Solution-processable porous graphitic carbon from bottom-up synthesis and low-temperature graphitization

Che, Sai; Li, Chenxuan; Wang, Chenxu; Zaheer, Wasif; Ji, Xiaozhou; Phillips, Bailey; Gurbandurdyyev, Guvanch; Glynn, Jessica; Guo, Zihao; Al‐Hashimi, Mohammed; Zhou, Hong‐Cai; Banerjee, Sarbajit; Fang, Lei

doi:10.1039/d1sc01902c

Cited by 21 publications

(28 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Seminal work by Kaskel et al demonstrated that molten p -toluenesulfonic acid and SiCl 4 (under solvothermal conditions) can be used to polymerize diacetylarenes to produce porous organic frameworks by the cyclotrimerization reaction (OFCs) . These and related methods have subsequently been employed to prepare a range of porous organic materials. − However, these polymers likely contain mixtures of dimerized α,β-unsaturated ketones and cyclotrimerized 1,3,5-substituted arenes (Figure a), as evidenced by residual carbonyl stretches in their infrared (IR) spectra . Likewise, the polymerization of triacetylarenes on Ag(111) surfaces was found to produce mixtures of dimers and cyclic trimers .…”

Section: Introductionmentioning

confidence: 99%

Conjugated Microporous Polymers via Solvent-Free Ionothermal Cyclotrimerization of Methyl Ketones

et al. 2021

View full text Add to dashboard Cite

Conjugated microporous polymers (CMPs) are porous organic materials that display (semi)conducting behavior due to their highly π-conjugated structures. As such, they are promising next-generation materials for applications requiring both conductivity and porosity, such as supercapacitive energy storage and electrochemical sensing. However, most CMPs and related porous aromatic frameworks (PAFs) are currently prepared using expensive transition metal-based catalysts under solvothermal conditions, significantly increasing their manufacturing costs. Herein, we demonstrate that the ionothermal cyclotrimerization of methyl ketones via the aldol reaction represents a new strategy for the solvent-free synthesis of CMPs and PAFs. Specifically, we show that 1,3,5-triacetylbenzene and tetrakis(4-acetylphenyl)methane can be polymerized in molten zinc chloride to produce highly conjugated and microporous materials, as confirmed by 77 K N 2 adsorption measurements in conjunction with UV−vis, Raman, and solid-state NMR spectroscopies. The CMP prepared from 1,3,5-triacetylbenzene demonstrates higher charge storage capacities (up to 172 F/g) than a commercially available supercapacitor carbon, reflecting the promise of cyclotrimerized CMPs for electrical energy storage applications.

show abstract

Section: Introductionmentioning

confidence: 99%

Conjugated Microporous Polymers via Solvent-Free Ionothermal Cyclotrimerization of Methyl Ketones

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Two characteristic peaks at 1350 and 1580 cm –1 were present in all four materials, which were assigned to D band and G band, respectively. In general, D band represents the edges and defects in carbon structures, which benefits the electrocatalytic performance by exposing more active sites . G band corresponds to the sp 2 hybridized graphitic carbons that provide the conductive backbone.…”

Section: Resultsmentioning

confidence: 99%

“…In general, D band represents the edges and defects in carbon structures, which benefits the electrocatalytic performance by exposing more active sites. 46 G band corresponds to the sp 2 hybridized graphitic carbons that provide the conductive backbone. After surface phosphidation, I D /I G ratios of Ni 2 P/NPC-P and Ni/NPC-P increased significantly compared to the corresponding precursors.…”

Section: Methodsmentioning

confidence: 99%

Highly Efficient Water Splitting Catalyst Composed of N,P-Doped Porous Carbon Decorated with Surface P-Enriched Ni₂P Nanoparticles

Yan

Che

Yang

et al. 2021

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

A non-noble-metal hybrid catalyst (Ni 2 P/NPC-P), composed of N,P-doped porous carbon decorated with surface P-enriched Ni 2 P nanoparticles, is developed to address the urgent challenges associated with mass production of clean hydrogen fuel. The synthesis features one-pot pyrolysis of inexpensive fluid catalytic cracking slurry, graphitic carbon nitride, and inorganic salts, followed by a feasible surface phosphidation process. As a non-noble metal catalyst, Ni 2 P/NPC-P demonstrates excellent performance in hydrogen evolution reaction in alkaline electrolytes with a low overpotential of 73 mV at a current density of 10 mA cm −2 (η 10 ) and a small Tafel slope of 56 mV dec −1 , meanwhile exhibits durability with no significant η 10 change after 2000 catalytic cycles. Theoretical calculation reveals that the negatively charged P-enriched surface accelerated the rate-determining transformation and desorption of OH*. In overall water splitting, the electrocatalyst achieves a low η 10 of 1.633 V, promising its potential in the cost-effective mass production of hydrogen fuel.

show abstract

“…The Brunauer–Emmett–Teller (BET) specific surface area of CoP@NC/GR heterostructures was 82.2 m 2 g –1 , while a wide distribution in the range from 1.8 to 233 nm, mainly concentrated in 8–63 nm, indicates the existence of the unique microporous/mesoporous/macroporous composite structure (Figure e). Raman spectra of CoP@NC/GR were analyzed to obtain further insight into the heterostructures (Figure f), which displayed two prominent peaks at 1355 and 1582 cm –1 , corresponding to the structural defects induced by disordered sp 3 -stretching carbon (D band) and ordered sp 2 -stretching graphitic carbon (G band). − Compared with NC/GR, the bigger I D / I G value of CoP@NC/GR implies increased structural defects caused by the encapsulated CoP NPs.…”

Section: Resultsmentioning

confidence: 99%

Active Site Engineering in CoP@NC/Graphene Heterostructures Enabling Enhanced Hydrogen Evolution

et al. 2021

View full text Add to dashboard Cite

As the core of an electrocatalyst, the active site is critical to determine its catalytic performance in the hydrogen evolution reaction (HER). In this work, porous N-doped carbon-encapsulated CoP nanoparticles on both sides of graphene (CoP@ NC/GR) are derived from a bimetallic metal−organic framework (MOF)@graphene oxide composite. Through active site engineering by tailoring the environment around CoP and engineering the structure, the HER activity of CoP@NC/GR heterostructures is significantly enhanced. Both X-ray photoelectron spectroscopy (XPS) results and density functional theory (DFT) calculations manifest that the electronic structure of CoP can be modulated by the carbon matrix of NC/GR, resulting in electron redistribution and a reduction in the adsorption energy of hydrogen (ΔG H* ) from −0.53 to 0.04 eV. By engineering the sandwich-like structure, active sites in CoP@NC/GR are further increased by optimizing the Zn/Co ratio in the bimetallic MOF. Benefiting from this active site engineering, the CoP@NC/GR electrocatalyst exhibits small overpotentials of 105 mV in 0.5 M H 2 SO 4 (or 125 mV in 1 M KOH) to 10 mA cm −2 , accelerated HER kinetics with a low Tafel slope of 47.5 mV dec −1 , and remarkable structural and HER stability.

show abstract

Solution-processable porous graphitic carbon from bottom-up synthesis and low-temperature graphitization

Abstract: It is urgently desired yet challenging to synthesize porous graphitic carbon (PGC) in a bottom-up manner while circumventing the need for high-temperature pyrolysis. Here we present an effective and scalable...

Cited by 21 publications

References 61 publications

Conjugated Microporous Polymers via Solvent-Free Ionothermal Cyclotrimerization of Methyl Ketones

Conjugated Microporous Polymers via Solvent-Free Ionothermal Cyclotrimerization of Methyl Ketones

Highly Efficient Water Splitting Catalyst Composed of N,P-Doped Porous Carbon Decorated with Surface P-Enriched Ni₂P Nanoparticles

Active Site Engineering in CoP@NC/Graphene Heterostructures Enabling Enhanced Hydrogen Evolution

Contact Info

Product

Resources

About

Solution-processable porous graphitic carbon from bottom-up synthesis and low-temperature graphitization

Abstract: It is urgently desired yet challenging to synthesize porous graphitic carbon (PGC) in a bottom-up manner while circumventing the need for high-temperature pyrolysis. Here we present an effective and scalable...

Cited by 21 publications

References 61 publications

Conjugated Microporous Polymers via Solvent-Free Ionothermal Cyclotrimerization of Methyl Ketones

Conjugated Microporous Polymers via Solvent-Free Ionothermal Cyclotrimerization of Methyl Ketones

Highly Efficient Water Splitting Catalyst Composed of N,P-Doped Porous Carbon Decorated with Surface P-Enriched Ni2P Nanoparticles

Active Site Engineering in CoP@NC/Graphene Heterostructures Enabling Enhanced Hydrogen Evolution

Contact Info

Product

Resources

About

Highly Efficient Water Splitting Catalyst Composed of N,P-Doped Porous Carbon Decorated with Surface P-Enriched Ni₂P Nanoparticles