Facile diazonium modification of pomegranate peel biochar: a stupendous derived relationship between thermal and Raman analyses

Khalil Ahmed M.,Msaadi Radhia,Sassi Wafa,Ghanmi Imen,Pires Rémy,Michely Laurent,Snoussi Youssef,Chevillot-Biraud Alexandre,Lau-Truong Stéphanie,Chehimi Mohamed M. 한국탄소학회 2022 Carbon Letters Vol.32 No.6

There is an ever growing interest in the development of biochar from a large variety of agrowastes. Herein, the main objective is the conversion of pomegranate peel powder biochar and its post-functionalization by phosphoric acid treatment, followed by arylation organic reaction. The latter was conducted using in situ-generated diazonium salts of 4-aminobenzoic acid (H2N-C6H4-COOH), sulfanilic acid (H2N-C6H4-SO3H) and Azure A dye. The effect of diazonium nature and concentration on the arylation process was monitored using thermal gravimetric analysis (TGA) and Raman spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). SEM pictures showed micrometer-sized biochar particles with tubular structure having about 10–20 µm-wide channels. SEM studies have shown that arylation did not affect the morphology upon arylation. The porous structure did not collapse and withstood the arylation organic reaction in acid medium did not collapse upon arylation. TGA and Raman indicated gradual changes in the arylation of biochar at initial concentrations 10–5, 10–4 and 10–3 mol L−1 of 4-aminobenzoic acid. The detailed Raman spectra peak fittings indicate that the D/G peak intensity ratio leveled off at 3.35 for 4-aminobenzoic acid initial concentration of 10–4 mol L−1, and no more change was observed, even at higher aryl group mass loading. This is in line with formation of oligoaryl grafts rather than the grafting of new aryl groups directly to the biochar surface. Interestingly, Azure A diazonium salt induced much lower extent of surface modification, likely due to steric hindrance. To the very best of our knowledge, this is the first report on diazonium modification of agrowaste-derived biochar and opens new avenues for arylated biochar and its applications.

Azoic Deep Dyeing of Silk and UV Protection Using Plant Polyphenols and Diazonium Coupling

Nattaya Vuthiganond,Monthon Nakpathom,Rattanaphol Mongkholrattanasit 한국섬유공학회 2020 Fibers and polymers Vol.21 No.5

This study investigated azoic dyeing as an approach to improving the natural dyeability of silk fabric whileavoiding the use of metallic mordants, which are toxic to health and the environment. An aryl diazonium salt was preparedfrom p-nitroaniline and used to couple with silk fabric pretreated with plant polyphenols. The interaction triggered in situproduction of azo dye within the silk fibers. This dyeing approach was demonstrated to overcome the poor tinctorial strengthand fastness of natural dyes. Plant polyphenols were extracted from oolong tea and mangrove bark. The CIE L*a*b* and K/Svalues were measured, and compared with the results of post-mordant dyeing using aluminum potassium sulfate. Even at lowconcentrations, aryl diazonium salt was shown to achieve deep dyeing, producing an intense brown/orange shade. The effectof azoic dyeing on color strength was strongly dependent on the primary aromatic amine concentration. At 7 % owf, theoolong tea extract produced a K/S value approximately six times that of the comparable post-mordant sample, and themangrove bark extract approximately three times. The grater color strength achieved by the tea extract was due to the higherTPC concentration. The natural extracts conferred UV protection greater than 50 in all dyeing processes.

Facile CH arylation using catalytically active terminal sulfurs of 2 dimensional molybdenum disulfide

Hwang, Eunhee,Mi Lee, Sae,Bak, Sora,Min Hwang, Hee,Kim, Hyunjung,Lee, Hyoyoung Elsevier 2018 Tetrahedron letters: the international organ for t Vol.59 No.44

<P><B>Abstract</B></P> <P>The first methodology of CH arylation of heteroarene via 2D transition metal dichalcogenides that have catalytically active edge functional groups was described. The terminal sulfur groups could effectively catalyze a formation of an azo-linked intermediate with aryl diazonium salts, leading to produce heteroarenes with good yields. This novel methodology using bulk 2D transition metal dichalcogenides that have catalytically active edge functional groups can apply for various reactions to achieve CC bond formation in the fields of heterogeneous catalysis that is easily separable, highly reusable, and inexpensive method.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Unprecedented MoS<SUB>2</SUB> catalyzed for direct CH arylation. </LI> <LI> Catalytically active terminal sulfurs of MoS<SUB>2</SUB> for CH arylation. </LI> <LI> High reusability and simple separation of heterogeneous catalyst. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

테트라플루오로보론산 3-클로로벤젠다이아조늄으로부터 아라인 첨가생성물 생성 반응 조건 연구(1)

양일우 ( Yang Il U ),정영진 ( Jeong Yeong Jin ) 한국공업화학회 2003 공업화학 Vol.14 No.5

테트라플루오로보론산 3-클로로벤젠다이아조늄과 초한 칼륨염의 반응을 벤젠 용매에서 18-크라운-6와 테트라페닐사이클로펜타다이인온(TPCP) 존재하에 실시하여 아라인 첨가 생성물인 5-클로로-1,2,3,4-테트라페닐나프탈린을 얻었으며 반응의 수득율은 반응 조건에 따라 달라짐을 확인하였다. 본 연구에서 18-크라운-6는 이온성 고체 반응물들인 테트라플루오로보론산 3-클로로벤젠다이아조늄과 유기산의 칼륨염을 비극성 유기 용매층으로 이동시키는 상이동 촉매로 사용된 것이며, TPCP는 효과적인 아라인 포획물질로서 [4+2] 사이클로 첨가반응 메카니즘을 따라 아라인의 첨가생성물을 형성케 하였다. 본 실험을 통하여 조사된 반응 조건들은 반응 온도 그리고 반응물간의 몰비 관계를 조사하였다. 3-클로로벤젠다이아조늄염과 초산 칼륨의 상이동 촉매반응을 환류조건에서 실시하면 동일한 반응을 실온에서 수행했을 때 보다 아라인 첨가 생성물의 수득율이 28% 증가된 73%로 얻었다. 다이아조늄염 : 초산 칼륨염 : TPCP : 18-크라운-6 간의 최적 몰수비가 1:1:0.5:0.03 이었을 때 가장 높은 첨가 생성물의 수득율을 나타내었다. Reactions of 3-chlorobenzenediazonium tetrafluoroborate with potassium acetate in the presence of 18-crown-6 and tetraphenylcyclo-pentadienone (TPCP) were investigated and found the formation of aryne adduct, 5-chloro-1,2,3,4-tetraphenylnaphtha-lene in poor to reasonable yield according to reaction conditions employed. In these reaction, 18-crown-6 was used as a phase transfer catalyst (PTC) for transfering solid ionic reactants into nonpolar solvent layer, and TPCP was used as an effective aryne scavenger to form an adduct by thermal [4+2] cycloaddition. The reaction was studied on the various temperature and molar ratio of reactants. When the reaction run in higher temperature, the yield increased up to 28%. It was found that the optimum molar ratio of reactants, diazonium salts : potassium acetate : TPCP : 18-crown-6 should be 1 : 1 : 0.5 : 0.03 for the maximum yield 73% of aryne adduct.

Tunable Sub-nanopores of Graphene Flake Interlayers with Conductive Molecular Linkers for Supercapacitors

Lee, Keunsik,Yoon, Yeoheung,Cho, Yunhee,Lee, Sae Mi,Shin, Yonghun,Lee, Hanleem,Lee, Hyoyoung American Chemical Society 2016 ACS NANO Vol.10 No.7

<P>Although there are numerous reports of high performance supercapacitors with porous graphene, there are few reports to control the interlayer gap between graphene sheets with conductive molecular linkers (or molecular pillars) through a pi-conjugated chemical carbon-carbon bond that can maintain high conductivity, which can explain the enhanced capacitive effect of supercapacitor mechanism about accessibility of electrolyte ions. For this, we designed molecularly gap-controlled reduced graphene oxides (rGOs) via diazotization of three different phenyl, biphenyl, and para-terphenyl bis-diazonium salts (BD1-3). The graphene interlayer sub-nanopores of rGO-BD1-3 are 0.49, 0.7, and 0.96 nm, respectively. Surprisingly, the rGO-BD2 0.7 nm gap shows the highest capacitance in 1 M TEABF(4) having 0.68 nm size of cation and 6 M KOH having 0.6 nm size of hydrated cation. The maximum energy density and power density of the rGO-BD2 were 129.67 W h kg(-1) and 30.3 kW kg(-1), respectively, demonstrating clearly that the optimized sub-nanopore of the rGO-BDs corresponding to the electrolyte ion size resulted in the best capacitive performance.</P>

3D 프린팅을 이용한 샤워기용 항균 볼의 제조 및 항균 평가

김재현,박지희,박수민,이인수,김운중,정종진 K-뷰티인그리에경영학회(구 한국인그리에학회) 2020 한국인그리에학회지 Vol.2 No.2

Anomalously Large Reactivity of Single Graphene Layers and Edges toward Electron Transfer Chemistries

Sharma, Richa,Baik, Joon Hyun,Perera, Chrisantha J.,Strano, Michael S. American Chemical Society 2010 NANO LETTERS Vol.10 No.2

<P>The reactivity of graphene and its various multilayers toward electron transfer chemistries with 4-nitrobenzene diazonium tetrafluoroborate is probed by Raman spectroscopy after reaction on-chip. Single graphene sheets are found to be almost 10 times more reactive than bi- or multilayers of graphene according to the relative disorder (<I>D</I>) peak in the Raman spectrum examined before and after chemical reaction in water. A model whereby electron puddles that shift the Dirac point locally to values below the Fermi level is consistent with the reactivity difference. Because the chemistry at the graphene edge is important for controlling its electronic properties, particularly in ribbon form, we have developed a spectroscopic test to examine the relative reactivity of graphene edges versus the bulk. We show, for the first time, that the reactivity of edges is at least two times higher than the reactivity of the bulk single graphene sheet, as supported by electron transfer theory. These differences in electron transfer rates may be important for selecting and manipulating graphitic materials on-chip.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/nalefd/2010/nalefd.2010.10.issue-2/nl902741x/production/images/medium/nl-2009-02741x_0009.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/nl902741x'>ACS Electronic Supporting Info</A></P>

Air and moisture stable robust bio-polymeric palladium catalyzed C-C bond formation and its application to the synthesis of fungicidal

Ke Chen,Guangzu He,Qiong Tang 한국공업화학회 2023 Journal of Industrial and Engineering Chemistry Vol.124 No.-

Cellulose supported bio-heterogeneous polymeric Pd(II) catalyst, stable to air and moisture, was designedand characterized with different spectroscopic techniques including FESEM, TEM, XPS, XRD, ICP-AES andEDX. The Pd(II) catalyst showed high catalytic performance (0.2 to 0.0009 mol%) to the Suzuki-MiyauraCAC cross-coupling reaction of aromatic halides and aryl diazonium salts with a range of organoboronicacids to produce the respective biaryl product in up to 97% yield. Biologically active Boscalid, a fungicidethat effectively inhibits the growth of fungal pathogens like ascomycetes on fruits and plants, could alsobe constructed through using this catalyst. Additionally, it was possible to recover the Pd(II) catalyst fromthe reaction medium and reused it repeatedly without significantly degrading its catalytic efficiency.

A Three-Bath Process for Dyeing Cotton with Bis-Azo Bi-Functional Reactive Dyes Based on Diazonium Salts

P. R. Hande,P. P. Badve,R. G. Dugane,S. S. Bhagwat,P. M. Bhate 한국섬유공학회 2020 Fibers and polymers Vol.21 No.12

Mono-azo dyes possessing a primary aromatic amino group have been shown to react with cotton by diazotizationfollowed by treatment with soda ash at 60-65 °C thereby acting as monofunctional reactive dyes. Bis-azo dyes bearing twoamino groups are expected to act as bi-functional reactive dyes and exhibit enhanced dye-cellulose fixation. This work showsthat the difference in fixation exhibited by mono-azo and bis-azo dyes is statistically significant at 95 % confidence level infavor of the latter group. This work describes a three-bath dyeing process which reduced the amount of consumed water by60.6 % and the environment factor by 62.2 %. The newly developed three-bath process also conserves energy by 74.1 %. Hence, a new class of bifunctional reactive dyes without externally attached reactive systems is, in principle, available. It willhave the advantage of reducing raw materials and manufacturing costs. It also employs a sustainable reactive dyeing process.

단신 : 테트라플루오로보론산 3-클로로벤젠다이아조늄으로부터 아라인 첨가생성물 생성 반응 조건 연구(2)

양일우 ( Yang Il U ),정영진 ( Jeong Yeong Jin ) 한국공업화학회 2003 공업화학 Vol.14 No.7