ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Guangjun Ji,CunYao Li,Xiangsong Lin,Xiao-Feng Wu,Li Yan,Yunjie Ding
To enhance the catalytic performance of single-metal-site catalysts (SMSCs), regulating the interaction between the active site and substrate is crucial but challenging. Herein, a series of Rh-based SMSCs (Rh/m-3vPAr3-POLs) were designed and synthesized on P-abundant porous organic polymers (POPs) with different electronegativities of frame phosphine. The Rh–P active sites on various POPs were modified by functional groups (−F, −H, −Me, or −OMe). Both the formation of HRh(CO)2(P)2 active species and the insertion of CO were promoted via the electron-accepting property of fluorine, which endowed Rh/m-3vPAr3-POL-F with the best activity (TOF = 3000 h–1), selectivity (>88.1%), l/b ratio (>6.8), and stability (1000 h) for 1-octene hydroformylation in a fixed-bed reactor. Multiple characterization techniques (extended X-ray absorption fine structure, scanning transmission electron microscopy, in situ Fourier-transform infrared spectroscopy, etc.) and density functional theory calculations were employed to get further insights into the microenvironment and active structure of Rh-based SMSCs. This work offers a promising avenue for designing efficient and stable SMSCs in heterogeneous catalysis.
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高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 7
·2257-2264
·
IF 6.177
Fei Zhang,Chunzheng Wu,Shuibo Wang,Shiwei Wang,Tong Li,Laixi Zou,Hongbo Yu,Hongfeng Yin
Although supported Rh nanoparticles (NPs) are one of the best catalysts for the selective hydrogenation of phenol to cyclohexanol, they still suffer from poor selectivity problems. In this study, we promoted the selectivity of Rh NPs with CoOx through an in situ transformation of the bimetallic RhCo NPs on SiO2. Among the obtained Rh–CoOx/SiO2 catalysts, the one with a Co/Rh molar ratio of 1/3 exhibited the highest phenol conversion (i.e., 98.1%) and the highest selectivity to cyclohexanol (i.e., 99.4%). Our study showed that CoOx promoters modified the electronic states of Rh and created new active sites at their interface, which are beneficial to the activation of phenol and the desorption of cyclohexanol. Excessive coverage of Rh by CoOx, however, would cause deactivation due to the less exposure of the Rh–CoOx interface.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2021
·
IF 5.316
Liang Li,Yongwei Lu,Xiaowei Liu,Xinran Wang,Siyue Zhou
Petal-like ultra-evenly Rh-doped Co 2 Fe-P composite was fabricated by a solvothermal and in-situ phosphorization strategy. Through doping a small amount of Rh within the Co 2 Fe-P structure, the catalytic activities of the composite for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) could be highly improved, and an excellent electrochemical bifunctional catalyst could be achieved. Under acidic reaction conditions, it only required an overpotential of 76 mV for HER to achieve a current density of 10 mA·cm −2 . Meanwhile, excellent electrochemical performance could also be obtained in alkaline electrolytes . The overpotential was 48 mV for HER and 303 mV for OER at 10 mA·cm −2 in 1 M KOH, respectively. Impressively, as a bifunctional electrode, the Rh doped Co 2 Fe-P composite can release a current density of 10 mA·cm −2 at a low cell voltage of 1.54 V in 1 M KOH for overall water splitting, which could be compared with that using commercial noble metal catalysts.
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Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 22
·13080-13086
·
IF 12.732
Mei Zhang,You Xu,Shengqi Wang,Mengying Liu,Lianbang Wang,Ziqiang Wang,Xiaonian Li,Liang Wang,Hongjing Wang
How to boost the electrocatalytic performance of non-Pt catalysts for the hydrogen evolution reaction (HER) to substitute Pt is an important research topic. Herein, by combining a one-pot wet-chemical method and the post surface functionalization, we successfully fabricated polyethylenimine (PEI)-modified bimetallic Au@Rh core–shell mesoporous nanospheres (Au@Rh@PEI MNs). Benefiting from the synergetic effects of Au@Rh core–shell mesoporous architectures and interfacial modification by PEI molecules, the resultant Au@Rh@PEI MNs exhibit excellent electrocatalytic activity and stability for the HER in all pH value solutions, which even surpass the benchmark commercial Pt/C catalyst. Our synthetic protocol may offer guidelines for the rational design of advanced catalysts for water splitting and other electrocatalytic applications.
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ACS Catalysis
·
2024
·
IF 11.3
Chenfan Gong,Hao Wang,Jian Zhang,Chengguang Yang,Xianni Bu,Haiyan Yang,Jiong Li,Peng Gao
Hydrogenation of CO2 to ethanol is an efficient process for the utilization of CO2 along with the production of value-added chemicals. However, CO2 hydrogenation to ethanol is a complicated reaction, requiring the catalyst to activate CO2 efficiently and accurately regulate the C–C coupling to achieve a high ethanol selectivity simultaneously. Herein, we report the synthesis of RhFeOx catalysts supported on TiO2 with different crystal phase compositions (anatase, rutile, and P25), which were applied for the selective CO2 hydrogenation to ethanol. The RhFeOx/P25 catalyst presented a high dispersion of Rh nanoparticles on the P25 support with abundant Rh0–Rhδ+–OV–Ti3+ (OV: oxygen vacancy) interfacial sites over the anatase/rutile junction. The optimized RhFeOx/P25 catalyst exhibited a high ethanol space–time yield of 18.7 mmol gcat–1 h–1 and a high Rh turnover frequency of 544.8 h–1 with 90.5% ethanol selectivity. An in-depth investigation via various ex situ and in situ characterizations as well as H2/D2 exchange and C2H4 pulse hydrogenation experiments demonstrated that the Rh0–Rhδ+–Ov–Ti3+ interfacial sites played a crucial role in the conversion of CO2 to ethanol. The surface Rh0 sites facilitated the CO2 activation and hydrogenation, while the Rh0–Rhδ+–Ov–Ti3+ interfacial sites boosted the C–C coupling to produce ethanol. The high-performance RhFeOx/P25 catalyst also provides an attractive route for highly efficient ethanol synthesis via CO2 hydrogenation.
研究领域:
催化化学
·
环境科学
·
材料科学
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INORGANIC CHEMISTRY
·
2026
·Vol. 65
·期 34
·19989-19997
·
IF 4.6
Yang Yuanyuan,Wang Xinyue,Zhang Chun-yang,Jia Henglei
Alloyed nanoframes (NFs), featuring high metal atomic
utilization
efficiency and large specific surface areas, have shown great promise
for electrocatalysis. However, the rational design and precise synthesis
of structurally stable NF catalysts remain considerable challenges.
Herein, we report a template-guided strategy for constructing alloyed
Cu x Rh y NFs
via the selective etching of Cu atoms from the low-energy facets of
Cu nanocubes (NCs) using a Cl – /O 2 pair,
followed by the galvanic replacement of Cu atoms with Rh at the frame
edges and vertices. Notably, the Cu 24 Rh 76 NFs
deliver outstanding electrocatalytic performance toward the nitrite
reduction reaction (NO 2 RR), achieving an NH 3 Faradaic efficiency (FE) of 99.6% at 0 V (vs the reversible hydrogen
electrode (RHE)) and an NH 3 yield rate of 676.7 mmol h –1 g –1 at −0.4 V. Such remarkable
electrocatalytic performance for NH 3 production arises
from not only the unique three-dimensional (3D) ultrathin frame architecture
but also a tandem catalytic mechanism. During the NO 2 RR
process, Cu sites adsorb and activate NO 2 – to produce the *NO intermediate, while Rh sites generate *H species
that migrate to the *NO intermediates adsorbed on Cu sites, effectively
promoting the subsequent hydrogenation steps toward NH 3 generation.
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PubMed
高影响因子
HYDROMETALLURGY
·
2025
·
IF 5.3
Feng Feng,Heda Ding,Jiaying Zhang,Lu Yu,Yuxue Yue,Yanxia Sun,Lingling Guo,Xiaoliang Xu,Chunshan Lu,Qunfeng Zhang,Xiaonian Li
The development of industrial technology has significantly promoted the production and accumulation of spent precious metal-based catalysts. This work describes the synthesis of an ionic liquid – [BIim][Cl 3 ] and its application as an alternative to toxic and corrosive reagents for precious metal leaching from waste catalysts. The leaching process using [BIim][Cl 3 ] is proved to be safe and green. It offers a higher stability and higher leaching efficiency compared to other reagents used in previous publications. The ionic liquid [BIim][Cl 3 ] enabled the efficient leaching of Pd and Au, as well as the extremely stable precious metals Pt, Rh under mild conditions. The highest leaching efficiencies achieved by [BIim][Cl 3 ] were 99.9 %, 98.5 %, 98.6 % and 90.6 % for Pd, Au, Pt and Rh under the optimal leaching conditions, respectively. In order to reveal the leaching mechanism, XPS, far infrared (FIR), NMR, and EDS were used to demonstrate the importance of imidazolium cations in the leaching process. The leaching pathway was proposed based on the DFT calculation results on transition state energy barrier.
研究领域:
化学工程
·
材料科学
·
环境科学
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Yuanjun Zhao,Chao Feng,Zihao Yang,Zhaozhan Wang,Yong Yang
Developing heterogeneous Rh catalysts with high stability and anti-leaching properties for hydroformylation remains a long-standing challenge. In this work, we present a bidentate Xantphos-functionalized hypercrosslinked porous polymer with a large specific surface area and hierarchical pore structure, serving as both a heterogeneous ligand and support to construct a durable single-Rh-site catalyst. The single-Rh sites are confined within the crosslinked polymer framework through Rh P bond coordination, forming a unique hemilabile Rh structure, which exhibits outstanding catalytic performance in the hydroformylation of challenging functionalized allyl acetate. The catalyst achieved an unprecedented chemoselectivity of 95.4% and a regioselectivity of 318/1 toward 4-oxybutyl acetate, substantially outperforming those previously reported catalysts. It also demonstrates broad applicability by efficiently converting diverse olefins into the corresponding C +1 aldehyde with high yields. Notably, the catalyst retains high stability over 10 recycling in batches and 700 h of continuous-flow operation without observable performance decay or Rh leaching. This work offers a practical strategy for regioselective hydroformylation of functionalized alkenes and establishes a design framework for robust single-site heterogeneous catalysts in demanding carbonylative transformations.
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ACTA PHYSICO-CHIMICA SINICA
·
2024
·
IF 10.8
Hailian Tang,Siyuan Chen,Qiaoyun Liu,Guoyi Bai,Botao Qiao,Fei Liu
The strong metal-support interaction (SMSI) is a widely recognized concept in heterogeneous catalysis, known for significantly enhancing catalyst stability and potentially modulating catalytic performance. However, because the SMSI effect is generally reversible, it tends to diminish under redox conditions opposite to those used for its construction. Consequently, its application is typically limited to conditions that are the same or similar to those under which it was formed. Herein, we report the application of oxidative SMSI (O-SMSI) constructed on hydroxyapatite-supported Rh catalyst (Rh/HAP) in a reductive reaction, the hydrogenation of furfuryl alcohol. In situ diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption and electron microscopy measurements reveal that high-temperature oxidation treatment at 500 °C induced the occurrence of O-SMSI on the Rh/HAP catalyst, accompanied by the encapsulation of Rh particles by the support. Upon the O-SMSI, the Rh species were effectively stabilized on the support surface, with significant suppression of sintering and leaching during liquid-phase reactions. As a result, the catalyst showed stable furfuryl alcohol conversion and cyclopentanone selectivity during recycling tests. Furthermore, it was found that the O-SMSI and the associated encapsulation behavior on the Rh/HAP system were only partially reversible rather than completely reversible. Even after high-temperature reduction at up to 600 °C, a portion of the SMSI effect remains, ensuring the stability of the catalysts in reductive reactions. This discovery greatly expands the application scope of SMSI catalysts and provides a new way to prepare stable hydrogenation catalysts.
研究领域:
催化化学
·
材料科学
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高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2018
·
IF 6.434
Xiaolong Liu,Li Chen,Tingyu Zhu,Ruliang Ning
Catalytic oxidation of chlorobenzene over noble metal catalysts Pd/TiO 2 , Pt/TiO 2 , Ru/TiO 2 , and Rh/TiO 2 was evaluated, and Ru/TiO 2 contributed the highest catalytic activity and CO 2 selectivity. During the oxidation, polychlorinated benzenes PhCl x (x ≥ 2) were observed, and Ru/TiO 2 showed apparently lower PhCl x concentrations than other three samples. With the improvement of temperature, the maximum concentration appeared in the sequence of dichlorobenzene (PhCl 2 ), trichlorobenzene (PhCl 3 ), tetrachlorobenzene (PhCl 4 ), and pentchlorobenzene (PhCl 5 ), whereas the concentration of hexachlorobenzene (PhCl 6 ) was always low and showed no apparent regularity. Besides, the dioxin-like PCBs (dl-PCBs) were collected and analyzed for Pd/TiO 2 and Ru/TiO 2 . The ∑dl-PCBs produced by Pd/TiO 2 (0.0055 ng WHO-TEQ/Nm 3 ) was about 1.5 times that of Ru/TiO 2 (0.0027 ng WHO-TEQ/Nm 3 ). XPS analyses revealed that Ru/TiO 2 -used and Rh/TiO 2 -used gave the lowest and the highest Cl content of 0.61% and 1.87%. Ru/TiO 2 -used afforded the lowest (Cl ad +Cl or )/Cl value (22.1%) and the highest Cl br /Cl value (77.9%), which might be an important reason for its strongest chlorine removal ability and the lowest yields of polychlorinated by-products, whereas other three catalysts showed similarity in the Cl distributions. Additionally, systematic in-situ FTIR studies were conducted, and a reaction mechanism for the catalytic oxidation of chlorobenzene was proposed.
研究领域:
环境化学
·
催化
·
污染控制
·
材料科学
·
化学工程
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高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2022
·
IF 4.198
Shihai Lv,Ya-Nan Tian,Yanyan Yang,Chaoying Wen,Shiqing Li
An efficient one-pot synthesis of 1,1′-biisoquinolines by a three-component reaction of commercially available raw materials (benzils, NH4OAc, and alkynes) is disclosed. This complicated reaction involves in situ diimine formation via benzil-NH4OAc condensation, Rh(III)-catalyzed 2-fold imine-directed C–H activation, and annulation with alkynes. Both symmetric and unsymmetric 1,1′-biisoquinolines could be assembled in moderate to high yields. The reaction mechanism is supported through ESI-MS, in which Cp*ClRh+, Cp*(OAc)Rh+, Cp*(OPiv)Rh+, and two rhodacycle intermediates are successfully detected to explain the evolution of rhodium species.
研究领域:
有机化学
·
合成化学
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高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2018
·Vol. 29
·期 2
·1806300
·
IF 13.325
Kai Liu,Wei Wang,Penghui Guo,Jinyu Ye,Yuanyuan Wang,Pingting Li,Zixi Lyu,Yongsheng Geng,Maochang Liu,Shuifen Xie
Metal nanostructures with an ultrathin Pt skin and abundant surface defects are attractive for electrocatalytic applications owing to the increased utilization efficiency of Pt atoms and the presence of highly reactive sites. This paper reports a conformal, layer-by-layer deposition of Pt atoms on defective Rh nanowires for the faithful replication of surface defects (i.e., grain boundaries) on the Rh nanowires. The thickness of the Pt shell can be controlled from one monolayer up to 5.3 atomic layers. This series of Rh@Pt n L ( n = 1–5.3) core–sheath nanowires show greatly enhanced activity and durability in catalyzing the ethanol oxidation reaction in an acidic medium. Among others, the Rh @ Pt 3.5L nanowires show the greatest mass activity (809 mA mg −1 Pt ) and specific activity (1.18 mA cm −2 ) after loaded on carbon support, which are 3.7 and 3.4 times those of the commercial Pt/C, respectively. In situ Fourier transform infrared spectroscopy studies indicate an enhanced interaction between the outermost Pt layer and the Rh nanowire can promote C C bond cleavage for complete oxidation of ethanol to CO 2 while depress the dehydrogenation of ethanol to acetic acid. As the Pt shell thickness is increased, the selectivity for the CO 2 pathway decreases while that for acetic acid is increased.
研究领域:
材料科学
·
电化学
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高影响因子
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