Chemical Science
·
2021
·Vol. 12
·期 20
·7125-7137
·
IF 9.825
Xuanbei Peng,Han-Xuan Liu,Yangyu Zhang,Zheng-Qing Huang,Linlin Yang,Yafei Jiang,Xiuyun Wang,Lirong Zheng,Chunran Chang,Chak-tong Au,Lilong Jiang,Jun Li
The desire for a carbon-free society and the continuously increasing demand for clean energy make it valuable to exploit green ammonia (NH3) synthesis that proceeds via the electrolysis driven Haber–Bosch (eHB) process. The key for successful operation is to develop advanced catalysts that can operate under mild conditions with efficacy. The main bottleneck of NH3 synthesis under mild conditions is the known scaling relation in which the feasibility of N2 dissociative adsorption of a catalyst is inversely related to that of the desorption of surface N-containing intermediate species, which leads to the dilemma that NH3 synthesis could not be catalyzed effectively under mild conditions. The present work offers a new strategy via introducing atomically dispersed Ru onto a single Co atom coordinated with pyrrolic N, which forms RuCo dual single-atom active sites. In this system the d-band centers of Ru and Co were both regulated to decouple the scaling relation. Detailed experimental and theoretical investigations demonstrate that the d-bands of Ru and Co both become narrow, and there is a significant overlapping of t2g and eg orbitals as well as the formation of a nearly uniform Co 3d ligand field, making the electronic structure of the Co atom resemble that of a “free-atom”. The “free-Co-atom” acts as a bridge to facilitate electron transfer from pyrrolic N to surface Ru single atoms, which enables the Ru atom to donate electrons to the antibonding π* orbitals of N2, thus resulting in promoted N2 adsorption and activation. Meanwhile, H2 adsorbs dissociatively on the Co center to form a hydride, which can transfer to the Ru site to cause the hydrogenation of the activated N2 to generate N2Hx (x = 1–4) intermediates. The narrow d-band centers of this RuCo catalyst facilitate desorption of surface *NH3 intermediates even at 50 °C. The cooperativity of the RuCo system decouples the sites for the activation of N2 from those for the desorption of *NH3 and *N2Hx intermediates, giving rise to a favorable pathway for efficient NH3 synthesis under mild conditions.
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ChemSusChem
·
2020
·Vol. 14
·期 2
·730-737
·
IF 7.962
Wei Li,Bomin Feng,Lingya Yi,Junying Li,Weihua Hu
Graphical Time for HER/OER : Tremella-like Ru-doped Co-V layered double hydroxide nanosheet exhibits excellent bifunctional catalytic activity toward HER and OER in alkaline media. It affords 10 mA cm −2 electrolytic current density at an extremely low cell voltage of 1.50 V. Incorporation of Ru changes the morphology to offer high surface areas and significantly boosts the electrocatalytic activity. Active electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are decisive for achieving efficient energy conversion from electricity to hydrogen fuel through water electrolysis. In this study, tremella-like Ru-doped Co-V layered double hydroxide nanosheets on Ni Foam (Ru-CoV-LDH@NF) was fabricated by a one-pot solvothermal reaction. As-prepared Ru-CoV-LDH@NF, with a nominal Ru loading of around 51.6 μg cm −2 exhibits excellent bifunctional catalytic activity towards HER and OER in alkaline media. To accomplish a current density of 10 mA cm −2 , it demands 32 mV and 230 mV overpotentials for HER and OER, respectively. The alkali electrolyzer utilizing Ru-CoV-LDH/NF as bifunctional electrocatalyst affords 10 mA cm −2 electrolytic current density at an extremely low cell voltage of 1.50 V, showing excellent performance compared to a Pt/C−RuO 2 -based electrolyzer and many other bifunctional electrocatalyst-based ones. The incorporation of Ru changes the morphology of the resultant nanosheets to offer high electrochemical surface areas for electrocatalysis; at the same time, it significantly boosts the intrinsic HER/OER electrocatalytic activity. For HER, the energy barrier of the Volmer step is efficiently reduced upon Ru doping, whereas the Ru dopants optimize the absorption strength of *O intermediates to facilitate the OER process. This work offers a feasible means to optimize the Co-based hydroxide materials for improved electrocatalysis in overall water splitting.
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SENSORS AND ACTUATORS B-CHEMICAL
·
2020
·
IF 7.1
Dandan Fang,Huizhu Ren,Yitian Huang,Hong Dai,Defu Huang,Yanyu Lin
Herein, an ultrasensitive electrochemiluminescence (ECL) immunosensor based on a high performance probe of Nb 2 CTx MXene immobilized ZnO quantum dots (QDs) was constructed for Thyroglobulin (Tg) detection. ZnO QDs with good biocompatibility and catalytic property was for the first time utilized as coreaction accelerator in Ru(bpy) 3 2+ /S 2 O 8 2− system and enhanced ECL signal. Specifically, ZnO QDs can facilitate S 2 O 8 2− reduction to generate more SO 4 − , and then reacted with cathodic radical of Ru(bpy) 3 2+ , realizing 2-fold enhancement in ECL intensity. Additionally, Nb 2 CTx MXene possesses excellent properties and was used as prominent supporter, improving the loading capacity of Ru(bpy) 3 2+ and ZnO QDs, and accelerating the electron transfer, resulting in ECL signal enhancement. Furthermore, Nb 2 CTx MXene acted as temperature controller and increased the electrode surface temperature by converting laser energy into heat, further amplified ECL signal. Because of the high sensitivity, good specificity and favorable stability, the proposed immunosensor realized sensitive detection of Thyroglobulin and had a great application prospect in bioanalysis and clinical diagnosis.
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Nanoscale Research Letters
·
2020
·Vol. 15
·期 1
·1-15
·
IF 3.578
Fan Li,Sun Qi,Zheng Wei,Tang Qinyuan,Zhang Ting,Tian Mengkui
The rutile Sn x Ti 1− x O 2 ( x = 0, 0.33, 0.5, 0.67, 1) solid solution was synthesized by a one-step hydrothermal method, in which tetrabutyl titanate and Tin (IV) chloride pentahydrate were used as raw materials. A series of Ru/Sn x Ti 1− x O 2 were then prepared by the impregnation process in RuCl 3 to investigate the performance and stability of CO and C 3 H 8 oxidation. These catalysts were characterized through XRD, N 2 adsorption-desorption, FT-IR, TEM, XPS, H 2 -TPR, and O 2 -TPD techniques. The effect of Sn/Ti molar ratio and hydrothermal condition on the low-temperature catalytic oxidized performance and stability of Ru/Sn x Ti 1− x O 2 were investigated. The results indicated that Ru/Sn 0.67 Ti 0.33 O 2 catalyst showed an excellent activity and stability at low temperatures. The CO conversion reached 50% at 180 °C and 90% at 240 °C. Besides, the C 3 H 8 conversion reached 50% at 320 °C, the complete conversion of C 3 H 8 realized at 500 °C, and no deactivation occurs after 12 h of catalytic reaction. The excellent low-temperature activity and stability of the Ru/Sn 0.67 Ti 0.33 O 2 were attributed to the following factors. Firstly, XRD results showed that Sn 4+ was successfully introduced into the lattice of TiO 2 to replace Ti 4+ forming a homogeneous solid solution (containing –Sn 4+ –O–Ti 4+ – species), which was consistent with TEM and N 2 adsorption-desorption results. The introduction of Sn could suppress the growth of anatase crystal and promote the formation of rutile phase, and this phase transition was helpful to improve the low-temperature activity of the catalysts. Secondly, TEM images showed that ultrafine Ru nanoparticles (~ 5 nm) were dispersed on Sn 0.67 Ti 0.33 O 2 support, suggesting that the formation of Sn x Ti 1− x O 2 solid solution was beneficial to the dispersion of Ru particles.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2020
·
IF 4.65
Siqi Zhang,Ying Wang,Dan Li,Ziye Kang,Feilong Dong,Haiming Xie,Jia Liu
The synergistic effect between noble metal and spinel-type compounds is beneficial for enhancing the electrochemical performance in a Li–O 2 battery. Herein, Ru-impregnated needle-like NCO embedded in porous carbon textiles (CTs) (x wt% Ru@NCO/CTs (x = 0, 0.5, 1, 2, and 5)) is applied as a flexible and binder-free O 2 electrode for Li–O 2 batteries. The NCO structure can benefit to the Li + migration, O 2 diffusion, and Li 2 O 2 accommodation. The Ru nanoparticles can promote OER and ORR reaction kinetics and lower the overpotential. A flexible Li–O 2 cell with 1 wt% Ru@NCO/CTs exhibits a good cyclic stability of 360 cycles with an overpotential of 0.78 V at a constant current density of 200 mA/g, a considerable rate performance, a high reversibility with the Li 2 O 2 formation and its reverse decomposition, and a good flexibility stability under bending and twisting at the different conditions. This work can contribute to the development of electrode material and its architecture design for portable and wearable devices .
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APPLIED CATALYSIS A-GENERAL
·
2020
·
IF 5.006
Sishi Zhang,Jie Xu,Hongmei Cheng,Cuicui Zang,Bin Sun,Heyan Jiang,Fengxia Bian
Atomic economy, non-toxicity, harmlessness and multidirectional selectivity advocated by green chemistry have increasingly become a hot and difficult research topic. Herein, we present a highly efficient, one-pot tandem and easy-to-operate method through which we could directly produce a broad range of multi-directional selective hydrogenated amines or N-alkyl aliphatic amines using aromatic nitro compounds as raw materials. Ru/LDH with characteristics of layered mesoporous structure, well dispersed small Ru nanoparticles and LDH stabilization to the Ru NPs was employed as the catalyst. It is remarkable that multi-directional superb chemoselectivity to aromatic amines, alicyclic amines as well as N-alkyl aliphatic amines could be achieved with excellent catalytic activity and recyclability by tuning reaction conditions over 5wt%Ru/LDH-2. Additionally, this catalytic system also exhibited attractive activity and multi-directional chemoselectivity in the hydrogenation of quinoline and its derivatives with solvents of different polarity. Chemoselectivity to 5,6,7,8-tetrahydroquinoline derivatives could reach as high as 95.6 %.
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Applied Materials Today
·
2020
·
IF 8.352
Fangman Chen,Fan Zhang,Dan Shao,Weibin Zhang,Liqin Zheng,Wei Wang,Wendi Yang,Zheng Wang,Jianxin Chen,Wen-fei Dong,Fangnan Xiao,Yunkun Wu
Ruthenium-based agents are promising in cancer chemotherapy but lack specific targeting and controlled release properties. Herein, a new class of bioreducible mer-[Ru(III)Cl 3 (dmso)(L)] prodrugs with highly DNA binding affinity were designed and synthesized for nucleus-targeted chemotherapy and selective activation in response to the tumor microenvironment. In this regard, ruthenium(III) prodrugs were reduced into highly active ruthenium(II) drugs in response to high intracellular glutathione levels, resulting in tumor apoptosis through synergistic intercalation that blocked DNA replication and coordination that cleaved nuclear DNA. In light of this, a multifunctional nanodrug (Ru-MSN-PLip) was constructed by integrating RuDPNI prodrug-loaded mesoporous silica nanoparticles (Ru-MSN) with a fusion protein-incorporated liposome (PLip) to achieve multiple targeting and eGFP-based fluorescence imaging of nonsmall cell lung cancer. Due to fusion protein-based cancer cell recognition and Ru(III) prodrug-mediated nuclear DNA targeting, Ru-MSN-PLip achieved sequential delivery and greater antitumor activity. In addition, Ru-MSN-PLip exhibited long-term blood circulation and selective accumulation in tumors, leading to significantly limited tumor growth in vivo without notable toxicity. Our findings indicated the potential applications of these types of bioreducible and traceable nanoprodrugs for efficient and safe nonsmall cell lung cancer therapy.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Wenlin Li,Feng Li,Junwen Chen,Luis E. Betancourt,Chunyan Tu,Mingjie Liao,Xing Ning,Jiajun Zheng,Ruifeng Li
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is an essential reaction step to produce value-added renewable chemicals and fuels. In this study, it is demonstrated that the dispersed state of metal and the acid properties of the support can be tuned directly in the synthesized stage for the Ru/MCM-49 catalysts. The average metal particle size of Ru was found at ∼2.0 nm, and strong metal–support interaction was observed for the Ru/MCM-49(DP) catalyst. Mesopores presented can enhance the conversion rate for LA to GVL. The presence of a higher amount of Lewis acid sites can promote the ring closure esterification of the intermediate 4-HPA. High catalytic activity with a TOF value of >3000 h–1, as well as excellent reusability, were achieved by Ru/MCM-49(DP). The agglomeration of Ru particles and the coke formation were thought to be responsible for the deactivation of the catalyst.
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Nano Energy
·
2019
·
IF 15.548
Shenghua Ye,Feiyan Luo,Tingting Xu,Pingyu Zhang,Hongdong Shi,Shiqi Qin,Jiaping Wu,Chuanxin He,Xiaoping Ouyang,Qianling Zhang,Jianhong Liu,Xueliang Sun
The development of the hydrogen evolution reaction (HER) in alkaline electrolyte is highly desirable but is hindered by sluggish water dissociation and the high cost of Pt–based catalysts. In this study, a facile pyrolyzation method is proposed for synthesizing the Ru nanoclusters (NCs) anchored on B/N–doped graphene (BNG) (denoted as Ru NCs/BNG). During the pyrolyzation, boron was doped into graphene and facilitated the formation of ultra−small Ru NCs with a diameter of 0.5–1 nm. The electronic interaction between B and Ru NCs accelerated the cleavage of H–OH, altering the HER mechanism and lowering the activation energy of H 2 formation, endowing Ru NCs/BNG with excellent alkaline HER activity, even surpassing that of Pt/C. This study reveals the importance of water dissociation barriers for alkaline HER activity and provides a new strategy for improving the HER catalytic activity .
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Journal of Materials Chemistry B
·
2019
·Vol. 7
·期 40
·6210-6223
·
IF 5.047
Yanan Liu,Yayu Wen,Xu Chen,Xufeng Zhu,Qianqian Yu,Youcong Gong,Guanglong Yuan,Jie Liu,Xiuying Qin
Due to the complexity and heterogeneity of solid tumors, traditional clinical treatments often only achieve limited therapeutic effects. Tumor-associated macrophages (TAMs) play a key role in the development of solid tumors, and the elimination of solid tumors based on the tumor microenvironment has proven to be an effective therapeutic strategy. Here, we successfully developed Ru-based nanoparticles, Ru@ICG–BLZ NPs, with inflammation-responsive release ability, which could repolarize TAMs into M1 macrophages (with an antitumor role) and further produce hyperthermia and ROS to eliminate cancer cells. In vitro experiments showed that Ru@ICG–BLZ NPs had superior drug (ICG and BLZ-945) loading capacity and sensitive inflammation-responsive drug release behavior, which enhanced CT26 cell uptake and penetration ability. Furthermore, in vivo experiments showed that Ru@ICG–BLZ NPs could effectively up-regulate the expression of M1 markers (iNOS, and IL-12) and exert phototherapy to ablate solid tumor, without causing obvious damage to the surrounding tissues of the tumor. The lower toxicity and excellent antitumor ability of Ru@ICG–BLZ NPs could provide new ideas for the clinical transformation of nanomedicine.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Dan Zhang,Jin Liu,Bin Song,Chenyu Li,Yuyao Chen,Huaifang Zhang,Yuanyuan Feng
“Time-amount” precise phosphidation successfully constructs amorphous/crystalline/metallic three-phase heterojunction. • Multiphase heterojunction functional synergy facilitates the spatial division of labor for HER pathway at the nanoscale. • Ru→Ru 2 P→a-Ru 2 P relay electron transfer mechanism ensures its excellent seawater HER at industrial current density. Sluggish water dissociation kinetics and stability issues caused by chloride ions pose severe challenges for hydrogen evolution reaction (HER) catalysts in alkaline seawater environments. This study proposes a design philosophy of “multiphase heterojunction functional synergy”. Through a precise microwave phosphidation strategy, a three-phase heterojunction catalyst composed of amorphous Ru 2 P, crystalline Ru 2 P, and metallic Ru (a/c-Ru 2 P@Ru/C) was successfully synthesized. Systematic modulation enabled controllable synthesis of the catalyst's microstructure (amorphous/crystalline phase ratio) and macroscopic composition. This catalyst demonstrates outstanding comprehensive performance in alkaline seawater media: it exhibits a low overpotential of only 36 mV at a current density of 10 mA cm −2 , maintains stable operation for over 200 h at a high current density of 500 mA cm −2 , and shows leading cell voltage for overall water splitting. A series of characterizations indicate that the successful formation of a three-phase heterostructure in a/c-Ru 2 P@Ru/C induces interfacial electron transfer from Ru to phosphides, thereby optimizing the electronic structure of active sites. This multiphase synergy achieves a “spatial division of labor” in the HER reaction pathway: electron-rich amorphous regions promote water dissociation, while electron-modulated metallic sites accelerate hydrogen desorption. Concurrently, the robust heterointerface ensures long-term stability under harsh seawater conditions.
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RARE METALS
·
2023
·Vol. 42
·期 12
·4015-4028
·
IF 8.8
Ma Xiao-Fang,Xiao He,Jing Yan-Ying,Gao Yang,He Ying-Luo,Zhao Man,Jia Jian-Feng,Wu Hai-Shun
Ru-based electrocatalysts have demonstrated excellent electrocatalytic performance toward hydrogen evolution reaction (HER). However, designing Ru nanoparticles/nanoclusters (Ru NPs/NCs) with abundant accessible active sites is challenging. Herein, a selective facile hydrothermal in situ polymerization strategy is described to accurately control the anchoring point of Ru in hollow mesoporous carbon spheres (HMCs) (outer surface, HMCs@Ru; cavity, Ru@HMCs; and pore channels, Ru/S-HMCs). The HER mechanisms of the three catalysts over a wide pH range were revealed by analyzing the loading position, content, dispersion, particle size, and valence state of Ru. HMCs@Ru shows excellent area activity, with overpotentials of 64.3, 2.8, and 78.1 mV at 10 mA·cm −2 in 0.5 mol⋅L −1 H 2 SO 4 , 1 mol⋅L −1 KOH, and 0.5 mol⋅L −1 phosphate buffer saline (PBS) solutions, respectively. Ru/S-HMCs exhibit high mass activity, with values 43.3, 2.9, and 12.7 times those of Pt/C in alkaline, acidic, and neutral media, respectively, at − 50 mV (vs. reversible hydrogen electrode (RHE)). After 2000 cyclic voltammetry cycles, the performances of HMCs@Ru and Ru/S-HMCs hardly decrease, indicating good stability. The excellent electrocatalytic activity can be attributed to two main factors: (1) the confinement effect, which not only promotes high Ru dispersion but also prevents the leaching of active metal under harsh conditions, and (2) their excellent structural characteristics. The catalyst structure features a large hollow located in the center (~ 160 nm in diameter) and an ultrathin monolayer of mesopores (~ 6 nm) uniformly distributed on the hollow shells, ensuring fast mass diffusion and electron transfer kinetics, as well as complete accessibility of catalytic sites. Graphical abstract
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危险品化学品经营许可证（带存储）