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JOURNAL OF ORGANOMETALLIC CHEMISTRY · 2023 · IF 2.3

Pincer-type complexes with B(3)-H selective bond activation of m-carborane

Run-Ze Yuan,Peng-Fei Cui,Guo-Xin Jin

Herein, we describe the synthesis of a series pincer-type half-sandwich complexes containing selective B(3)-H activation of m -carborane. Four pincer-type complexes containing Cp*M (M = Ir/Rh) and (η 6 -pcym)Ru metal-corner, ionic Cp*M[ m -C 2 B 10 H 9 (CS 2 CH 3 ) 2 ](CF 3 SO 3 ) (M = Ir ( 2 ), Rh ( 3 )), (η 6 -pcym)Ru[ m -C 2 B 10 H 9 (CS 2 CH 3 ) 2 ](CF 3 SO 3 ) ( 4 ) and neutral solvolysis product Cp*Ir[ m -C 2 B 10 H 9 (CS 2 CH 3 )(COS)] (Complex 5 ), have been prepared. The addition reaction of MeO − toward 2 3 and 4 causes the formation of moderately stable neutral unsymmetrical pincer-type complexes Cp*M{ m -C 2 B 10 H 9 (CS 2 CH 3 )[CS(SCH 3 )(OCH 3 )]} (M = Ir ( 6 ), Rh ( 7 )) and (η 6 -pcym)Ru{ m -C 2 B 10 H 9 (CS 2 CH 3 )[CS(SCH 3 )(OCH 3 )]} ( 8 ). The substitution reaction of 2 3 and 4 have also been also explored, unsymmetrical chelate complexes Cp*M( t BuNC)[ m -C 2 B 10 H 9 (CS 2 CH 3 ) 2 ](BPh 4 ) (M = Ir ( 9 ), Rh ( 10 )) can be obtained by using t BuNC and NaBPh 4 . All of these complexes have been characterized, including X-Ray single crystal diffraction, NMR spectroscopy, IR spectroscopy and elemental analysis methods.

研究领域: 无机化学 · 配位化学
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JOURNAL OF RARE EARTHS · 2022 · IF 4.632

La2O3-promoted Ni/H-ZSM-5 catalyzed aqueous-phase guaiacol hydrodeoxygenation to cyclohexanol

Feng Lin,Yudan Zhong,Yulong Ma,Yonggang Sun,Xiuqin Men,Yingbo Zhu

Hydrodeoxygenation (HDO) of renewable lignin-derived biomass in aqueous-phase to produce high value-added products is of great significance. However, developing new catalysts with high activity and excellent stability in an aqueous phase faces considerable challenges. Rare earth doping can effectively regulate the water exchange rate constant (WERC) value of the catalyst and play an important role in promoting the hydrolysis of ether bonds. Therefore, in this paper the bimetallic supported catalyst Ni–La 2 O 3 /H-ZSM-5 doped with rare earth metal La 2 O 3 was prepared, and used to catalyze the conversion of the lignin model compound guaiacol to cyclohexanol in the aqueous phase. The conversion of guaiacol catalyzed by 10Ni–3La 2 O 3 /H-ZSM-5 reaches 100%, and the selectivity of the product cyclohexanol is 85%. A series of characterizations illustrate that the doping of La 2 O 3 causes the electron transfer between La 2 O 3 –Ni and changes the distribution of Ni, and a strong metal carrier interaction occurs between the bimetallic Ni–La 2 O 3 and H-ZSM-5. This can effectively promote the hydrolysis of the C–O ether bond in guaiacol and significantly improve the activity of the catalyst. The possible catalytic reaction mechanism of Ni–La 2 O 3 /H-ZSM-5 catalytic conversion of guaiacol was proposed.

CAS / MDL: 90-05-1 10277-43-7
研究领域: 催化化学 · 生物质转化 · 能源化学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2019 · IF 4.084

Cu-MOF assisted synthesis of CuS/CdS(H)/CdS(C): Enhanced photocatalytic hydrogen production under visible light

Liangfeng Luo,Yidi Wang,Siping Huo,Peng Lv,Jun Fang,Yang Yang,Bin Fei

CuS/CdS(H)/CdS(C) photocatalysts were synthesized via the hydrothermal method by employing thiourea , Cd(CH 3 COO) 2 ·3H 2 O and copper 1,4-benzenedicarboxylate MOF (CuBDC). The photocatalysts were characterized by XRD , XPS , BET, TEM and UV–vis diffuse reflectance spectra. Interestingly, hexagonal CdS (CdS(H)) and cubic CdS (CdS(C)) were formed with phase junctions in one step when CuBDC was introduced in the synthesis process, in addition, CuS nanoparticles were deposited on CdS. However, only hexagonal CdS was obtained without CuBDC. It demonstrated that CuBDC was not only the precursor of CuS but also the structural modifier for CdS. With the reduction of re-combination of photo-induced electrons and holes caused by phase junctions and the enhancement of visible-light absorptions due to the loading of CuS, all CuS/CdS(H)/CdS(C) photocatalysts had higher photocurrent densities under visible-light irradiation, and consequently the higher rates of H 2 production than pure CdS(H). Typically, the catalyst with 2.89 wt% of Cu showed a highest rate of H 2 evolution at 2042 μmol/g/h.

CAS / MDL: 10031-43-3
研究领域: 材料科学 · 能源科学
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Frontiers of Chemical Science and Engineering · 2024 ·Vol. 18 ·期 10 ·1-10 · IF 4.3

Rhodium complex-anchored and supramolecular polymer-grafted CdS nanoflower for enhanced photosynthesis of H2O2 and photobiocatalytic C-H bond oxyfunctionalization

Jia Hongwei,Yue Xiaoyang,Hou Yuying,Huang Fei,Cao Cuiyao,Jia Feifei,Liu Guanhua,Zheng Xiaobing,Liu Yunting,Jiang Yanjun

Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp 3 )-H bonds using only H 2 O 2 as a clean oxidant, while also exhibiting sensitivity to H 2 O 2 concentration. CdS-based semiconductors are promising for the photosynthesis of H 2 O 2 owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process, however, they suffer from fast H 2 O 2 decomposition on the surface of pristine CdS. Therefore, [Cp*Rh(bpy)H 2 O] 2+ , a highly selective proton-coupled electron transfer catalyst, was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H 2 O 2 , mitigating the surface issue of pristine CdS, increasing light absorption, accelerating photonic carrier separation, and enhancing oxygen reduction reaction selectivity to H 2 O 2 . This photocatalyst promoted the light driven H 2 O 2 generation rate up to 1345 µmol·L −1 ·g −1 ·h −1 , which was 2.4 times that of pristine CdS. The constructed heterojunction photocatalyst could supply H 2 O 2 in situ for nonspecific peroxygenases to catalyze the C-H oxyfunctionalization of ethylbenzene, achieving a yield of 81% and an ee value of 99% under optimum conditions. A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system, achieving the corresponding chiral alcohols in good yield (51%–88%) and excellent enantioselectivity (90%–99% ee).

研究领域: 生物化学 · 材料科学 · 催化化学
✓ 已验证 DOI 高影响因子
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CERAMICS INTERNATIONAL · 2020 · IF 3.83

Addition of h-BN for enhanced machinability and high mechanical strength of AlN/Mo composites

Yunzi Li,Fei Chen,Xiaoyu Li,Qiang Shen,Lianmeng Zhang

Ceramic/metal composites, as high-temperature structural materials, have limited applications because of their poor machinability . AlN/Mo/Mo 2 B machinable composites were fabricated by adding h-BN to AlN/Mo composites by plasma-activated sintering at various temperatures and at an axial pressure of 30 MPa under argon atmosphere. The sample sintered at 1500 °C exhibited excellent machinability for cemented carbide tools, with a bending strength of approximately 500 MPa and a Vickers hardness value of 9.34 GPa. The effects of sintering temperature on the microstructure, mechanical properties, and machinability were investigated, and the reactions introduced by adding h-BN were studied. These reactions reinforced the composite and newly introduced a Mo 2 B phase, which showed better ability to deflect cracks and prevent them from moving deep inside the composite, thus improving its machinability. This research provides a possible solution for improving the machinability of ceramic/metal composites without sacrificing the strength .

研究领域: 材料科学 · 机械工程
✓ 已验证 DOI 高影响因子
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PROGRESS IN ORGANIC COATINGS · 2024 · IF 6.5

Enhanced mechanical and tribological performance of epoxy nanocomposite coating by non-covalent bonded h-BN nanosheets/graphene oxide

Beibei Chen,Wenquan Dong,Wenchao Shi,Xuanlin Li,Bi Yang,Yang Tong,Lin Zhang,Jianzhang Wang

Developing high-performance of organic solid lubricating coating is of great significance for extending the life of the moving systems/parts. Herein, the non-covalently modified h-BN nanosheets by graphene oxide (BNNSs/GO) were elaborately constructed to enhance the mechanical, friction and wear properties of epoxy nanocomposite coating. The microstructure feature and chemical composition of BNNSs/GO were determined by various spectroscopic techniques. The tribological performance of nanocomposite coatings were tested using ball-on-disc friction tester, and 440C stainless-steel ball with diameter of 8 mm was used as the counterface material. The GO nanosheets acted an active platform for BNNSs, which improved the dispersion of BNNSs and interface interaction with epoxy. The anchoring BNNSs could break the strong π-π, and van der Walls forces among GO nanosheets. The thickness of epoxy nanocomposite coatings was about 60 μm. And the epoxy-1.0 wt%BNNSs/GO demonstrated much higher hardness and elastic modulus than epoxy, increased by 112.62 % and 53.37 %, respectively. The coefficient of friction (COF) and wear rate of epoxy-1.0 wt%BNNSs/GO were the lowest, with a reduction of 89.7 % and 97.5 %, respectively. The synergistic lubricating mechanism of epoxy-BNNSs/GO coating was proposed, which could provide a new light on the design of high antifriction and wear resistance of organic nanocomposite coating.

CAS / MDL: 10043-11-5
研究领域: 材料科学 · 表面工程
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ENVIRONMENTAL RESEARCH · 2024 · IF 7.7

H*ads dynamics engineering via bimetallic Pd–Cu@MXene catalyst for enhanced electrocatalytic hydrodechlorination

Lan-Ying Liu,Min-Hua Cui,John Justo Ambuchi,Shi-Ming Niu,Xin-Hui Li,Wo-Long Wang,He Liu,Guo-Shuai Liu,Ai-Jie Wang

Electrocatalytic hydrodechlorination (EHDC) is a promising approach to safely remove halogenated emerging contaminants (HECs) pollutants. However, sluggish production dynamics of adsorbed atomic H (H* ads ) limit the applicability of this green process. In this study, bimetallic Pd–Cu@MXene catalysts were synthesized to achieve highly efficient removal of HECs. The alloy electrode (Pd–Cu@MX/CC) exhibited better EHDC performance in comparison to Pd@MX/CC electrode, resulting in diclofenac degradation efficiency of 93.3 ± 0.1%. The characterization analysis revealed that the Pd 0 /Pd II ratio decreased by forming bimetallic Pd–Cu alloy. Density functional theory calculations further demonstrated the electronic configuration modulation of the Pd–Cu@MXene catalysts, optimizing binging energies for H* and thereby facilitating H* ads production and tuning the reduction capability of H* ads . Noteably, the amounts and reduction potential of H* ads for Pd–Cu@MXene catalysts were 1.5 times higher and 0.37 eV lower than those observed for the mono Pd electrode. Hence, the introduction of Cu into the Pd catalyst optimized the dynamics of H* ads production, thereby conferring significant advantages to EHDC reactions. This augmentation was underscored by the successful application of the alloy catalysts supported by MXene in EHDC experiments involving other HECs, which represented a new paradigm for EHDC for efficient recalcitrant pollutant removal by H* ads .

CAS / MDL: 15307-86-5
研究领域: 环境科学 · 材料科学 · 催化化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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POLYMER SCIENCE SERIES B · 2015 ·Vol. 57 ·期 5 ·460-472 · IF 0.577

H-Shaped copolymer ((His)PHEMA)2-b-PEG-b-(PHEMA(His))2 with histidine modified: Synthesis, characterization and its drug release study

Sa Zongpeng,Li Yapeng,Zhao Haochen,Hu Qi,Wei Jia,Wang Jingyuan

Through H-shaped macroinitiator glycol-chlorine((Cl) 2 -PEG-(Cl) 2 ) to initiate the ATRP reaction of 2-Hydroxyethyl Methacrylate (HEMA) we synthesized H-shaped copolymer (PHEMA) 2 - b -PEG- b -(PHEMA) 2 . After we modified the copolymer with histidine (His), the self-assembling and drug release behavior was studied. The morphology of the copolymer micelles and drug loaded micelles were examined by transmission electron microscope (TEM). Spherical micelles and core-shell structure with a diameter of 165 nm were obtained (at pH = 7.0). Due to the presence of imidazole-ring in histidine the copolymer show commendable pH-sensitivity, which made the copolymer potential application as drug carrier exhibiting good control-released property.

研究领域: 高分子化学 · 药物递送系统 · 生物材料
✓ 已验证 DOI 高影响因子
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Journal of Physical Chemistry C · 2022 · IF 4.177

Low-Temperature C–H Bond Activation: Ethylbenzene-to-Styrene Conversion on Rutile TiO2(110)

Yuemiao Lai,Zhengtian Pu,Peng Liu,Fangliang Li,Jie Zeng,Xueming Yang,Qing Guo

The low-temperature C–H bond activation of alkanes remains a big challenge in alkane dehydrogenation. In this work, ethylbenzene (EB) oxidative dehydrogenation has been investigated on rutile(R)-TiO2(110) under both ultrahigh vacuum (UHV) and ambient conditions. Under UHV conditions, styrene is produced with nearly 100% selectivity in a stepwise manner, in which the first C–H bond dissociation of EB occurs at <285 K with the help of surface O22– species, followed by the second C–H bond dissociation at about 400 K. However, styrene, acetophenone, and 2,3-diphenylbutane products are produced from EB oxidative dehydrogenation under ambient conditions, suggesting that α-H dissociation is the initial step of EB oxidative dehydrogenation. This may be also possible for EB oxidative dehydrogenation on R-TiO2(110) under UHV conditions. The different pathways of EB oxidative dehydrogenation under UHV and ambient conditions may originate from different intermediates and O2 concentrations. This work provides new insight into the fundamental understandings of the low-temperature C–H bond activation of alkyl chains of aromatic hydrocarbons, which may promote the development of new catalysts for efficient styrene production from EB oxidative dehydrogenation under mild conditions.

研究领域: 催化化学 · 表面科学
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JOURNAL OF ORGANIC CHEMISTRY · 2021 · IF 4.354

One-Pot Tandem Access to Phenothiazine Derivatives from Acetanilide and 2-Bromothiophenol via Rhodium-Catalyzed C–H Thiolation and Copper-Catalyzed C–N Amination

Xiyan Rui,Chao Wang,Dongjuan Si,Xuechao Hui,Keting Li,Hongmei Wen,Wei Li,Jian Liu

A one-pot and step economic reaction involving Rh(III)-catalyzed C–H thiolation and relay Cu(II)-catalyzed C–N amination of acetanilide and 2-bromothiophenol is reported here, with several valuable phenothiazine products obtained. This synthesis protocol proceeds from easily starting materials, demonstrating high atom economy, broad substrate scope, and good yield. Furthermore, the directing group can be easily eliminated, and chlorpromazine is provided in a large scale; thus this synthesis protocol could be utilized to construct phenothiazine scaffolds.

CAS / MDL: 3422-01-3
研究领域: 有机化学 · 药物化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Frontiers of Chemical Science and Engineering · 2024 ·Vol. 18 ·期 11 ·1-11 · IF 4.3

Enhanced formic acid production for CO2 photocatalytic reduction over Pd/H-TiO2 catalyst

Gao Huimin,Zhang Jinpeng,Zhang Fangyuan,Jing Jieying,Li Wen-Ying

The photocatalytic reduction of CO 2 into formic acid is a feasible approach to alleviate the effects of global climate change and achieve chemical energy storage. It is important to design highly active photocatalysts to improve the selectivity and yield of formic acid. In this study, TiO 2 -based catalysts were prepared and loaded with Pd nanoparticles via an impregnation process. The Pd/H-TiO 2 catalyst demonstrated superior CO 2 reduction activity and a high formic acid production rate of 14.14 mmol cat ·g −1 ·h −1 . The excellent catalytic performance observed in the presence of a Pd/H-TiO 2 catalyst is ascribed to the synergy between O v and Pd. The presence of O v led to increase in CO 2 adsorption while Pd loading enhanced the photogenerated electron-hole pair separation. Electron transfer from H-TiO 2 to Pd also contributed to CO 2 activation.

研究领域: 环境科学 · 材料科学
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JOURNAL OF ORGANIC CHEMISTRY · 2025 · IF 3.6

Pd(II)-Catalyzed Csp2–H Carbonylative Amidation of Groebke–Blackburn–Bienaymé Reaction Products: Access to Imidazo[1,2-a]pyridine-Fused δ-Lactams

Jingru Zou,Lingmeng Xie,Wen Qin,Xingang Xie,Xing Huo

The Groebke–Blackburn–Bienaymé (GBB) reaction provides efficient access to imidazole-fused heterocycles, yet it is inevitably endowed with an isocyanide-derived secondary amino group in products. Herein, we report a Pd(II)-catalyzed sp2 C–H carbonylative amidation strategy using Co2(CO)8 as a safe CO surrogate. Leveraging the native aryl amino group as a directing motif, this protocol enables direct conversion of GBB adducts into pharmaceutically relevant imidazo[1,2-a]pyridine-fused δ-lactams with up to 86% yield. The method demonstrates exceptional functional group tolerance and eliminates prefunctionalization requirements, offering a streamlined approach to access complex nitrogen-rich architectures.

研究领域: 有机化学 · 药物化学 · 杂环化学 · 转化医学 · 分子药理学
✓ 已验证 DOI PubMed 高影响因子
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