查找使用阿拉丁产品的科研文献

Regulating the d-band center of Ru/CoMoO4 ternary heterostructure by interface engineering for accelerated hydrogen adsorption kinetics

Miao Ma,Min Yang,Cai-Yue Zhang,Hai-Yi Sun,Rong-Jing Su,Xiao-Rui Yue,Chen-Xi Li,Yong-Ming Chai,Bin Dong

Developing low-cost, high-performance Ru-based hydrogen evolution reaction (HER) catalysts is crucial for advancing anion exchange membrane water electrolysis (AEMWE) technology. In this study, based on the Sabatier principle, a Ru/CoMoO 4 heterojunction catalyst with a ternary “nanorod-macroparticle-microparticle” structure is designed. Benefiting from the strong electronic interactions, a lower d-band center of Ru/CoMoO 4 is observed, resulting in optimal adsorption between Ru species and the key H* intermediates to greatly enhance the hydrogen desorption kinetics. Importantly, this interface engineering effect prevents the Volmer-Tafel step from becoming rate-limiting step, thereby promoting electron and mass transport. As a consequence, Ru/CoMoO 4 outperforms most of the reported HER catalysts at an ultra-low Ru loading of only 0.2 wt%. In alkaline media, it only requires an overpotential of 55 mV to achieve 100 mA cm −2 , with a low Tafel slope of 16 mV dec -1 , and operates stably for over 230 h at an industrial-grade current density of 1000 mA cm -2 . The AEMWE electrolyzer based on the Ru/CoMoO 4 catalyst achieves efficient and stable hydrogen production at 1000 mA cm⁻ 2 @ 1.93 V. This work not only provides a high-performance catalyst, but also elucidates a strategy for precisely controlling d-band center through heterojunction interface engineering to optimize reaction [email protected]

Demethylation-modified sodium lignosulfonate-templated Ru-Co nanoparticles for mild hydrogenation of lignin-derived diphenylmethanes to cyclic hydrocarbons

Shan Gao,Jiahui Wei,Mengxing Yu,Ningbo Yang,Lei Wang,Fengli Yu,Bing Yuan

An aqueous Ru-Co bimetallic catalyst system was successfully constructed. • The activity of Ru-Co catalyst was enhanced via sodium lignosulfonate demethylation. • Dicyclohexylmethane and perhydrofluorene were produced under mild conditions. An aqueous bimetallic nanoparticle catalyst system (Ru-Co@DMSLS aq ) was successfully constructed by first modifying sodium lignosulfonate (SLS) via a Na 2 SO 3 -mediated, NaOH-catalyzed method to obtain demethylated SLS (DMSLS). 1 H NMR analysis revealed that the increased hydroxyl content in optimized DMSLS was the key factor enhancing the reduction ability toward metal ions in aqueous solution, thereby yielding Ru and Co nanoparticles with improved catalytic activity. With a precursor ratio of n (Ru 3 O(OAc) 7 )/ n (Co(OAc) 2 ) = 3/2, the resulting Ru-Co@DMSLS aq system featured uniformly dispersed nanoparticles and exhibited outstanding catalytic performance in the hydrogenation of diphenylmethane (DPM) and the hydrodeoxygenation (HDO) of o -hydroxydiphenylmethane ( o -HDPM). Under the conditions of 80 °C, 1.5 MPa H 2 , and 4 h, nearly complete conversion of DPM was achieved with 99.2% selectivity toward dicyclohexylmethane (DCHM). Additionally, a yield of 98.5% for perhydrofluorene (PHF) was attained at 90 °C, 1.5 MPa H 2 , and 4 h in the HDO of o -HDPM. The aqueous bimetallic system enabled favorable product-catalyst self-separation and could be reused five times. This work presents a feasible strategy for valorizing lignin derivatives into low-cost, efficient catalysts for biomass-related hydrogenation processes. Download: Download high-res image (269KB) Download: Download full-size image

Ru-Co bimetallic catalysts with synergistic crystalline phase regulation and hydrogen spillover for deep hydrodeoxygenation of lignin oil

Jing-jing Wu,Jia-yuan Tian,Feng Lin,Yu-long Ma,Yong-gang Sun,Pei Ma,Shuai-lei Li,Xue Zhang,Yi-shu Ma,Xiao-lin Xue

The efficient hydrodeoxygenation (HDO) of lignin oil to produce high-value-added cycloalkanes is a key route for biomass resource utilization. However, developing catalysts with both high catalytic activity and product selectivity remains a crucial challenge in this field. Herein, a strategy integrating crystalline-phase regulation and hydrogen spillover was proposed. Ru was doped into the ZIF-67 precursor via a one-pot method. After controlled calcination and hydrogen reduction, a nitrogen-doped carbon-coated Ru-Co bimetallic catalyst (RuCo@NC) was successfully prepared. Characterization results showed that the introduction of Ru induced the phase transformation of Co from face-centered cubic (FCC) to hexagonal close-packed (HCP) and precisely regulated the electron density distribution of catalytic active sites through Ru to Co electron transfer. H 2 -TPR/TPD confirmed that Ru, as a hydrogen spillover site, significantly enhanced low-temperature reducibility and hydrogen adsorption capacity. DFT calculations indicated that Ru sites dominated the efficient dissociation and activation of H₂ molecules, while Co sites were responsible for the selective adsorption of substrate molecules. The synergistic effect between the two metals greatly improved the HDO activity of the catalyst. The optimized 0.009RuCo@NC-400 catalyst achieved 100% conversion of lignin oil at 240 °C and 2 MPa H₂, with a cycloalkane selectivity of 73.7%. Moreover, the conversions of ten lignin derivatives were all above 97%. This study reveals a synergistic catalytic mechanism of the 0.009RuCo@NC-400 catalyst, integrating crystalline phase structure, electronic effects, and hydrogen spillover, providing theoretical guidance for the design of efficient HDO catalysts.

Green diesel production via biodiesel upgrading over Ru/nitrogen-doped carbon catalysts derived from yeast cell wall waste

Yuwei Chen,Mingxin Zhong,Yujie Xu,Sijie Hua,Lingxin Bao,Yongsheng Fan,Jianchun Jiang,Feng Long,Xincheng Cao,Junming Xu

Multiple-atom-site catalysts for highly efficient hydrogen production from ammonia decomposition over Ru/LaxTiyAz (A = O, N)

Xiao-Yu Guo,Jun-Hao Wang,Ting-Zhou Li,Kai Xu,Chun-Jiang Jia,Hao Dong,Ding Ma,Chen Li,Ya-Wen Zhang

The efficient ammonia decomposition catalysts are crucial for advancing the application of hydrogen energy produced from ammonia. Herein, La 2 Ti 2 O 7 and LaTiO 2 N are developed as supports for constructing efficient Ru/La 2 Ti 2 O 7 and Ru/LaTiO 2 N ammonia decomposition catalysts. Compared with monoxide supported catalysts such as Ru/La 2 O 3 , Ru/TiO 2 and Ru/SiO 2 , Ru/La 2 Ti 2 O 7 shows higher activity, achieving an NH 3 conversion rate of 66.5% at 450 °C with a fairly low Ru loading amount (about 1.4 wt%). Using Ru/LaTiO 2 N, we achieve an even higher NH 3 conversion rate (76.1%), hydrogen production rate (1556 mmol/(g Ru ·min)), and 140-hour catalytic stability at 450 °C with a GHSV of 30000 mL/(g cat ·h). Various characterizations demonstrate that the presence of Ti n + is conductive to the adsorption of NH 3 , while the presence of La 3+ with its coordinated O 2– endows La 2 Ti 2 O 7 and LaTiO 2 N with robust surface basicity facilitating the recombination and desorption of N*, together assisting the active metal Ru to catalyze ammonia decomposition. This study provides new material options and design insights from the collective contribution of multiple atom sites in a complex multicomponent heterogeneous catalytic system for the development of efficient Ru-based ammonia decomposition catalysts.

CRISPR/Cas12a-assisted electrochemiluminescent detection of ochratoxin A based on COF@Ru coupled with a DNA tetrahedral scaffold

Yang Cao,Chun Huang,Kui Li,Xi Zhang,Mengfei Tong,Jiale Tu,Kun Yang,Shuai Yuan,Hong Zhang

To sensitively detect ochratoxin A (OTA), a CRISPR/Cas12a-assisted electrochemiluminescence (ECL) aptasensor based on COF@Ru coupled with a DNA tetrahedral scaffold (DTS) was successfully fabricated. The covalent organic framework (COF) acted as a confined micro-reactor for the tris(2,2′-bipyridyl)ruthenium(II)/tri-n-propylamine (Ru(bpy)32+/TPrA) system and hence, evidently enhanced ECL signals. Au nanoparticles (AuNPs) coupled with DTS caused more ferrocene (Fc)-modified quenching DNA probe molecules to be attached to the surface of the sensing electrode, which could reduce the detection background. Activated CRISPR/Cas12a could effectively amplify the ECL signal since it could cut off a considerable amount of quenching DNA probe molecules and make them move away from the electrode. Owing to these strategies, the fabricated ECL aptasensor could detect OTA as low as 3.5 fg mL−1 in a linear detection range of 10−5–100 ng mL−1. Furthermore, the CRISPR/Cas12a and COF@Ru coupled with DTS-based ECL biosensor possessed high stability and specificity. More importantly, the ECL biosensor could effectively detect OTA in food samples, indicating that it can play a role in monitoring OTA levels in the field of food safety.

Ru-Mo2C nanoclusters anchored on N, P crownshaft-derived porous carbon for efficient hydrogen evolution in alkaline seawater

Daniel Kobina Sam,Zhen Tang,Yan Cao

Noble-metal-based electrocatalysts have long been the top choice for hydrogen evolution reaction (HER) electrocatalysts, offering low overpotentials and Tafel slopes. Nonetheless, their use in alkaline media has been limited due to the sluggish kinetics of the Volmer process. Herein, we develop a unique biomass-derived heteroatom-doped porous carbon material via self-templating to anchor ruthenium‑molybdenum carbide (Ru-Mo 2 C) nanoclusters. The synthesized Ru-Mo 2 C-supported heteroatom-doped porous carbon (RuMo-NPCSPC) shows exceptional electrocatalytic ability for alkaline HER, achieving low overpotentials of 49, 85, and 92 mV to realize 10 mA cm −2 in 1 M KOH, alkaline seawater, and simulated alkaline seawater, respectively. The RuMo-NPCSPC also boasts low Tafel slopes and ultrahigh Faradaic Efficiencies (98–100 %) in alkaline media, outperforming most noble metal-based catalysts and mercantile Pt/C. Most importantly, the catalyst demonstrates outstanding stability, signifying its potential for industrial hydrogen production. This work delivers profound perspectives into synthesizing advanced nanostructured porous carbon materials using abundant biomass resources for alkaline HER.

Switching of the CO2 hydrogenation selectivity via organic amines over ionic porous polymer-supported Ru single atom catalyst

Huiying Liao,Huihui Zhang,Xinjia Wei,Xiuge Zhao,Ji Ding,Ning An,Pengfei An,Sheng Dai,Zhenshan Hou

Converting carbon dioxide into high-value chemicals through catalytic means is one of the most promising approaches for CO 2 utilization. In this work, the ionic porous polymer-supported Ru single-atom catalysts were constructed for CO 2 hydrogenation reactions. It is noteworthy that the anions of the polymers exerted a significant influence on porosity and CO 2 adsorption capacity, which are crucial for achieving efficient CO 2 hydrogenation under mild conditions. Especially, the products of CO 2 hydrogenation on the polymer catalyst can be switched by tuning the type of amines, i.e. , with the assistance of tertiary amine, CO 2 /H 2 and methanol can produce methyl formate efficiently. However, CO 2 /H 2 , the primary and secondary amines switched to afford the corresponding formamides by N-formylation reaction with the identical catalyst. The detailed characterization demonstrates that Ru is only partially coordinated with phosphine ligand tethered in the polymer framework, while the remaining uncoordinated free phosphine bearing lone-pair electrons can activate CO 2 through a synergistic interaction with the moiety of ionic liquids, thereby enhancing the catalytic activity. The catalytic system exhibits high efficiency, stability and ease of recyclability, allowing for reuse up to ten times.

Supported Ru Single Atoms and Clusters on P-Doped Carbon Nitride as an Efficient Photocatalyst for H2O2 Production

Lulu Bai,Hao Sun,Qiang Wu,Weifeng Yao

Graphical Photocatalytic H 2 O 2 evolution : A new P-doped carbon nitride loaded with ruthenium single atoms and clusters was successfully synthesized by photoreduction method. It has exhibited an excellent photocatalytic activity toward H 2 O 2 evolution. This study surmounts people‘s understanding that precious metal loading is not conducive to H 2 O 2 selectivity and provides ideas for the design of extremely active and stable single-atom and clusters. Photocatalytic H 2 O 2 evolution via two-electron oxygen reduction is a promising path for renewable and on-the-spot H 2 O 2 production compared with the traditional anthraquinone method. However, the efficiency of photocatalytic production of H 2 O 2 is usually very low. Herein, P-doped carbon nitride loaded with ruthenium single atoms and clusters (Ru atom /P-CN) is reported as an efficient photocatalyst for H 2 O 2 production. The yield of H 2 O 2 over Ru atom /P-CN (385.8 mmol g −1 h −1 ) is about 4.3 times higher than that of P-CN (88.9 mmol g −1 h −1 ) and 3.6 times higher than that of ruthenium nanoparticles loaded P-CN (105.9 mmol g −1 h −1 ). Further mechanistic study indicates that the presence of Ru in the form of single atoms and clusters not only improves the separation efficiency of photogenerated carriers and inhibits the recombination of photogenerated electron-hole pairs, but also increases the reactive sites of this catalytic system. This study breaks through people‘s understanding that precious metal loading is not conducive to H 2 O 2 selectivity and provides a new way to prepare low-metal loading, high-activity photocatalysts for H 2 O 2 production.

Hydrodeoxygenation of Lignin-Derived Monomers and Dimers over a Ru Supported Solid Super Acid Catalyst for Cycloalkane Production

Xing Zhang,Hui Yan,Lingjun Zhu,Tian Li,Shurong Wang

The monomers and dimers produced via lignin depolymerization are a promising alternative to transportation fuels after hydrodeoxygenation (HDO). However, these compounds contain numerous oxygen-containing functional groups that are strongly bonded to aromatic rings. Therefore, the conventional HDO of lignin-derived compounds faces serious problems of catalyst deactivation due to coke deposition and low hydrocarbon yields. A metal–solid super acid catalyst, i.e., Ru(SO 4 2− )/ZrO 2 –CeO 2 , is synthesized, characterized, and evaluated for the HDO of various lignin-derived monomers and dimers in a biphasic n -dodecane/H 2 O system. A high cyclohexane yield of 98.5% is obtained by the HDO of phenol performed at 200 °C and 5 MPa. The “hydrated” configuration can be formed between the hydrogenation intermediates and H 2 O on the Ru sites. In addition, the anionic vacancies of ZrO 2 –CeO 2 can be occupied by H − derived from the heterolytic cleavage of H 2 , leading to the formation of metal hydrides. The strong acidity of SO 4 2− /ZrO 2 –CeO 2 is beneficial for the subsequent deoxygenation of the hydrotreated products. In addition, the biphasic system can minimize the side reactions induced by the strong acidity of the catalyst. The catalytic system also exhibits a good catalytic performance for the HDO of other lignin-derived monomers and dimers to produce cycloalkanes.

Unraveling How Crystal Phase and Dispersion of Mesoporous Carbon-Confined Ru Nanoclusters Govern Full-pH Hydrogen Evolution Performance

Xiaofang Ma,Yuhao Cai,Yang Gao,Hairong Zhao,Xiaxia Liu,Yuanyuan Tian,He Xiao

The design and fabrication of highly active hydrogen evolution reaction (HER) electrocatalysts that can outperform Pt/C are extremely desirable but remain challenging. Herein, the fabrication of S-doped hollow mesoporous carbon anchored Ru nanoclusters (Ru NCs/S-HMCs) is reported as a novel and highly active HER electrocatalyst through modified Stöber process and subsequent hydrothermal treatment, in which Ru NCs (1.64 nm in size) are uniformly anchored into S-HMCs channels. Benefiting from the unique electronic structure induced by S doping and the spatial confinement effect of the mesoporous carbon, the Ru NCs/S-HMCs catalyst exhibits excellent pH-universal HER activity, requiring only 3.5, 61.0, and 63.5 mV of overpotential to achieve a current density of 10 mA cm-2 in alkaline, neutral, and acidic electrolytes, respectively. In 1 M KOH, 0.5 M H2SO4, and 0.5 M PBS solutions, Ru NCs/S0.5-HMCs exhibits high mass activities of 21542, 2998 and 7088 mA mgRu−1 at an overpotential of -50 mV, respectively. The excellent activity stems from: (1) the pore confinement effect, which promotes the formation of ultrasmall Ru NCs (1.64 nm) and suppresses metal leaching; (2) S doping, which modulates the electronic structure of Ru and reduces the water dissociation barrier; and (3) the hollow mesoporous architecture, which accelerates mass and electron transport. This work provides insights for designing high-efficiency pH-universal electrocatalysts.

Constructing Ru single-atomic sites through potential-induced self-reconstruction to accelerate electrocatalytic nitrate reduction for ammonia production

Huiqun Cao,Bin Liang,Shenghua Ye,Ziqiong Zhuang,Lirong Zheng,Wenda Chen,Weibin Chen,Jie Zhang,Qinghao Zhang,Jianhong Liu,Xueqing Yan,Qianling Zhang

Conversion of NO 3 − -to-NH 3 via the electrocatalytic nitrate reduction reaction (NO 3 - RR) is an emerging strategy for ammonia production and storage of “green hydrogen”, but is limited by the dissatisfactory activity and selectivity. In this study, we discovered that cobalt carbonate hydroxide (Co 2 (OH) 2 CO 3 ) underwent a potential-induced self-reconstruction to cobalt hydroxide (Co(OH) 2 ) during NO 3 - RR. The incorporation of Ru into Co 2 (OH) 2 CO 3 expedited the aforementioned self-reconstruction process and resulted in the formation of Ru single-atomic sites (Ru SASs) anchored on Co(OH) 2 nanosheets. This structure is reported as a highly efficient electrocatalyst for NO 3 − -to-NH 3 conversion and exhibits exceptional electrochemical performance in zinc-NO 3 − batteries. Theoretical analysis revealed that the conversion of NO 3 − -to-NH 3 occurred on Ru SASs through an N-end pathway with *NO as a characteristic intermediate. Furthermore, Ru SASs facilitated the thermodynamic-determining step of *NH 2 -to-*NH 3 , thus promoting the overall NO 3 − -to-NH 3 conversion process.