ni@NC with single chainmail, Ni@NC/NCNT with Ni@NC sitting on the walls of NCNT, bare NCNT and most state‐of‐the‐art catalysts, demonstrating structural superiority of Ni@NC@NCNT. This work sheds light on designing unique architectures to improve electrochemical performances.

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“…[8] For example, immobilization of a CO 2 RR molecular catalyst is possible without any functionalization of the ligand when the ligand is highly conjugated as in the case of metal porphyrins and phthalocyanines. [9][10][11] In contrast, when a ligand, such as a bipyridine or benzene-based pincer derivative, has a limited electronic delocalized structure, an aromatic group, most often pyrene, has to be covalently added to the ligand; the pyrene group allows tight grafting of the molecular complex on the carbon electrode surfaces by π-π stacking interactions. Regarding such simple ligands functionalized with a pyrene group, the most representative reports concern bipyridine-pyrene derivatives used to immobilize a [Re(bpy)(CO) 3 Cl] complex on a graphite support [12] or a [Mn(bpy)(CO) 3 Br] complex on carbon nanotubes [13] as well as a pincer-pyrene ligand used to immobilize an iridium complex onto a gas diffusion electrode via carbon nanotubes.…”

Section: Introductionmentioning

confidence: 99%

Functionalization of Carbon Nanotubes with Nickel Cyclam for the Electrochemical Reduction of CO₂

et al. 2020

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The exploitation of molecular catalysts for CO 2 electrolysis requires their immobilization on the cathode of the electrolyzer. As an illustration of this approach, a Ni-cyclam complex with a cyclam derivative functionalized with a pyrene moiety is synthesized, found to be a selective catalyst for CO 2 electroreduction to CO, and immobilized on a carbon nanotubecoated gas diffusion electrode by using a noncovalent binding strategy. The as-prepared electrode is efficient, selective, and robust for electrocatalytic reduction of CO 2 to CO. Very high turnover numbers (ca. 61460) and turnover frequencies (ca. 4.27 s À 1) are enabled by the novel electrode material in organic solvent-water mixtures saturated with CO 2. This material provides an interesting platform for further improvement.

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Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction

Cited by 465 publications

References 62 publications

Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO₂Reduction

Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO₂Reduction

Confining Chainmail‐Bearing Ni Nanoparticles in N‐doped Carbon Nanotubes for Robust and Efficient Electroreduction of CO₂

Functionalization of Carbon Nanotubes with Nickel Cyclam for the Electrochemical Reduction of CO₂

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Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction

Cited by 465 publications

References 62 publications

Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO2Reduction

Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO2Reduction

Confining Chainmail‐Bearing Ni Nanoparticles in N‐doped Carbon Nanotubes for Robust and Efficient Electroreduction of CO2

Functionalization of Carbon Nanotubes with Nickel Cyclam for the Electrochemical Reduction of CO2

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Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO₂Reduction

Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO₂Reduction

Confining Chainmail‐Bearing Ni Nanoparticles in N‐doped Carbon Nanotubes for Robust and Efficient Electroreduction of CO₂

Functionalization of Carbon Nanotubes with Nickel Cyclam for the Electrochemical Reduction of CO₂