CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Yan Duan,Mifeng Xue,Bin Liu,Man Zhang,Yuchen Wang,Baojun Wang,Riguang Zhang,Kai Yan
Electrocatalytic refinery of low-value biomass-based glycerol into value-added chemicals formic acid (FA) is an attractive alternative to traditional thermochemical refineries. However, constructing non-precious catalysts with abundant active hydroxyl (OH*) is the main obstacle to the electrocatalytic glycerol oxidation reaction (EGOR). Herein, we combine density functional theory (DFT) and experiments to investigate EGOR over the finely constructed NiCo 2 O 4 nanosheets. DFT results firstly indicate that the NiCo 2 O 4 nanosheets exhibit the highly hydroxylated (311)-OH* surface with the lowest Gibbs free energy, which significantly improves the electrochemical reaction kinetics and can achieve desirable FA yield by adjusting the adsorption energy of the adsorption intermediate. Following the theoretical prediction, ultrathin NiCo 2 O 4 nanosheets (~1.70 nm) are fabricated by a facile electrodeposition method with sufficient OH* on the surface. The charge-transfer resistance of NiCo 2 O 4 nanosheets in EGOR is only 0.94 Ω and the anode power consumption can be reduced by up to 320 mV at 10 mA cm −2 , keeping the high glycerol conversion (89%) and FA selectivity (70%) during the 120-h stability test. DFT calculations and experimental tools (e.g., multi-potential step experiments, operational electrochemical impedance spectroscopy) confirm that OH* in-situ generated on the thin nanosheets structure is essential in facilitating charge transfer between catalysts and adsorbed molecules to enhance C–C bond cleavage. This work offers a guideline for the rational design of robust catalysts for the selective upgrading of biomass-derived chemicals.
研究领域:
电化学
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催化材料
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理论计算
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生物质转化
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
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IF 9.7
Lin Huang,Maoqing Chen,Ying Yang,Qingshou Zheng,Li Gu,Ruobing Cheng,Xuebo Cao
Electro-reforming of organics such as alcohols into commodity chemicals and H 2 powered by renewables is intriguing and prevailing with the remarkable renaissance of electrochemical technology. Integrating Pt/Pd with an auxiliary metal, metal oxide, and metal hydroxide are feasible strategies to design the desirable catalysts toward alcohols electro-oxidation reactions. These catalysts however have high affinity toward carbonyl intermediates that occupy and poison the active sites. Thus, the target products suffer from poor selectivity. To address these issues, a facile binary Pt–Ag alloy nanowires (NWs) catalytic system was reported for efficient electro-oxidative reforming of ethylene glycol (EG), yielding glycolate with a selectivity of 91.5 %, an EG conversion of 96.4 %, and Faradaic efficiency (FE) of 87.4 %. Experimental and theoretical investigations revealed that Ag-induced electronic structure perturbations in Pt 0.66 Ag catalyst boosted the kinetics and robustness as a conventional promoter toward EG electro-oxidation reaction (EGOR). Moreover, the one-electron oxidation of water/hydroxide ion to generate abundant hydroxyl adspecies (OH ad ) on Ag served as another crucial promoter for efficient dehydrogenation, glycolate formation, and carbonyl intermediates release via a highly efficient, noncompetitive Langmuir–Hinshelwood (L–H) mechanism, but not the competitive L–H mechanism or the Eley–Rideal (E–R) mechanism. These findings provide new insights into the selective alcohol electro-oxidation reaction, and facilitate the generation of commodity chemicals via partial electro-oxidation reactions.
研究领域:
电化学
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催化材料
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可再生能源
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
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IF 9.4
Yumei Zhu,Jinlv Wei,Jia Wu,Rong Chen,Panagiotis Tsiakaras,Shibin Yin
The development of catalysts with suitable adsorption behavior for the reaction molecules and the elucidation of their internal structure-adsorption-catalytic activity relationships are crucial for the electrooxidation of 5-hydroxymethylfurfural (HMF). In this work, NiO-CuO heterostructures with a spontaneous built-in electric field (BEF) are specifically designed and used to regulate the OH − adsorption site for freeing up the active site of HMF for the HMF oxidation reaction (HMFOR). The mechanism driving electron pumping/accumulation of the BEF is examined by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). Electrochemical data and theoretical calculations show that BEF modulates the adsorption energy and adsorption site of substrate molecules, thereby enhancing the performance of HMFOR and hydrogen evolution reaction (HER). Notably, the NiO-CuO electrode demonstrates high 2,5-Furandicarboxylic acid (FDCA) selectivity (99.76 %) and generation rate (13.79 mmol gcat −1 h −1 ). It only requires 1.33 V to obtain a current density of 10 mA cm −2 for HMFOR-coupled H 2 evolution. This research introduces a novel approach by regulating the adsorption of reactive molecules for HMFOR-assisted H 2 evolution.
研究领域:
材料科学
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电化学
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催化反应
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产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
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2025
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IF 6.9
Jialin Fan,Xiaoxing Ke,Ge Chen,Yong Yan
The industrial synthesis of ethylene glycol (EG) via ethylene oxide hydration is energy-intensive and environmentally harmful due to high greenhouse gas emissions. Although electrochemical oxidation presents a more sustainable route for the direct synthesis of EG from ethylene, existing technologies are hampered by limited catalytic performance stemming from inadequate regulation of the key intermediate, adsorbed hydroxyl radicals (*OH). Herein, we employ a structural engineering strategy to fabricate a PdPtRh trimetallic alloy catalyst by introducing highly electronegative platinum (Pt) and rhodium (Rh) into a palladium (Pd) matrix. By precisely tuning the catalyst’s electronic structure, we effectively optimize the adsorption strength of *OH. Benefiting from this alloying effect, the developed PdPtRh catalyst demonstrates exceptional performance in the ethylene-to-EG conversion, achieving a peak Faradaic efficiency of 52 % and a production rate of 7.61 μmol/cm 2 /h-markedly superior to conventional monometallic Pd catalysts. Density Functional Theory (DFT) calculations further reveal that the alloy structure facilitates charge redistribution among the metals, effectively lowering key energy barriers in the reaction process. This work not only offers a novel design paradigm for developing efficient, eco-friendly catalysts for EG electrosynthesis but also highlights the immense potential of harnessing multimetallic synergistic effects to optimize performance in the field of electrocatalysis.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Libo Zhu,Tiantian Wu,Shuo Bi,Changchun Ke,Chang Chen,Han Tian,Fantao Kong,Xiangzhi Cui,Jianlin Shi
The electrode mass transport limitation during borohydride oxidation reaction (BOR) involving three-phase interfaces greatly deteriorates the performance and energy efficiency of direct sodium borohydride fuel cells (DBFCs). Here we develope a hierarchical structure electrode (HSE) strategy via dispersing Pd clusters on needle-structured CoP-O nanoarrays in situ grown on optimized macro-porous nickel foam (NF), to enhance the solution/gas transport, catalyst utilization and across electrode conductivity, and meanwhile to regulate the OH – -enrichment local environments at the anode of DBFC. The fabricated Pd@CoP-O/NF HSE exhibits excellent BOR catalytic activity featuring a rather low overpotential of 433 mV at 1 A cm −2 and an electron transfer number up to 7.8, and particularly an extra-high power density of 1.23 W cm −2 under O 2 conditions. The watt-level power density of DBFCs is achieved by the adsorption regulations of H*/OH – species on the catalyst and the effective separation and dissipation of bubbles from electrode, which provides an alternative but highly promising pathway for DBFC applications.
研究领域:
能源材料科学
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电化学工程
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燃料电池技术
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DOI
高影响因子
Nature Protocols
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2024
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IF 13.1
Zheng Jia-Jia,Zhu Feiyan,Song Ningning,Deng Fang,Chen Qi,Chen Chen,He Jiuyang,Gao Xingfa,Liang Minmin
Nanozymes are nanomaterials with enzyme-like catalytic properties. They are attractive reagents because they do not have the same limitations of natural enzymes (e.g., high cost, low stability and difficult storage). To test, optimize and compare nanozymes, it is important to establish fundamental principles and systematic standards to fully characterize their catalytic performance. Our 2018 protocol describes how to characterize the catalytic activity and kinetics of peroxidase nanozymes, the most widely used type of nanozyme. This approach was based on Michaelis–Menten enzyme kinetics and is now updated to take into account the unique physicochemical properties of nanomaterials that determine the catalytic kinetics of nanozymes. The updated procedure describes how to determine the number of active sites as well as other physicochemical properties such as surface area, shape and size. It also outlines how to calculate the hydroxyl adsorption energy from the crystal structure using the density functional theory method. The calculations now incorporate these measurements and computations to better characterize the catalytic kinetics of peroxidase nanozymes that have different shapes, sizes and compositions. This updated protocol better describes the catalytic performance of nanozymes and benefits the development of nanozyme research since further nanozyme development requires precise control of activity by engineering the electronic, geometric structure and atomic configuration of the catalytic sites of nanozymes. The characterization of the catalytic activity of peroxidase nanozymes and the evaluation of their kinetics can be performed in 4 h. The procedure is suitable for users with expertise in nano- and materials technology.
研究领域:
纳米技术
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材料科学
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催化
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生物化学
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产品关联
DOI
PubMed
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2025
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IF 19
Leilei Yin,Yuyan Liu,Shuai Zhang,Jin-Cheng Liu,Yong Jiang,Yaping Du
Excessive adsorption of oxygen-containing intermediates during oxygen reduction reactions (ORR) on palladium (Pd)-based materials is a critical factor limiting their catalytic activity. Alloying presents a powerful strategy to overcome this inherent challenge. In this study, the alloying of the low electronegativity lanthanide gadolinium (Gd) with Pd is explored. Pioneering theoretical calculations indicate that Gd, acting as an electron donor, induces charge redistribution between the metals. This process weakens the over-adsorption of OH* intermediates on the Pd surface and reduces the reaction overpotential. Subsequent experiments yield Pd 3 Gd solid-solution nano-alloys supported on conductive carbon black (Pd 3 Gd/C-600), resulting in a 30 mV enhancement in half-wave potential and a 4.5 fold increase in mass activity in an alkaline medium compared to Pd/C-600. Due to its superior performance in ORR, Zn-air batteries utilizing Pd 3 Gd/C-600 cathodes demonstrate remarkable peak power density and stability over 330 h. This study offers valuable insights into the rational design of rare earth alloys and their catalytic chemistry in ORR.
研究领域:
电催化
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材料科学
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能量存储与转换
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纳米材料
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稀土合金
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2025
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IF 8.3
Mingxin Cai,Qinghua Ye,Ziru Wang,Peilei He
Electrochemical water splitting for hydrogen production is currently constrained by the sluggish kinetics of the anodic oxygen evolution reaction (OER). NiFe-based catalysts have emerged as promising alternatives to precious metal OER catalysts due to their low cost and relatively high electrocatalytic activity. However, NiFe-based catalysts prepared by conventional synthesis methods suffer from a low density of exposed active sites and ambiguous structures. Herein, we report a straightforward solution-thermal strategy for constructing two-dimensional sub-1 nm nanosheets (SNSs) through the self-assembly of an iron-substituted polyoxometalate (FeMo 6 ) cluster with Ni 3 S 2 . The Ni 3 S 2 –FeMo 6 SNSs exhibit excellent electrocatalytic performance in 1 M KOH, achieving an overpotential of only 342 mV at a current density of 100 mA cm −2 and maintaining stability for 100 h at 10 mA cm −2 . The synergistic effect between Fe and Ni 3 S 2 effectively modulates the electronic structure of the catalyst, accelerating the formation of the active NiOOH phase. Furthermore, Fe incorporation actively enhances hydroxyl groups adsorption on the catalyst surface and facilitates lattice oxygen participation in the reaction. This work clarifies the role of Fe in NiFe-based electrocatalysts, providing new perspectives for developing facile-to-synthesize and high-performance electrocatalysts.
研究领域:
电化学
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纳米材料
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催化
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能量转换
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材料科学
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产品关联
DOI
高影响因子
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