JOURNAL OF RARE EARTHS
·
2024
·
IF 5.2
Shuai Zhang,Leilei Yin,Yaping Du
The construction of rare earth (RE) alloy catalysts offers a route to harness the unique electronic structure of RE. Within the alloy, RE can fine-tune the electronic configuration of the active element, such as rhodium (Rh), via the ligand effect, optimizing the electrochemical reaction pathway. However, the challenging negative reduction potential of RE has impeded the progress in developing RE alloys, particularly nanoalloy catalysts. In this study, Rh 3 Sc/C and Rh 3 Y/C nanoalloys were synthesized using a sodium vapor reduction strategy for application as hydrogen evolution reaction (HER) catalysts. Electrochemical tests reveal that Rh-RE alloy catalysts exhibit significantly improved electrocatalytic activity in 1 mol/L KOH. Notably, Rh 3 Y/C demonstrates exceptional HER performance, achieving a low overpotential of only 31 mV at 10 mA/cm 2 , surpassing the 50 mV observed for Rh/C. Furthermore, the current density of Rh 3 Y/C at an 80 mV overpotential is 3.9 times that of Rh/C. This study sheds light on the remarkable catalytic potential of Rh-RE alloys, paving the way for the future expansion of RE nanoalloy systems.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Applied Nano Materials
·
2021
·
IF 5.097
Yongdi Zhang,Shaowen Wu,Yuanzhi Li,An Zhang,Qianqian Hu,Jichun Wu,Xin Tan
A unique nanocomposite of Rh quasi-monolayer clusters supported on spinel MgAl2O4 nanosheets with a low Rh loading of 0.15 wt % (Rh/MgAl2O4-MC) was synthesized by a facile method. By the catalyst design, nearly all of Rh atoms are utilized like well-known surface single-atom catalysts. More importantly and surprisingly, Rh/MgAl2O4-MC shows extremely high specific reaction rates of CH4 (rCH4) and CO2 (rCO2) per mole Rh and turnover frequency (TOF) for catalytic CO2 reforming of CH4 (DRM). Its rCH4 and rCO2 are as high as 51.14 and 62.65 mol molRh–1 s–1, which are 4.7 and 4.8 times higher than those of conventional Rh nanoparticles supported on spinel MgAl2O4 nanosheets with a higher Rh loading of 0.96 wt % (Rh/MgAl2O4-NP), respectively. Its TOF values of CH4 and CO2 are as much as 53.9 and 66.1 s–1, which are 3.5 and 3.5 times higher than those of Rh/MgAl2O4-NP, respectively. Meanwhile, Rh/MgAl2O4-MC retains the excellent catalytic durability of supported nanoparticles with negligible side reaction of carbon deposition, which is in striking contrast to the prone deactivation of the single-atom catalysts of precious metals (e.g., Rh and Ru) reported. Experimental evidence and DFT calculations reveal the presence of a strong interaction between Rh quasi-monolayer clusters and MgAl2O4 for Rh/MgAl2O4-MC. The interaction not only makes energetically unstable clusters stable but also alters the reaction pathway of DRM. Compared to DRM on Rh nanoparticles, the oxidations of C* and CH* species as the rate-determining step of DRM are significantly accelerated on Rh quasi-monolayer clusters due to their activation energies being considerably reduced, thus improving intrinsic catalytic activity and inhibiting the side reaction of carbon deposition.
研究领域:
材料科学
·
催化化学
·
能源化学
✓ 已验证
DOI
高影响因子
NANOTECHNOLOGY
·
2025
·Vol. 36
·期 18
·185401
·
IF 2.8
Chen Zhang,Ruipeng Hou,Shufang Chang,Rong Wu,Shunhang Wei
Cocatalysts generally serve as active sites accelerating carrier separation. However, when the hydrophilicity of photocatalyst itself is poor, the trapped electrons or holes on cocatalysts are difficult to react with reactants quickly. In this work, Bi4Ti3O12 nanosheets with excellent hydrophilicity was prepared and then thermally deposited Rh on their surface (Bi4Ti3O12(Rh)), and finally in-suit grew ZnIn2S4 on the surface of Bi4Ti3O12(Rh). Based on the results of photocatalytic performance and materials characterization, it was found that the Bi4Ti3O12(Rh) in the photocatalytic system could be considered as a special cocatalyst rather than formed heterojunction with the ZnIn2S4. Under visible-light irradiation, the Rh acted as an electron trapping site to conduct photogenerated electrons trapping from ZnIn2S4 to the surface of Bi4Ti3O12. This process not only further accelerated carrier separation, but also facilitated electrons reacting with water due to the excellent hydrophilicity of Bi4Ti3O12(Rh), thereby achieving enhanced photocatalytic H2 production performance in the absence of sacrificial agents.
研究领域:
材料科学
·
能源科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2023
·
IF 4.6
Hongjing Wang,Yuqin Liang,Songliang Liu,Hongjie Yu,Kai Deng,You Xu,Xiaonian Li,Ziqiang Wang,Liang Wang
The research on high-efficiency two-dimensional (2D) catalytic materials for the small-molecule oxidation-assisted hydrogen evolution reaction (HER) is prospective for efficient hydrogen production. Herein, we report heterostructured Pt/Rh metallene with Pt nanoparticles (NPs) uniformly anchored on Rh metallene for the HER and ethylene glycol oxidation reaction (EGOR). The ultrathin sheet structure of the Pt/Rh metallene offers high surface areas and sufficient active sites. More importantly, the Pt/Rh heterostructure can optimize catalytic active centers and adjust electronic structure. Thus, Pt/Rh metallene exhibits superior electrocatalytic HER activity with a low overpotential of 28 mV in 1 M KOH at 10 mA cm–2 and EGOR activity with a specific activity of 8.39 mA cm–2 in 1 M KOH with 3 M EG, along with outstanding CO tolerance. In a two-electrode system, Pt/Rh metallene requires a low potential of 0.51 V for stable and efficient hydrogen production at 10 mA cm–2 in 1 M KOH + 3 M EG, with the simultaneous production of high-value-added products. The job proposes an attractive strategy for the synthesis of 0D/2D metallene toward simultaneous energy-saving hydrogen production and chemical update.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
AICHE JOURNAL
·
2024
·
IF 3.5
Jinyan Zhang,Yan Shao,Feng Zeng,Huanhao Chen
Secondary-metals promotion is key to tune the CO 2 hydrogenation performance of Rh-based catalyst. We describe the addition of Cu or Co in TiO 2 nanorods supported Rh catalyst (viz., RhM x /TiO 2 ), showing significant impact on the CO 2 hydrogenation activity and productivity. Cu addition can promote the partial hydrogenation to alcohols (methanol and ethanol), whereas Co led to the deep hydrogenation to alkanes (CH 4 , C 2 H 6 ). Comparative time-resolved in situ DRIFTS studies with H 2 /D 2 isotopic exchange further reveal that both surface adsorbed CO* and formates could be the key reaction intermediates during the CO 2 hydrogenation over RhM x /TiO 2 (especially the RhCu 2.5 /TiO 2 ), in which the interaction strength of CO* regulated by secondary-metals addition was key to tune the reaction pathways and productivity. The findings suggested that rational design of active metal sites, for example the synergy between Rh and secondary-metals, is highly needed to promote the CO insertion and C C coupling to produce ethanol.
研究领域:
催化化学
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材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2017
·Vol. 7
·期 4
·125
·
IF 3.082
Liqiong Wang,Liang Huang,Chengpeng Jiao,Zili Huang,Feng Liang,Simin Liu,Yuhua Wang,Haijun Zhang
ISOBAM-104 protected Rh/Ni bimetallic nanoparticles (BNPs) of 3.1 nm in diameter were synthesized by a co-reduction method with a rapid injection of KBH4solution. The catalytic activities of as-prepared BNPs for hydrogen generation from hydrolysis of a basic KBH4solution were evaluated. Ultraviolet-visible spectrophotometry (UV-Vis), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) were employed to characterize the structure, particle size, and chemical composition of the resultant BNPs. Catalytic activities for hydrolysis of KBH4and catalytic kinetics of prepared BNPs were also investigated. It was shown that Rh/Ni BNPs displayed much higher catalytic activities than that of Rh or Ni monometallic nanoparticles (MNPs), and the prepared Rh10Ni90BNPs possessed the highest catalytic activities, with a value of 11,580 mol-H2·h−1·mol-Rh−1. The high catalytic activities of Rh/Ni BNPs could be attributed to the electron transfer effect between Rh and Ni atoms, which was confirmed by a density functional theory (DFT) calculation. The apparent activation energy for hydrogen generation of the prepared Rh10Ni90BNPs was about 47.2 ± 2.1 kJ/mol, according to a kinetic study.Keywords:Rh/Ni BNPs;hydrogen generation;catalytic activities;electron transfer effect
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·
IF 19
Jiali Mu,Guifa Long,Xiangen Song,Siquan Feng,Xingju Li,Qiao Yuan,Bin Li,Zheng Jiang,Li Yan,Yunjie Ding
The local coordination environment of central active sites plays a critical role in tuning the catalytic properties of heterogeneous single-metal-site catalysts (HSMSCs). However, carbon supports with inert surface properties provide weak interaction with the active sites, which hamper the effective modulation of the coordination structure of HSMSCs. Herein, this work shows that introducing N and S atoms into carbon support can modify the coordination environment of single-Rh-site and effectively improves the catalytic activity for the methanol carbonylation reaction. The synthesized Rh/AC-NS with single-Rh-site exhibits a high methanol conversion of 88% and a stable acetyl production rate of 2812 h −1 , in contrast with 1285 h −1 of Rh/AC without N- and S- functional groups, and meanwhile remarkably higher than those of Rh/AC-N and Rh/AC-S with only N- or S- functional group under the same mild reaction conditions. As revealed by the experimental result and density functional theory (DFT) calculations, the special combination of N- and S- functional groups offers favorable coordination configuration and also beneficial electronic structure for facilitated CH 3 I oxidative addition and CO insertion steps of single-Rh-site. This work offers new opportunities for rationally tuning the coordination structure of HSMSCs for heterogeneous catalysis.
研究领域:
化学工程
·
催化科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Hongjing Wang,Shiqian Jiao,Songliang Liu,Shengqi Wang,Tongqing Zhou,You Xu,Xiaonian Li,Ziqiang Wang,Liang Wang
Electrochemical water splitting is one hopeful strategy for hydrogen production, and designing efficient hydrogen evolution electrocatalysts under universal pH is one of the most critical topics. Here, we have successfully prepared mesoporous bimetallic core–shell nanostructures with Au nanowires (Au NWs) as cores and mesoporous Rh as shells (Au@mRh NWs). Due to the one-dimensional structure and mesoporous core–shell structure, Au@mRh NWs possess more active sites and provide the synergistic effect, leading to the great improvement of the electrochemical activity toward the hydrogen evolution reaction under a wide range of pH. The present work proposes a versatile strategy for preparing a bimetallic core–shell structure with a mesoporous shell, which is highly promising for more electrocatalytic applications.
研究领域:
材料科学
·
电化学
·
催化化学
✓ 已验证
DOI
高影响因子
CRYSTENGCOMM
·
2023
·Vol. 25
·期 9
·1365-1373
·
IF 3.1
Xin Wu,Xingzhong Zhu,Caixia Kan,Daning Shi
Boosting the electrocatalytic performance of non-Pt catalysts for the hydrogen evolution reaction (HER) is of great importance in the context of the high price and scarcity of Pt. In this work, we successfully synthesized bimetallic core–shell nanostructures with Au nanostars as cores and Rh clusters as shells (Au@Rh nanostars) based on a two-step wet-chemistry strategy. We have demonstrated that the interaction strength between Rh and intermediate(s) involved in the HER could be effectively manipulated due to the existence of a strong electronic effect in bimetallic Au@Rh nanostars. The results from FDTD simulation suggested that the E-M field enhancement of the Au@Rh nanostar is inferior to that of the Au nanostar but there is a more localized distribution between the Au core and Rh shell. Benefiting from the synergistic effect and the plasmon-induced accelerated molecular transformations, the Au@Rh nanostars manifest outstanding plasmon-enhanced electrochemical activity toward the HER with a low overpotential of 28.5 mV for achieving the current density of 10 mA cm−2, which surpasses the commercial Pt/C. Furthermore, the obtained Au@Rh nanostars exhibited remarkable stability during the durability test with only a 3 mV shift in HER polarization curves after 5000 potential cycles. This study provides a versatile strategy for designing bimetallic core–shell nanostructures with plasmon-enhanced electrocatalytic performance.
研究领域:
材料科学
·
电化学
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 39
·13955-13961
·
IF 4
Xiaorui Yan,Lele Chen,Haisheng Wei,Tiantian Liu,Kairui Li,Jing Li
The stability of Rh-based heterogeneous catalysts is a key issue in the hydroformylation of olefins. Confinement of active Rh species has been considered an effective strategy to achieve stable catalysts. In this work, a phosphine ligand was successfully confined in ZIF-8 material and coordinated with Rh metal by a reduction procedure to develop an efficient and stable Rh-based catalyst for hydroformylation of 1-octene. The results indicate that the catalyst reduced at 300 °C under H2 atmosphere exhibits better stability than that with NaBH4 as reductant and undoped P catalyst. Various characterization studies demonstrate that the superior performance is due to the strong interaction between Rh metal and P, which inhibits the leaching of active Rh species. This work reveals an effective strategy for the synthesis of highly stable catalysts for use in the hydroformylation reaction.
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2017
·
IF 9.446
Mei Ming,Yanlin Ren,Min Hu,Yun Zhang,Ting Sun,Yuling Ma,Xiaojing Li,Weidong Jiang,Daojiang Gao,Jian Bi,Guangyin Fan
Exploring MXenes as supports for synthesis of highly efficient catalysts are extremely important for hydrodechlorination of chlorophenols because of the acute toxicity and strong potential bioaccumulation of chlorophenols. We reported a facile strategy to synthesize Rh nanoparticles deposited on 2D alk-Ti 3 C 2 X 2 (X = O, F) (alk-Ti 3 C 2 X 2 for short) MXene, which was prepared through the removal of the Al layers of Ti 3 AlC 2 and post-treatment by alkalization. Modifying the Ti 3 C 2 X 2 support by alkalization triggered the substitution of surface fluorine groups with surface oxygen species. The changes in the surface chemistry of alk-Ti 3 C 2 X 2 effectively prevented particle aggregation to form well-dispersed Rh nanoparticles in small sizes with relative high metal dispersion, thereafter improving the hydrogen uptake capacity of the catalyst. Consequently, the Rh/alk-Ti 3 C 2 X 2 catalyst significantly enhanced the catalytic performance for the HDC reaction, which could be assigned to the large number of active components from small Rh nanoparticles. This strategy provides a basis for investigating the use of MXenes as supports to synthesize well-defined metal nanoparticles in 2D layered structures for potential applications.
研究领域:
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2019
·Vol. 29
·期 32
·1902101
·
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.
研究领域:
材料科学
·
电化学
·
能源转换
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）