Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks

Crawley, Matthew R.; Zhang, Daoyang; Oldacre, Amanda N.; Beavers, Christine M.; Friedman, Alan E.; Cook, Timothy R.

doi:10.1021/jacs.0c11895

Cited by 37 publications

(38 citation statements)

References 51 publications

(78 reference statements)

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“…through coordination‐driven self‐assembly methods, although Ru‐based molecular clips were required Figure 17 a). [ 36 ] Meanwhile, cofacial separated Co‐based bisporphyrin dyad resembling a Pacman shape very similar to theoretical catalysts in Figures 5c and 10c has been produced by Cao's group for O 2 reduction (Figure 6d). [ 35 ] These methods of producing molecular cofacial DACs would require functionalization to an appropriately conductive support and be resistive to harsh pH environments for realistic applications in electrochemical reactions.…”

Section: Synthesis Techniquesmentioning

confidence: 68%

Section: Synthesis Techniquesmentioning

confidence: 99%

“…Co 2 /Ru (pink square) in 0.5 m H 2 SO 4 electrolyte. Co-Tolyl prism with Ru represented by pink spheres (see Section 3.3) [36]. Co 2 FTF (blue dash-dot line) in 0.5 m CF 3 CO 2 H at 250 rpm [37].…”

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confidence: 99%

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Dual‐Metal Atom Electrocatalysts: Theory, Synthesis, Characterization, and Applications

Pedersen

Barrio

et al. 2021

Advanced Energy Materials

104

106

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a required reduction in emissions per unit production of 75% by 2050 in order to have a 50% chance of limiting global mean temperature rise by 2 °C compared to pre-industrial levels. [1,2] Improvements in the field of electrocatalysts, especially in relation to electrolyzers and fuel cells, will help these devices become part of the solution to the looming sustainable energy and chemical production needs. [3] For these devices to be entirely renewable, H 2 (and O 2 ) needs to be produced by water splitting in electrolyzers through H 2 and O 2 evolution (green hydrogen production), rather than from methane reforming (grey hydrogen production). [4,5] H 2 can then be used in electrochemical O 2 reduction in fuel cells to produce electricity. [6,7] Meanwhile, electrochemical reduction of N 2 to NH 3 can provide a sustainable means to a critical fertilization source for the agricultural industry and a carrier for H 2 . [8] Moreover, a way of producing value-added products and a "circular economy" for industry from CO 2 emissions is via the electrocatalytically driven CO 2 reduction, which converts CO 2 to essential feedstocks, such as ethylene or ethanol for the chemical industry. [9] Low-temperature fuel cells and electrolyzers typically utilize catalysts based on platinum group metal (PGM) nanoparticles, [10] which limits device commercialization due to increasing global demand, low uptake of recycling, and high cost of PGMs. [11] Consequently, many researchers have turned their attention to reducing PGM loading or entirely replacing them with lower-cost earth-abundant metals, such as Fe, Cu, Ni, Co, Mn, and, most recently, Sn. [12] Regardless of the catalyst composition, improvements in the electrochemical activity have been highly sought after with two general options available; increasing the number of accessible catalytic sites and/or increasing the intrinsic activity of the catalytic sites. [13] Many different catalyst designs have been explored in order to raise the activity, such as alloying [14] or nanostructuring. [15] While increasing the density of catalytic sites improves activity, this method becomes physically limited when catalyst loading affects charge and mass transport. [13] Thus, improving the activity per catalytic site (intrinsic activity) through controlling local geometry and electronic structure has garnered research attention, with successful methods including shrinking the catalytic site down to atomic scale, as well as locally introducing light heteroatoms or hosting the catalytic site at edges. [10,[16][17][18] Electrochemical clean energy conversion and the production of sustainable chemicals are critical in the journey to realizing a truly sustainable society. To progress electrochemical storage and conversion devices to commercialization, improving the electrocatalyst performance and cost are of utmost importance. Research into dual-metal atom catalysts (DACs) is rising in prominence due to the advantages of these sites over single-metal atom catalysts (SACs), such as breaking scaling ...

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Section: Synthesis Techniquesmentioning

confidence: 68%

Section: Synthesis Techniquesmentioning

confidence: 99%

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Dual‐Metal Atom Electrocatalysts: Theory, Synthesis, Characterization, and Applications

Pedersen

Barrio

et al. 2021

Advanced Energy Materials

104

106

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“…[98] 。为了使产物高水溶性，使用 1，4-二(吡啶-4-基)苯(DPB)单元被甲基化是一个可行的思路。Yang 等人在最近的研究中，用四个中间吡啶亚基的甲基化也有望削弱锌卟啉主链的堆积，以促进双层超分子靶的可控形成，而苯基吡啶亚基的引入有助于增强的分子间聚集，从而产生新的 2D 超分子有机框架 [99] [80] 。Xu 等人在典型的溶剂热条件下缩合得到了具有四方微孔的卟啉基共价骨架 TAPP -TFPP -COF，热重分析表明该晶体结构在 450℃以上仍保持高度稳定 [101] 。Wang 等人构建了基于卟啉基团的三维共价有机框架。实验结构表明所合成的三维体系具有互传拓扑结构，并展现出高表面积。此外，卟啉环的金属化可以对孔径分布有有效的调节作用 [102] [105] 。与传统的粉末-晶体 COF 相比，它们通过溶解-重构机制调控乙酸浓度(5 mL/6 M)，实现了纳米片组成超分子结构。超分子自组装是制备高有序有机功能分子材料的一种重要策略 [57] [106, 107] 。含有卟啉、酞菁结构单元的超分子体系可以与其他功能分子如富勒烯、冠醚、二茂铁等通过非共价键形成更为复杂的多级组装体系。在这一过程中，有效的控制所制备体系的选择性、方向性和稳定性是亟待解决的问题。例如，利用卟啉配合物的特性, 研究金属卟啉与氨基酸、多肽、核酸等生物功能分子的自组装正在引起人们的日益重视, 籍此可望通过人工合成出仿生性高的自组装卟啉超分子体系。更为重要的是：通过不同类型相互作用的协同搭配，可 F o r R e v i e w O n l y 图 5 基于卟啉、酞菁结构的聚集态相貌调控：(a) 纳米线 [104] ; (b) 纳米片 [105] ；(c) 石墨炔/酞菁复合物 [108] ；(d) 卟啉/组氨酸多级自组装结构 [109] Figure 5 Regulation of aggregation state appearance based on porphyrin and phthalocyanine structure:(a) nanowires [104] ; (b) Nanosheets [105] ; (c) graphdiyne/phthalocyanine complex [108] ; (d) Multistage self-assembly structure based on porphyrin and histidine [109]. 以将单一材料体系整合到一个复杂的多级结构中，从而实现特定的功能。近年来，大量报导了以卟啉、酞菁结构单元为砌块, 加入小分子(有机、无机分子)、大环分子(冠醚、富勒烯、环糊精等)及碳基材料等, 通过分子间的弱相互作用的超分子体系。近期，Zhang 等通过无共价键的范德瓦尔斯相互作用，以石墨炔/石墨烯异质结构作为导电骨架来锚定单分散钴酞菁(图 5c) [108] 。在该体系中，三类材料展现出不同的功能：石墨烯为导电层，石墨炔为吸附层，钴酞菁分子作为功能催化层 [110,111] 。特别是石墨炔层提供了特定的螯合位点，有效的抑制了酞菁类分子团聚，大大提高了催化选择性和稳定性 [112][113][114] 。 Liu 等通过卟啉羧基与组氨酸的氢键/静电相互作用制备了多阶手性微米花。手性纳米级和多阶手性微米花与手性组氨酸两亲性分子共组装(图 5d) [109] [46] 。通过有效控制钙钛矿薄膜的结晶和缺陷是影响钙钛矿太阳能电池(PSCs)性能和稳定性的关键因素，特别是对于大面积 PSCs 器件的制备。近期，Cao 等人将表面活性剂类单铵锌卟啉(ZnP) 化合物直接嵌入到甲基铵(MA+)碘化铅钙钛矿薄膜中，形成以叶片状覆盖面积达 16 cm 2 的大面积均匀钙钛矿薄膜。使用 ZnP 制备的叶片涂层大面积(1. 96 F o r R e v i e w O n l y cm 2 ) PSCs 的效率高达 18.3%，而小面积(0.1 cm 2 )器件的效率最高可达 20.5%(图 6) [116] 。图 6 铵基卟啉用于稳定大面积钙钛矿太阳能电池.…”

Section: 平面并在卟啉两侧相连的配位结构。同时，参与配位的金刚烷还能与其中的氮原子与卟啉中间的锌原子配位，从而连接锌卟啉与钌卟...unclassified

Porphyrin and phthalocyanine: from molecular materials to aggregates

Li¹,

Lai²,

Wang³

2022

Sci. Sin.-Chim

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“…45 The coordination-driven approach to prepare the cofacial prism of Figure 1 obviates the complicated syntheses needed to generate other cofacial porphyrinoids and delivers highly selective platforms for ORR catalysis. 46,47 The self-assembly approach requires the "molecular clips" to be based on kinetically inert ions such that eight Ru(II) centers are used for the construction of each catalytically active prism, which increases the cost associated with their fabrication/use.…”

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confidence: 99%

An Easily Prepared Monomeric Cobalt(II) Tetrapyrrole Complex that Efficiently Promotes the 4e–/4H+ Peractivation of O2 to Water

Cai

Tran

Qiu

et al. 2021

Preprint

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The selective 4e–/4H+ reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. How- ever, these systems have been repeatedly shown to be selective for O2 reduction by the less desired 2e –/2H+ pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based upon a non-aromatic isocorrole scaffold that is competent for 4e–/4H+ ORR. This Co(II) 10,10-dimethyl isocorrole (Co[10- DMIC]) is obtained in a just four simple steps and excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co(II) porphyrin ([Co(TPFPP)]) and corrole ([Co(TPFPC)(PPh3)]) homologs demonstrated that the light harvesting and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ~85% selective for the 4e–/4H+ reduction of O2 to H2O over the more kinetically facile 2e–/2H+ process that delivers H2O2. By contrast, the same ORR evaluations conducted for the Co(II) porphyrin and corrole homologs demonstrated that these traditional aromatic systems catalyze the 2e–/2H+ conversion of O2 to H2O2 with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups, ditopic molecular clefts, or which impose cofacially ori- ented O2 binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and which shows a privileged performance for the 4e–/4H+ peractivation of O2 to water as compared to other simple Co(II) tetrapyrroles.

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Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks

Cited by 37 publications

References 51 publications

Dual‐Metal Atom Electrocatalysts: Theory, Synthesis, Characterization, and Applications

Dual‐Metal Atom Electrocatalysts: Theory, Synthesis, Characterization, and Applications

Porphyrin and phthalocyanine: from molecular materials to aggregates

An Easily Prepared Monomeric Cobalt(II) Tetrapyrrole Complex that Efficiently Promotes the 4e–/4H+ Peractivation of O2 to Water

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