Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution on Phosphorus-Doped Covalent Triazine-Based Frameworks

Cheng, Zhi; Fang, Wei; Zhao, Tiansu; Fang, Shengqiong; Bi, Jinhong; Liang, Shijing; Li, Liuyi; Yu, Yan; Wu, Ling

doi:10.1021/acsami.8b16013

Cited by 90 publications

(67 citation statements)

References 42 publications

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“…Under AM 1.5 G irradiation and at 0.3 V versus RHE, the three 2D conjugated polymers on fluorine‐doped tin oxide (FTO) electrodes show photocurrents of ≈5.5 µA cm −2 for 2D CCP‐Th, ≈2.8 µA cm −2 for 2D CCP‐BD, and ≈0.06 µA cm −2 for 2D CN COF‐B ( Figure a,b). Moreover, 2D CCP‐Th achieves a photocurrent of ≈7.9 µA cm −2 at 0 V versus RHE, which exceeds those of the reported 2D COFs (0.09–6.0 µA cm −2 ) [ 8,9,13,27–32 ] and most carbon nitride materials (g‐C 3 N 4 , 0.3–1.2 µA cm −2 ) (Table S6, Supporting Information). [ 33–37 ] As a key parameter to evaluate the intrinsic PEC performance of photoelectrode materials, the incident‐photon‐to‐current efficiency (IPCE) was measured (Figure S30, Supporting Information).…”

Section: Figurementioning

confidence: 79%

“…Benefitting from the D–A structure, the bithiophene‐bridged 2D CCP‐Th shows a much narrower optical energy bandgap (2.04 eV), a higher‐lying LUMO energy level (−3.41 eV), and higher charge separation and transport than those of biphenyl‐bridged 2D CCP‐BD and 2D CN COF‐B. Therefore, as the cathode material for PEC water reduction, 2D CCP‐Th demonstrates a superb saturated photocurrent density up to 5.5 µA cm −2 at 0.3 V and 7.9 µA cm −2 at 0 V versus reversible hydrogen electrode (RHE), which is superior to the reported 2D COFs [ 8,9,13,27–32 ] and most carbon nitride (g‐C 3 N 4 ) materials (0.09–6.0 µA cm −2 ) [ 33–37 ] (Table S6, Supporting Information). Furthermore, density functional theory (DFT) simulations further suggest that the sulfur atoms in the thiophene as well as the cyano groups at the vinylene linkage serve as the active sites for water reduction.…”

Section: Figurementioning

confidence: 99%

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Thiophene‐Bridged Donor–Acceptor sp²‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

et al. 2020

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Photoelectrochemical (PEC) water reduction, which can convert solar energy into clean, storable hydrogen fuel, has attracted considerable attention to address energy and environmental issues. [1-3] A PEC water splitting cell is an innovative H 2-production device consisting of solar energy collection (semiconductors) and water electrolysis (catalysts) units. [4-6] Principally, the semiconductors need to comply with several requirements for efficient PEC applications, such as a wide-range light harvesting ability, efficient charge transfer, corrosion stability, and a higher-lying lowest unoccupied molecular orbital (LUMO) energy level than the reduction potential of the proton (H + /H 2). [1,7] 2D covalent organic frameworks (2D COFs), as crystalline, layer-stacked, 2D porous polymers, have emerged as a promi sing class of materials for photocatalysis and PEC applications recently. [3,8-12] Their energy bandgaps, positions of the frontier orbitals, and active centers can be facilely tailored by bottom-up organic synthesis with abundant building blocks, linkages, and topologies. [6,13,14] In particular, 2D π-conjugated COFs, which belong to the class of 2D conjugated polymers, show notable advantages for PEC applications due to the π-stacked columns Photoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene-bridged donor-acceptorbased 2D sp 2-carbon-linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron-accepting building block 2,3,8,9,14,15-hexa(4-formylphenyl) diquinoxalino[2,3a:2′,3′-c]phenazine (HATN-6CHO) and the first electron-donating linker 2,2′-([2,2′-bithiophene]-5,5′-diyl)diacetonitrile (ThDAN) provides the 2D CCP-HATNThDAN (2D CCP-Th). Compared with the corresponding biphenyl-bridged 2D CCP-HATN-BDAN (2D CCP-BD), the bithiophenebased 2D CCP-Th exhibits a wide light-harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital-lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP-Th a promising candidate for PEC water reduction. As a result, 2D CCP-Th presents a superb H 2-evolution photocurrent density up to ≈7.9 µA cm −2 at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09-6.0 µA cm −2). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H 2. The ORCID identification number(s) for the author(s) of this article can be found under

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Section: Figurementioning

confidence: 79%

Section: Figurementioning

confidence: 99%

Thiophene‐Bridged Donor–Acceptor sp²‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

et al. 2020

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“…Together with the nitrogen rich backbone, tunable band gap and energy levels, this makes CTFs interesting candidates for photocatalytic CO2 reduction and water splitting. 14,15,177,182,184,[189][190][191][192] This feasibility was initially predicted by calculations and it was observed that the band gap of these semiconducting materials should decrease with decreasing nitrogen content in the structures. 193 At the same time, a smaller pore size was calculated to induce a larger band gap by quantum confinement effects.…”

Section: <Table 3>mentioning

confidence: 86%

Polymer photocatalysts for solar-to-chemical energy conversion

et al. 2020

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Solar-to-chemical energy conversion for the generation of high energy chemicals is one of the most viable, non-intermittent solutions to the present-day lookout for sustainable energy resources. Recently, organic polymeric photocatalysts have garnered significant attention in this field of research, which has long been dominated by inorganic semiconductors. Revisiting the lessons learnt from the latter, we reevaluate the fundamental concepts of photocatalysis in the context of the different classes of polymeric photocatalysts known to date, ranging from carbon nitrides and conjugated polymers, to covalent triazine frameworks and covalent organic frameworks. We then analyze the photophysical and physicochemical concepts that govern the photocatalytic performance of these materials, and thereby derive pertinent design principles and possible future research directions in this emerging field of "soft photocatalysis".

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“…Heteroatom substitution vary the charge polarity of COFs efficiently and then affects the charges transfer and the band structures of polymers. Both sulfur‐doped CTFs (CTFS 10 ) and phosphorus‐doped CTFs (P 5 CTF‐1) delivered higher photocatalytic hydrogen activity than the pristine CTFs.…”

Section: Photochemical Applicationsmentioning

confidence: 99%

Stable Covalent Organic Frameworks for Photochemical Applications

Guo

Jin

2019

ChemPhotoChem

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Covalent organic frameworks (COFs) are a type of intriguing crystalline porous network material which has attracted extensive research attention in many fields. In particular, the crystalline and designable structures which can be constructed with diverse building blocks and topologies endow covalent organic frameworks (COFs) with high photoconductivity and multiple potential applications in photochemistry. The chemical stability of the host COF is fundamental to guarantee the durability of the photocatalytic performance, which can be realized by robust linkages. For this reason, significant attention has recently focused on the development of stable COFs. Herein, advances achieved in the development of stable COFs for photochemical applications are described, including photocatalytic hydrogen production and reduction of CO 2 , photocatalytic organic reaction transformations, photocatalytic environmental remediation, and other applications. Furthermore, the future of COFs for application in photocatalysis are discussed.[a] L.

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Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution on Phosphorus-Doped Covalent Triazine-Based Frameworks

Cited by 90 publications

References 42 publications

Thiophene‐Bridged Donor–Acceptor sp²‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Thiophene‐Bridged Donor–Acceptor sp²‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Polymer photocatalysts for solar-to-chemical energy conversion

Stable Covalent Organic Frameworks for Photochemical Applications

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Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution on Phosphorus-Doped Covalent Triazine-Based Frameworks

Cited by 90 publications

References 42 publications

Thiophene‐Bridged Donor–Acceptor sp2‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Thiophene‐Bridged Donor–Acceptor sp2‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Polymer photocatalysts for solar-to-chemical energy conversion

Stable Covalent Organic Frameworks for Photochemical Applications

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Thiophene‐Bridged Donor–Acceptor sp²‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Thiophene‐Bridged Donor–Acceptor sp²‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction