JOURNAL OF CATALYSIS
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2025
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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
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材料化学
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有机合成
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可持续化学
✓ 已验证
DOI
高影响因子
Advanced Composites and Hybrid Materials
·
2024
·Vol. 7
·期 1
·1-12
·
IF 23.2
Zhang Ying,Liang Hao
The utilization of photocatalytic enzyme-coupled systems is considered a promising solution to the solar energy conversion challenge, but it is hampered by its low cofactor regeneration efficiency. Herein, a biomimetic catalytic system was designed inspired by photosynthesis for cofactor regeneration and CO 2 reduction. The Rh complexes were anchored in the core of metal-organic framework UiO67 and chitosan (CS) on the UiO67@Rh surface skillfully helped the in situ growth of CdS. In this core-shell nanoreactor, UiO67@Rh accepted the electrons produced by CdS for cofactor regeneration. CS acted as a bifunctional bio-scaffold to attach CdS and prevent CdS photocorrosion. Besides, CS spatially separated Rh complexes and CdS, preventing deactivation of Rh complexes by CdS and leakage of Rh complexes. Surprisingly, CS improved the photocatalytic activity and photostability of CdS, while other biomacromolecules did not have this function. The photocatalyst regeneration NADH cooperated with formate dehydrogenase (FDH) for CO 2 reduction. The results showed that 0.72 mM formic acid was produced in 5 h (TOF = 0.14 mmol/mg/h), which was triple as much as in the system of UiO67@Rh@CdS and FDH. This cyclic process could be repeated up to 10 time cycles, where long-term stability of the system was observed and the active state of the enzymes was preserved. This study demonstrated a new and promising organometallic photocatalyst-based artificial cofactor regeneration system, paving the path for further research into the bespoke synthesis of fine chemicals and solar fuels from CO 2 utilizing solar energy. Graphical abstract CdS nanoparticles compositing with chitosan and metal-organic frameworks for cofactor regeneration and CO 2 reduction
研究领域:
光催化
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纳米技术
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生物无机化学
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环境化学
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人工光合作用
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二氧化碳转化
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太阳能转化
✓ 已验证
DOI
高影响因子
Reaction Chemistry & Engineering
·
2025
·
IF 3.1
Zhangxinyu Fan,Muhan Li,Yifan Sun,Weixiang Wang,Qin Zhong,Boyang Liu
Since its discovery by Otto Roelen, hydroformylation has attracted extensive attention for its ability to extend the carbon chain of olefins. Aldehydes, which are converted by the hydroformylation of olefins and syngas (CO/H2), are not only high-value products, but also intermediates to produce fine chemicals, such as alcohols, esters and amines. The currently used homogeneous catalysts bring about the loss of precious metals and the discharge of phosphorus-containing wastes. Therefore, heterogeneous catalysts are developed to simplify the separation process and enhance catalyst recovery. However, the reaction kinetics of heterogeneous hydroformylation, especially the hydroformylation of long-chain olefins, remain unclear. Unlike homogeneous hydroformylation, terminal olefins can be isomerized to internal olefins on heterogeneous catalysts, and can be further converted to different branched aldehydes. Thus, the reaction kinetic of heterogeneous hydroformylation is more complex. In this work, we established a kinetic model for the heterogeneous hydroformylation of long-chain terminal olefins on Rh-based phosphides, using 1-hexene as the model reactant. This kinetic model agrees well with the density functional theory (DFT) results, and can be used to predict the regioselectivity under different reaction conditions. This study reveals the kinetic mechanism of heterogeneous hydroformylation of long-chain terminal olefins, which paves the way for the rational design of heterogeneous catalysts and the theoretical optimization of reaction conditions.
研究领域:
化学反应工程
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催化化学
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有机化学
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
RARE METALS
·
2024
·
IF 9.6
Wan Si-Jie,Hou Yan-Ting,Wang Wang,Luo Guo-Qiang,Wang Chuan-Bin,Tu Rong,Cao Shao-Wen
Photocatalytic reduction of CO 2 has attracted considerable interest owing to its potential to resolve the energy and environmental problems. Nevertheless, the lack of proficient photocatalysts has restricted the application of solar-driven photocatalytic CO 2 reduction. Herein, we reported an S-scheme heterojunction by combining g-C 3 N 4 with La 3+ and Rh 3+ co-doped SrTiO 3 through the electrostatic self-assembly method for the efficient photocatalytic CO 2 reduction. In comparison with g-C 3 N 4 , the as-prepared CN/LRSTO-30 wt% S-scheme heterojunction not only possesses a broadened visible-light response due to the defect states in La, Rh co-doped SrTiO 3 induced by co-doped La 3+ and Rh 3+ but also has more adsorption sites for the capture and activation of CO 2 molecules. Additionally, separation and transfer efficiency of the photoinduced charge carriers is much enhanced in the CN/LRSTO-30 wt% S-scheme heterojunction via its robust internal electric field, which is firmly demonstrated by in situ irradiation X-ray photoelectron spectroscopy technology. Consequently, the prepared S-scheme heterojunction achieves impressive photocatalytic CO 2 reduction performance with an average CO and CH 4 evolution rate of 4.1–1.8 μmol·g −1 ·h −1 , respectively, which are ~ 1.9 and ~ 22.5-fold higher than those of pure g-C 3 N 4 . This study provides innovative perspectives on the design of creative S-scheme heterojunctions for applications in photocatalytic CO 2 reduction. Graphical abstract
研究领域:
材料科学
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环境科学
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化学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Zexiang Wang,Ruijie Fu,Jinjie Hou,Hong Hu,Jiuhong Yi,Peiyu Yang,Rubing Zou,Yunlei Xianyu,Yirong Guo
Traditional lateral flow immunoassay (LFIA) using single-color labels has limitations in indistinct color change and restriction to the single-mode readout, which can hardly meet the demands of high-performance detection. Inspired by the multiple colors of the rainbow, we outline a multicolor LFIA using multibranched trimetallic platinum–rhodium-cobalt nanoparticles (PRCNPs) as signal labels to initiate multicolor conversion for diverse and multicolor readouts. The intrinsic properties of PRCNPs including their trimetallic composition, multibranched morphology, and strong absorption in the visible spectrum, confer advantages in catalytic activity, antibody utilization, and signal readout. Through the synergistic integration of the catalytic PRCNPs with the etching of gold nanorods, PRCNPs-LFIA enables multicolor readouts in a rainbow-like manner. PRCNPs-LFIA allows for qualitative analysis of acetamiprid, a widely-used neonicotinoid insecticide, at 2 ng mL −1 . It also provides semi-quantitative analysis based on the discrimination of at least 10 colors. Furthermore, quantitative analysis can be conducted across multiple color spaces within the range of 0.01-10 ng mL −1 , achieving a lowest detection result of 0.006 ng mL −1 . The recoveries of acetamiprid in food samples detected by PRCNPs-LFIA in grayscale and multiple color space modes are 87.35%-103.59%, 85.56%-114.33%, 86.14%-114.77%, and 87.81%-112.01%, respectively, with all coefficients of variation below 15%. These results demonstrate the feasibility and accuracy of PRCNPs-LFIA in practical applications. Overall, this study illustrates the potential of multifunctional PRCNPs in the development of multicolor LFIA and broadens the biosensing strategies for point-of-care testing.
研究领域:
分析化学
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纳米技术
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生物传感器
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环境科学
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食品安全
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2014
·
IF 6.007
Moa Z. Granlund,Kjell Jansson,Marita Nilsson,Jazaer Dawody,Lars J. Pettersson
The objective of this paper was to study the influence three promoters (Co, La, Mn) had on the catalytic activity of Rh-based catalysts for autothermal reforming of diesel. The catalysts were supported on CeO 2 -ZrO 2 and the loading was 1 wt.% Rh and 6 wt.% promoter. The catalytic activity was evaluated in a monolith bench scale reactor with Swedish Environmental diesel, MK1. The process parameters employed at the ATR experiments were; O 2 /C ∼ 0.45, H 2 O/C ∼ 2.5 and GHSV ∼ 50,000 h −1 , meanwhile the reactor temperature was ramped from 700 °C to 950 °C. The catalysts were compared based on their fuel conversion, H 2 yield and the selectivity of different short-chain hydrocarbons. The results showed that all three catalysts had both high fuel conversion and H 2 yield in the optimal ATR operation temperatures. The H 2 yield and fuel conversion were increasing in the order Rh/Mn, Rh/La, Rh/Co. To get further insight in the difference between the materials the fresh and aged catalytic materials were characterized. The characterization methods used were H 2 -temperature programmed reduction (H 2 -TPR), powder X-ray diffraction (XRD), and BET surface measurements. The BET surface measurements showed that promotion with La gave improved thermal stability of the material. The XRD showed a high dispersion of all metals except Co, which was present as crystals in the size range of the particles of the support.
研究领域:
催化
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化学工程
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环境科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MEDICINAL CHEMISTRY
·
2024
·
IF 6.8
Feng-Yang Wang,Liang-Mei Yang,Xiao-Lin Xiong,Jing Yang,Yan Yang,Jiu-Qin Tang,Lei Gao,Yuan Lu,Yuan Wang,Taotao Zou,Hong Liang,Ke-Bin Huang
Metal-based chemoimmunotherapy has recently garnered significant attention for its capacity to stimulate tumor-specific immunity beyond direct cytotoxic effects. Such effects are usually caused by ICD via the activation of DAMP signals. However, metal complexes that can elicit antitumor immune responses other than ICD have not yet been described. Herein, we report that a rhodium complex (Rh-1) triggers potent antitumor immune responses by downregulating Wnt/β-catenin signaling with subsequent activation of T lymphocyte infiltration to the tumor site. The results of mechanistic experiments suggest that ROS accumulation following Rh-1 treatment is a critical trigger of a decrease in β-catenin and enhanced secretion of CCL4, a key mediator of T cell infiltration. Through these properties, Rh-1 exerts a synergistic effect in combination with PD-1 inhibitors against tumor growth in vivo. Taken together, our work describes a promising metal-based antitumor agent with a noncanonical mode of action to sensitize tumor tissues to ICB therapy.
研究领域:
肿瘤学
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免疫学
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化学
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药理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Xintai Chen,Mengqi Yang,Qiying Liu,Xiaoling Mou,Linbin Ying,Yu Meng,Ronghe Lin,Yunjie Ding
Halides with strong affiliation to metals are traditionally viewed as positions in heterogeneous catalysis. This study introduces a method to enhance the selective hydrogenation performance of noble metal nanoparticle catalysts (Pd, Pt, and Rh hosted on N-doped carbon, SiO 2 , and Al 2 O 3 ) by gas-phase bromination with 1-bromooctane. Brominated Pd catalysts, particularly those supported on N-doped carbon, show significant improvements in total butene selectivity and stability in butadiene hydrogenation reactions, displaying >97.5 % selectivity to total butenes at complete conversion with 50 h stable performance even at excessive H 2 (H 2 :butadiene = 50) and a high temperature of 473 K. Comprehensive characterizations coupled with density functional theory calculations reveal that bromide species enhance selective hydrogenation by preferentially adsorbing at stepped Pd sites, altering reaction kinetics and preventing over-hydrogenation. Bromination influences reactant and intermediate adsorption, leading to increased competitive adsorption compared to pristine catalysts. Chemisorption studies on butadiene and 1-butene support altered kinetic behaviors post-bromination. X-ray photoelectron spectroscopy analysis demonstrate an increase in surface Pd δ + species, owing to the electron-pulling character of nearby adsorbed bromide. In situ diffuse reflection infrared Fourier transform spectroscopy with CO probe molecules confirms Br species adsorption at unsaturated Pd sites. Overall, the study provides an effective approach to tuning the electronic properties of metal catalysts and highlights the positive impact of bromination on improving the hydrogenation performance.
研究领域:
催化
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材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Nano Materials
·
2025
·
IF 5.5
Xintong Dong,Mengyuan Li,Xueyan Zhong,Mingqi Sun,Xiaoying Zhang,Ying Wang,Yao Wang,Ying Guo
Electrochemical biosensors based on nicotinamide adenine dinucleotide (NADH)-dependent dehydrogenases hold great potential in analytical applications. However, previous biosensors can lead to enzyme detachment and inactivation, thus limiting their applications. This study presents a novel sensing platform based on a three-dimensional MXene-graphene oxide sponge (3D MG). The nanoporous sponge was synthesized by polyethylene glycol (PEG) assisted cross-linking of MXene and small-sized graphene oxide (GO) nanosheets, thereby forming a high-strength porous conductive network and addressing the instability of enzyme-based biosensors. This sponge significantly enhances enzyme immobilization (reducing leaching by 62.27% compared to MXene films) and maintains enzymatic activity under extreme conditions. The 3D MG sensing platform was further fabricated into two biosensors by immobilizing NADH-dependent dehydrogenases (with glutamate dehydrogenase and formate dehydrogenase employed as model enzymes, respectively), using the (2,2′-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complex ([Cp*Rh(bpy)Cl]+) as a mediator that enables the regeneration of bioactive NADH. The two biosensors exhibited low detection limits (0.332 μM for NH4+ and 0.188 mM for HCO3–), excellent reproducibility (relative standard deviation < 4%), and long-term stability (94.82% and 92.63% signal retention after 60 days). The fabrication of 3D MG with a robust nanoporous structure and an enzyme-friendly environment provides a strategy for designing long-life multifunctional enzyme-based biosensors.
研究领域:
生物传感器
·
纳米材料
·
电化学
·
酶工程
·
分析化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2025
·
IF 2.9
Chunhua Zhang,Bowen Li,Xiang Gao,Wei Xiao,Mingfang Chen,Qilong Bian
This work demonstrates a wireless electroenzymatic platform using carbon microsphere electrodes co-immobilized with a rhodium catalyst and lactate dehydrogenase (LDH) for integrated NADH regeneration and pyruvate-to-L-lactate conversion in a bipolar electrochemical system. The 3D "aggregate reactor" architecture, functionalized via diazonium grafting, Rh coordination, and covalent enzyme coupling, enables spatial coupling of cofactor recycling and biocatalysis, while HPLC revealed a L-lactate production rate of 0.04 mM cm-2 h⁻¹ under 12.5 V cm⁻¹ with a plenty of carbon beads attributed to enhanced mass transport. This wireless, scalable design eliminates wiring constraints and offers modular adaptability for sustainable synthesis of chiral chemicals.
研究领域:
电化学
·
催化
·
生物催化
·
材料科学
·
化学工程
·
分析化学
·
可持续化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）