CHINESE JOURNAL OF CATALYSIS
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2021
·
IF 8.271
Weiyin Wang,Lu Lin,Haifeng Qi,Wenxiu Cao,Zhi Li,Shaohua Chen,Xiaoxuan Zou,Tiehong Chen,Nanfang Tang,Weiyu Song,Aiqin Wang,Wenhao Luo
The catalytic hydrogenation of halonitroarenes to haloanilines is a green and sustainable process for the production of key nitrogen-containing intermediates in fine chemical industry. Chemoselective hydrogenation poses a significant challenge, which requires the rational design of the catalysts with proper hydrogenation ability for nitro group and simultaneously preventing dehalogenation of halogen group. Herein, a highly effective Rh@Al 2 O 3 @C single-atom catalyst (SAC) was developed for the hydrogenation of m -chloronitrobenzene ( m -CNB) to m -chloroaniline ( m -CAN), through an in-situ grafting of metal during the assembly of MIL-53 (Al), followed by confined pyrolysis . Extensive characterizations reveal an exquisite structure of the Rh@Al 2 O 3 @C, containing atomically dispersed Rh sites onto Al 2 O 3 confined by the amorphous carbon. The five-coordinated aluminum (Al V ) species are essential for achieving the atomic dispersion of Rh atoms, providing the unsaturated coordinative sites for metal. Compared to the benchmark Rh/γ-Al 2 O 3 and Rh/C nanocatalysts, the Rh@Al 2 O 3 @C SAC affords an excellent turnover frequency of 2317 mol m -CNB ·mol Rh –1 ·h –1 , the highest value to date in heterogeneous catalyst systems for the hydrogenation of m -CNB at 313 K and 20 bar H 2 , together with a sustained selectivity to m -CAN (~98%) during five consecutive runs. The superior catalytic performance of the Rh@Al 2 O 3 @C is attributed to a proper modulation of electronic structure of hydrogenation metal by forming SAC, together with an enhanced accessibility of acid function sites.
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Nano-Micro Letters
·
2021
·Vol. 13
·期 1
·1-13
·
IF 16.419
Chen Keng,Wang Zeming,Wang Liang,Wu Xiuzhen,Hu Bingjie,Liu Zheng,Wu Minghong
High-efficiency electrochemical hydrogen evolution reaction (HER) offers a promising strategy to address energy and environmental crisis. Platinum is the most effective electrocatalyst for the HER. However, challenging scarcity, valuableness, and poor electrochemical stability still hinder its wide application. Here, we designed an outstanding HER electrocatalyst, highly dispersed rhodium (Rh) nanoparticles with an average diameter of only 3 nm supported on boron (B) nanosheets. The HER catalytic activity is even comparable to that of commercial platinum catalysts, with an overpotential of only 66 mV in 0.5 M H 2 SO 4 and 101 mV in 1 M KOH to reach the current density of 10 mA cm −2 . Meanwhile, the catalyst exhibited impressive electrochemical durability during long-term electrochemical processes in acidic and alkaline media, even the simulated seawater environment. Theoretical calculations unraveled that the structure–activity relationship between B(104) crystal plane and Rh(111) crystal plane is beneficial to the release of hydrogen, and surface O plays a vital role in the catalysis process. Our work may gain insights into the development of supported metal catalysts with robust catalytic performance through precise engineering of the strong metal-supported interaction effect.
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Catalysts
·
2022
·Vol. 13
·期 1
·37
·
IF 4.501
Qizhen Yang,Zhengyu Tang,Jiale Xiong,Yucai He
Valorization of the abundant renewable lignocellulose through an efficient chemoenzymatic strategy to produce the furan-based platform compounds has raised great interest in recent years. In this work, a newly prepared sulfonated tin-loaded rice husk-based heterogeneous chemocatalyst UST-Sn-RH was utilized to transform corncob (75.0 g/L) into furfural (72.1 mM) at 170 °C for 30 min in an aqueous system. To upgrade furfural into furfuryl alcohol, whole cells of recombinantE. coli KPADH harboring alcohol dehydrogenase were employed to transform corncob-derived furfural into furfuryl alcohol at 30 °C and pH 7.5. In the established chemoenzymatic cascade process, corncob was efficiently transformed to furfuryl alcohol with a productivity of 0.304 g furfuryl alcohol/(g xylan in corncob). In general, biomass could be efficiently valorized into valuable furan-based chemicals in this tandem reaction with the chemocatalyst (bio-based UST-Sn-RH) and the biocatalyst (KPADH cell) in an aqueous system, which has potential application.Keywords:furfural;furfuryl alcohol;heterogeneous catalyst;chemoenzymatic strategy
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ACS Nano
·
2022
·
IF 18.027
Qiqi Mao,Xu Mu,Kai Deng,Hongjie Yu,Ziqiang Wang,You Xu,Xiaonian Li,Liang Wang,Hongjing Wang
The construction of efficient and stable electrocatalysts is of widespread research significance for electrocatalytic coupling reactions. Herein, an amorphous Rh metallene sulfide with sulfur-rich vacancies (a-RhS2–x metallene) is synthesized for the cathodic nitrobenzene (Ph-NO2) electroreduction reaction (ERR) to aniline (Ph-NH2) coupled with the anodic sulfur ion (S2–) oxidation reaction (SOR) in a coelectrolysis system. On the one hand, the amorphous Rh metallene structure can provide enough of a reactive site. On the other hand, the amorphization and the introduced S vacancies can generate rich defects and ligand unsaturated sites to improve the intrinsic activity of the active sites. Due to these advantages, the a-RhS2–x metallene exhibits superior electrocatalytic performance for Ph-NO2 ERR and SOR. Inspiringly, in the assembled electrocatalytic coupling system, the required overpotential is only 0.442 V at 10 mA cm–2 to drive the cathodic Ph-NO2 ERR and anodic SOR, which allows for promising energy-efficient electrolysis to generate high value-added chemicals.
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高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2019
·Vol. 29
·期 32
·1902101
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IF 15.621
Yaping Zhang,Yang Li,Diqing Ni,Zhiwei Chen,Xiao Wang,Yuyu Bu,Jin-Ping Ao
In this work, a water splitting photoanode composed of a BiVO 4 thin film surface modified by the deposition of a rhodium (Rh)-doped SrTiO 3 perovskite is fabricated, and the Rh-doped SrTiO 3 outer layer exhibits special photoelectrochemical (PEC) oxygen evolution co-catalytic activity. Controlled intensity modulated photo-current spectroscopy, electrochemical impedance spectroscopy, and other electrochemical results indicate that the Rh on the perovskite provide an oxidation active site during the PEC water oxidation process by reducing the reaction energy barrier for water oxidation. Theoretical calculations indicate that the water oxidation reaction is more likely to occur on the (110) crystal plane of Rh-SrTiO 3 because the oxygen evolution reaction overpotential on the (110) crystal plane is reduced significantly. Therefore, the obtained BiVO 4 /Rh5%-SrTiO 3 photoanode exhibits an optimized PEC performance. In particular, it facilitates the saturation of the photocurrent density. Thus, the presence of doped Rh in SrTiO 3 can reduce the amount of noble metals required while achieving excellent and stable oxygen evolution properties.
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Catalysts
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2019
·Vol. 9
·期 3
·215
·
IF 3.444
Penghe Su,Ya Chen,Xiaotong Liu,Hongyuan Chuai,Hongchi Liu,Baolin Zhu,Shoumin Zhang,Weiping Huang
A simple and practical Rh-catalyzed hydroformylation of vinyl acetate has been synthesized via impregnation-calcination method using silicate nanotubes (MgSNTs) as the supporter. The Rh0(zero valent state of rhodium) was obtained by calcination. The influence of calcination temperature on catalytic performance of the catalysts was investigated in detail. The catalysts were characterized in detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), atomic emission spectrometer (ICP), and Brunauer–Emmett–Teller (BET) surface-area analyzers. The Rh/MgSNTs(a2) catalyst shows excellent catalytic activity, selectivity and superior cyclicity. The catalyst could be easily recovered by phase separation and was used up to four times.Keywords:silicate nanotubes;Rh;hydroformylation;vinyl acetate
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Nature Communications
·
2017
·Vol. 8
·期 1
·1-7
·
IF 12.124
Lin Jin,Li Zhi,Kan Jian,Huang Shijun,Su Weiping,Li Yadong
Catalytic oxidative C–H bond functionalization reactions that proceed without requiring stoichiometric amounts of external oxidants or pre-functionalized oxidizing reagents could maximize the atom- and step-economy in chemical syntheses. However, such a transformation remains elusive. Here, we report that a photo-driven catalytic process enables decarboxylative C–H trifluoromethylation of (hetero)arenes with trifluoroacetic acid as a trifluoromethyl source in good yields in the presence of an external oxidant in far lower than stoichiometric amounts (for example, 0.2 equivalents of Na 2 S 2 O 8 ) using Rh-modified TiO 2 nanoparticles as a photocatalyst, in which H 2 release is an important driving force for the reaction. Our findings not only provide an approach to accessing valuable decarboxylative C–H trifluoromethylations via activation of abundant but inert trifluoroacetic acid towards oxidative decarboxylation and trifluoromethyl radical formation, but also demonstrate that a photo-driven catalytic process is a promising way to achieve external oxidant-free C–H functionalization reactions.
研究领域:
有机化学
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催化
·
光化学
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高影响因子
Science Translational Medicine
·
2017
·Vol. 9
·期 381
·
IF 16.761
Hong Zhang,Xiaopei Qiu,Yurui Zou,Yanyao Ye,Chao Qi,Lingyun Zou,Xiang Yang,Ke Yang,Yuanfeng Zhu,Yongjun Yang,Yang Zhou,Yang Luo
Fast and simultaneous forward and reverse blood grouping has long remained elusive. Forward blood grouping detects antigens on red blood cells, whereas reverse grouping identifies specific antibodies present in plasma. We developed a paper-based assay using immobilized antibodies and bromocresol green dye for rapid and reliable blood grouping, where dye-assisted color changes corresponding to distinct blood components provide a visual readout. ABO antigens and five major Rhesus antigens could be detected within 30 s, and simultaneous forward and reverse ABO blood grouping using small volumes (100 μl) of whole blood was achieved within 2 min through on-chip plasma separation without centrifugation. A machine-learning method was developed to classify the spectral plots corresponding to dye-based color changes, which enabled reproducible automatic grouping. Using optimized operating parameters, the dye-assisted paper assay exhibited comparable accuracy and reproducibility to the classical gel-card assays in grouping 3550 human blood samples. When translated to the assembly line and low-cost manufacturing, the proposed approach may be developed into a cost-effective and robust universal blood-grouping platform.
研究领域:
医学诊断
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即时检测技术
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生物化学
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医学中的机器学习
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Green Energy & Environment
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2017
·
IF 0
Peng Wang,Xia Chen,Dong-Liang Wang,Yong-Qi Li,Ye Liu
The phosphine-functionalized phosphonium-based ionic liquids ( dppm-Q , dppe-Q , dppp-Q and dppb-Q ) as the bi-functional ligands enable the efficient one-pot tandem hydroformylation–acetalization. It was found that, in dppm-Q , dppe-Q , dppp-Q and dppb-Q , the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/ dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.
研究领域:
化学
·
催化科学
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Inorganic Chemistry Frontiers
·
2026
·
IF 6.4
Rui Feng,Wei Wang,Tianbo Li,Feifei Yang,Xiaoyan Hu,Xinlong Yan,Lianming Zhao,Shijian Lu
The selective production of linear aldehydes from long-chain α-olefins using heterogeneous Rh catalysts faces a challenge, as non-selective sites in unconfined environments severely compromise regioselectivity. Herein, we report a strategy to achieve high regioselectivity and activity in 1-hexene hydroformylation by confining atomically dispersed Rh sites within the micropores of a silicalite-1 (S-1) zeolite, followed by the selective poisoning of external Rh sites. A series of Rh@S-1 catalysts with varying loadings were synthesized by an in situ hydrothermal method. Comprehensive characterization (XRD, XPS, STEM) confirmed the successful incorporation of Rh as atomically dispersed species within the MFI framework while preserving the zeolite’s textural properties. In the hydroformylation of 1-hexene, the unpoisoned catalyst exhibited high conversion (98.3%) but poor regioselectivity (n/i = 2.7). The introduction of bulky thiol poisons (DMBT and TPMT), which are size-excluded from the zeolite micropores, selectively passivated the external Rh sites. Consequently, the reaction was confined predominantly to the internal Rh sites, thereby dramatically boosting the n/i ratio to 59.9 and 9.3 for DMBT and TPMT poisoned catalysts, respectively, at a low 1-hexene concentration. The superior regioselectivity achieved with DMBT over TPMT is attributed to its more effective poisoning of pore-mouth Rh sites. However, it also introduced higher diffusion resistance, leading to lower conversion and higher apparent activation energy. Moreover, the catalysts demonstrated excellent recyclability. This work elucidates the decisive roles of confined internal versus unconfined external Rh sites in the atomically dispersed Rh@S-1 catalyst for 1-hexene hydroformylation. This finding provides a key design principle for developing efficient heterogeneous Rh catalysts for long-chain α-olefin hydroformylation.
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ACS Catalysis
·
2026
·
IF 13.6
Shidong Bao,Wenxu Deng,Shourong Zheng,Xiaolei Qu,Heyun Fu
Revealing the multiple interactions in heterogeneous catalysts and the potential structural evolution under the reaction conditions is crucial for the rational design of catalysts. Herein, we elucidate the complex interactions within P-doped Rh catalysts supported on rutile TiO2 (r-TiO2) and anatase TiO2 (a-TiO2) as well as their structural evolution behavior during CO2 hydrogenation. Before P-doping, Rh/r-TiO2 with Rh ensemble sites primarily catalyzes CO2 methanation, while Rh/a-TiO2 with TiOx-encapsulated Rh sites originating from strong metal–support interaction (SMSI) shows high CO selectivity. P-doping into Rh/r-TiO2 transforms Rh ensemble sites into separated Rh sites, switching the catalytic selectivity from CH4 to CO at low reaction temperatures. Interestingly, the selectivity reverses from 100% CO to 95% CH4 with increasing temperature, demonstrating a dynamic structural evolution. The metastable P-doped Rh species is reconstructed into Rh ensemble and phosphate species due to electronic metal–support interaction and O* intermediate oxidation in a weakly oxidative reaction atmosphere, while it can be regenerated in a H2 atmosphere. For the a-TiO2-supported P-doped Rh catalyst, moderate TiOx encapsulation originating from SMSI contributes to stabilizing the P-doped Rh species during CO2 hydrogenation. Our study reveals that regulating metal–support interaction within TiO2-supported P-doped Rh catalysts can modulate their structural evolution behavior during the reaction, guiding the rational design of P-doped metal catalysts on reducible supports.
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JOURNAL OF CATALYSIS
·
2025
·
IF 6.5
Xin Zhou,Yuanjun Zhao,Pengzhen Yin,Zhaozhan Wang,Xingtao Zhao,Fengqi Zhang,Huibing Shi,Dmitry Gorbunov,Yong Yang
Developing heterogeneous catalysts capable of efficient and regioselective hydroformylation of sterically hindered alkenes remains a significant challenge. In this work, we develop a stable and active Rh single-atom catalyst (Rh@POP-X) anchored on a hybrid phosphine-functionalized porous organic polymer (POP) with tailored porosity and high specific surface area, allowing for hydroformylation of sterically hindered diisobutylene (DIB). Comprehensive characterizations including solid-state NMR, AC HAADF-STEM, XPS, in-situ CO-DRIFTS, XAS confirm the atomic dispersion of Rh sites coordinated by phosphine ligands within the crosslinked polymeric network. The optimal catalyst Rh@POP-2 exhibits exceptional performance, achieving >98 % conversion with excellent regioselectivity toward linear isononanal. Remarkably, the Rh@POP-2 catalyst demonstrates high stability, maintaining its catalytic performance over 10 times successive reaction cycles without significant deactivation. The versatility of this catalytic system is further demonstrated by its broad substrate adaptability, enabling efficient hydroformylation of various olefins, including linear, terminal, aromatic, and sterically hindered olefins, to yield their corresponding C 1+ aldehydes. This work provides a general strategy for designing robust single-atom catalysts for challenging hydroformylation of sterically hindered olefins.
研究领域:
催化化学
·
材料化学
·
有机合成
·
可持续化学
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