ACS Catalysis
·
2024
·
IF 11.3
Haoquan Guo,Jiwu Zhao,Yu Chen,Xinyu Lu,Yue Yang,Chenrong Ding,Lizhi Wu,Li Tan,Jinlin Long,Guohui Yang,Yu Tang,Noritatsu Tsubaki,Xiaoli Gu
Lignin derivatives are one class of attractive alternative feedstocks for the production of renewable biofuels. Herein, hydrodeoxygenation (HDO) of lignin derivatives was carried out using a single-atom catalyst (SAC) comprised of Ni1 SAC on β-Mo2C. A number of lignin-derived compounds have been investigated, and nearly 100% yield of biofuel molecules was converted from various lignin derivatives through the HDO reaction, demonstrating that Ni1/β-Mo2C has remarkable potential for the production biofuels through catalytic hydrodeoxygenation of lignin derivatives. The reaction mechanism of DHE over single-atom catalyst Ni1/β-Mo2C was confirmed based on comprehensive characterizations of catalysts and DFT calculations. Interestingly, the Ni single-atom active sites alter the reaction pathway by shifting the geometry of the adsorbed intermediate from a vertical to horizontal conformation, which lowered the reaction energy barrier and improved the selectivity to biofuel molecules, resulting in extraordinary catalytic activity. This study suggests an avenue for single-atom catalysis in chemical transformations of lignin derivatives into biofuels.
研究领域:
化学工程
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催化科学
·
可再生能源
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DOI
高影响因子
Nanoscale
·
2022
·Vol. 14
·期 42
·15889-15896
·
IF 8.307
Yuxiang Ma,Yumin Zhang,Yiwen Ma,Tianping Lv,Bin Xiao,Xinya Kuang,Xiyu Deng,Jin Zhang,Jianhong Zhao,Qingju Liu
Single atom catalysts (SACs) have an extremely high atom utilization and distinctive structures and properties in the field of photocatalysis. However, the premise of conducting scientific research and applications is still the stability and catalytic activity of single atoms on suitable substrates. Metal organic frameworks (MOFs), as one of the most suitable single-atom substrates, have tunable internal structures, unsaturated coordination bonds, and high specific surface areas. In this work, Ti-based MOF, MIL-125, was adopted as the precursor to prepare mesoporous Cu-loaded TiO2. During the synthesis of MIL-125, a Cu source was added, and Cu atoms were fixed by partly replacing Ti atoms in the Ti–O octahedron to coordinate with O atoms, resulting in a good dispersity, good stability and high loading amount. Experimental investigations demonstrated that dispersed Cu single atoms act as reaction centres, besides being able to accelerate the transfer of photoelectrons. Under simulated sunlight, the H2 evolution rate of the optimum Cu–TiO2 sample reaches 17.77 mmol g−1 h−1, nearly 101 times higher than that of the pure mesoporous TiO2. The apparent quantum efficiency (AQE) is 20.15% under 365 nm irradiation. This research opens a new thinking to preparing high stability and high activity single atom photocatalysts.
研究领域:
材料科学
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光催化
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能源科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
·
IF 19.503
Xiongwei Zhong,Shulong Ye,Jun Tang,Yuanmin Zhu,Duojie Wu,Meng Gu,Hui Pan,Baomin Xu
Fabrication of Pt-based electrocatalysts with high activity and excellent durability is critical for the practical applications into zinc-air battery (ZAB). In this work. A novel strategy for the encapsulation of Pt species into the cavities of Fe-doped zeolite imidazolate framework is proposed to increase the density of active metal atoms and improve the activity effectively, where both isolated Pt and Fe single atoms anchored on nitrogen-doped carbon (PtFeNC) are obtained by a simple pyrolysis. Impressively, PtFeNC delivers a half-wave potential of 0.895 V (vs. RHE), Moreover, PtFeNC exhibits a lower yield of peroxide species than FeNC. Importantly, the ZAB battery shows a specific capacity of as high as 807 mA h/g at a discharge current density of 10 mA/cm 2 . Our findings show that dual- and multi- metallic single atom catalysts with abundant active sites can be achieved to boost electrocatalytic activity for their practical applications in energy storage though the new tactic.
研究领域:
材料科学
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电化学
·
能源存储
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DOI
高影响因子
ACS Nano
·
2022
·
IF 18.027
Xianyu Zhu,Jiabin Wu,Ruixue Liu,Huandong Xiang,Wenqi Zhang,Qingchao Chang,Shanshan Wang,Rui Jiang,Feng Zhao,Qiqiang Li,Liang Huang,Liang Yan,Yuliang Zhao
Single-atom nanozymes (SAzymes), with individually isolated metal atom as active sites, have shown tremendous potential as enzyme-based drugs for enzymatic therapy. However, using SAzymes in tumor theranostics remains challenging because of deficient enzymatic activity and insufficient endogenous H2O2. We develop an external-field-enhanced catalysis by an atom-level engineered FeN4-centered nanozyme (FeN4-SAzyme) for radio-enzymatic therapy. This FeN4-SAzyme exhibits peroxidase-like activity capable of catalyzing H2O2 into hydroxyl radicals and converting single-site FeII species to FeIII for subsequent glutathione oxidase-like activity. Density functional theory calculations are used to rationalize the origin of the single-site self-cascade enzymatic activity. Importantly, using X-rays can improve the overall single-site cascade enzymatic reaction process via promoting the conversion frequency of FeII/FeIII. As a H2O2 producer, natural glucose oxidase is further decorated onto the surface of FeN4-SAzyme to yield the final construct GOD@FeN4-SAzyme. The resulting GOD@FeN4-SAzyme not only supplies in situ H2O2 to continuously produce highly toxic hydroxyl radicals but also induces the localized deposition of radiation dose, subsequently inducing intensive apoptosis and ferroptosis in vitro. Such a synergistic effect of radiotherapy and self-cascade enzymatic therapy allows for improved tumor growth inhibition with minimal side effects in vivo. Collectively, this work demonstrates the introduction of external fields to enhance enzyme-like performance of nanozymes without changing their properties and highlights a robust therapeutic capable of self-supplying H2O2 and amplifying self-cascade reactions to address the limitations of enzymatic treatment.
研究领域:
生物医学工程
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肿瘤学
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纳米医学
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DOI
PubMed
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·Vol. 33
·期 28
·2301729
·
IF 19
Youyu Duan,Yang Wang,Weixuan Zhang,Jiangwei Zhang,Chaogang Ban,Danmei Yu,Kai Zhou,Jinjing Tang,Xu Zhang,Xiaodong Han,Liyong Gan,Xiaoping Tao,Xiaoyuan Zhou
Photocatalytic conversion of CO 2 into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO 2 photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO 2 reduction and H 2 O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu 1 /N 2C V-CN). Experimental and theoretical results show that Cu single-atom centers promote CO 2 chemisorption and activation via accumulating photogenerated electrons, and the N 2C V sites enhance the dissociation of H 2 O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu 1 /N 2C V-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g −1 h −1 . An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO 2 photoreduction process.
研究领域:
催化化学
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环境科学
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材料科学
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产品关联
DOI
高影响因子
Nano Research
·
2021
·Vol. 15
·期 4
·3026-3033
·
IF 8.897
Sun Hao,Yin Hua-Qing,Shi Wenxiong,Yang Lu-Lu,Guo Xiang-Wei,Lin Hong,Zhang Jiangwei,Lu Tong-Bu,Zhang Zhi-Ming
Electrochemical nitrogen reduction reaction (NRR) under ambient conditions is highly desirable to achieve sustainable ammonia (NH 3 ) production via an alternative carbon free strategy. Single-atom catalysts (SACs) with super high atomic utilization and catalytic efficiency exhibit great potential for NRR. Herein, a high-performance NRR SAC is facilely prepared via a simple deposition method to anchor Au single atoms onto porous β-FeOOH nanotubes. The resulting Au-SA/FeOOH can efficiently drive NRR under ambient conditions, and the NH 3 yield reaches as high as 2,860 µg·h −1 ·mg Au −1 at −0.4 V vs. reversible hydrogen electrode (RHE) with 14.2% faradaic efficiency, much superior to those of all the reported Au-based electrocatalysts. Systematic investigations demonstrate that the synergy of much enhanced N 2 adsorption, directional electron export, and mass transfer ability in Au-SA/FeOOH greatly contributes to the superior NRR activity. This work highlights a new insight into the design of high efficient NRR electrocatalysts by combination of porous metal oxide matrix and highly active single-atom sites.
研究领域:
材料科学
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电化学
·
催化反应
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Jun Li,Xiaosi Liang,Liying Cai,Shuke Huang,Chenyang Zhao
Single atom alloys (SAA) have recently drawn increased attention due to their unique structure, high atomic utilization, and fascinating catalytic performance. However, their controllable synthesis still presents a challenge. This study proposes an electrochemical self-catalysis (ESC) strategy to synthesize Pd@Pt/C SAA catalysts, that is, depositing Pt atoms on Pd nanocrystals through in situ decomposition of sodium formate. The relationship between composition and structure of Pd@Pt/C is distinguished through a combination of electrochemical analysis, sphere-corrected scanning transmission electron microscopy, and X-ray adsorption spectra. That relationship evolved from SAA to a sea-island structure and even a core–shell structure with composition-controllable atomic ratios, highlighting the great diversity and convenience of this method in nanostructure construction. The Pd@Pt/C SAA catalyst showed excellent catalytic activity to formic acid oxidation with a peak current density of 5.2 A/mgmetal, which is about 18.6 times that of the commercial Pd/C. density functional theory calculations revealed that the enhanced activity was due to the “passivation” of Pd sites near the Pt single atoms, which attenuated the adsorption of CO. Based on electrochemical principles, this ESC strategy was also expanded to prepare a series of Pd-based SAA, including Pd–Au, Pd–Ir, and Pd–Bi.
研究领域:
材料科学
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电化学
·
催化化学
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DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Shilong Zhong,Haixian Shi,Chengwei Xiao,Xirui Gu,Jing Wu,Shaolin Lu,Zhongke Yuan,Yuzhao Yang,Dingshan Yu,Xudong Chen
Constructing single-atom catalysts (SACs) using organic porous framework materials as supports presents a promising approach for developing highly efficient photocatalysts for hydrogen evolution. However, the fabrication of SACs that are both highly stable and active poses a significant challenge, particularly in the precise anchoring of metal single atoms. In this study, we utilized 1,3,6,8-tetra (p-methyl benzoate) pyrene as a ligand to synthesize pyrene-based hydrogen-bonded organic frameworks (denoted as PFC-1) through a self-assembly approach. Subsequently, a liquid-phase photoreduction process was employed to deposit noble metal platinum (Pt) onto PFC-1, resulting in the fabrication of SACs (PFC-1@Pt). Characterization results confirmed that Pt existed in a monatomic state, anchored through Pt C and Pt O coordination bonds with PFC-1. Serving as electron capture and separation centers, the Pt single atoms effectively suppressed electron-hole recombination, thereby prolonging carrier lifetimes. Consequently, the PFC-1@Pt SAC exhibited efficient hydrogen evolution performance with a rate of 2202.5 μmol g −1 h −1 and maintained photocatalytic activity for over 40 h. Our findings provide a systematic approach for developing efficient and stable SACs based on HOFs, expanding the potential applications of HOF materials in photocatalysis.
研究领域:
材料科学
·
催化化学
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产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2022
·
IF 12.92
Lei Cheng,Peng Zhang,Qiye Wen,Jiajie Fan,Quanjun Xiang
ABSTRACT Single-atom Pt catalysts are designed to promote efficient atom utilization, whereas effective decrease of Pt loading and improvement of photocatalytic activity in monoatomic Pt-deposited systems is still ongoing. Atomically dispersed metal species in crystalline carbon nitride are still challenging owing to their high crystallization and structural stability. In this study, we developed a novel single-atomic Pt-Cu catalyst for reducing noble metal loading by combining Pt with earth-abundant Cu atoms and enhancing photocatalytic CO 2 reduction. N-vacancy-rich crystalline carbon nitride was used as a fine-tuning ligand for isolated Pt-Cu atom dispersion based on its accessible functional N vacancies as the seeded centers. The synthesized dimetal Pt-Cu atoms on crystalline carbon nitride (PtCu-crCN) exhibited high selectivity and activity for CO 2 conversion without the addition of any cocatalyst or sacrificial agent. In particular, we demonstrated that the diatomic Pt-Cu exhibited high mass activity with only 0.32 wt% Pt loading and showed excellent photocatalytic selectivity toward CH 4 generation. The mechanism of CO 2 photoreduction for PtCu-crCN was proposed based on the observations and analysis of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images, in situ irradiated X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The findings of this work provide insights for abrogating specific bifunctional atomic metal sites in noble metal-based photocatalysts by reducing noble metal loading and maximizing their effective mass activity.
研究领域:
材料科学
·
环境科学
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DOI
高影响因子
Journal of Materials Chemistry A
·
2024
·Vol. 12
·期 25
·15386-15397
·
IF 10.7
Qi Zhang,Peiyao Pan,Xuewen Xia,Shujuan Wang,Zhongya Pang,Guangshi Li,Li Ji,Xing Yu,Xionggang Lu,Xingli Zou
Constructing multiple nanosized heterogeneous structures with an in situ optimized coordination environment for dispersing and stabilizing noble metal single atoms (SAs) is a highly effective strategy for high-efficiency utilization of SAs and improving the electrocatalytic performances of the oxygen evolution reaction (OER). Herein, a multi-crystalline-amorphous heterogeneous composite (CoP2@CN–Ir(200)) composed of crystalline CoP2, amorphous CoOx and amorphous N-doped carbon was constructed for in situ loading of Ir SAs by cyclic voltammetry (CV) electrodeposition in an ionic liquid. By precisely controlling the electrodeposition cycles, the loading matrix of Ir SAs was simultaneously reconstructed and optimized. Some of the crystalline CoP2 is transformed into amorphous CoOx with activated high-valence Co; a coordination environment toward oxygenated species is built with more lattice oxygen and stronger adsorption ability of oxygen; the abundant heterointerfaces and the enhancement of the oxidation state disperse and stabilize Ir atoms in the form of OER-favorable high-valence Ir3+/Ir4+ by covalent Ir–O bonds (including Ir–O–Co bonds). As a result, abundant active sites with high intrinsic activity are exposed, and an accelerated charge transfer rate can be achieved, endowing CoP2@CN–Ir(200) with an outstanding electrocatalytic activity. Ultralow overpotentials of 189 and 300 mV at 10 and 100 mA cm−2, respectively, are achieved with a small Tafel slope of 36.9 mV dec−1, surpassing most reported remarkable Ir-related catalysts.
研究领域:
材料科学
·
电化学
·
催化科学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2025
·
IF 17.7
Yangyang Li,Jingyi Yang,Botao Qiao,Tao Zhang
Supported metal catalysts are the backbone of heterogeneous catalysis, playing a crucial role in the modern chemical industry. Metal-support interactions (MSIs) are known important in determining the catalytic performance of supported metal catalysts. This is particularly true for single-atom catalysts (SACs) and pseudo-single-atom catalysts (pseudo-SACs), where all metal atoms are dispersed on, and interact directly with the support. Consequently, the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts. In this work, we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation. We fabricated CoFe 2 O 4 supported Pt pseudo-SACs and nanoparticle catalysts, followed by a straightforward water treatment process. It was found that the covalent strong metal-support interaction (CMSI) in pseudo-SACs can be weakened, leading to a significant activity improvement in methane combustion reaction. This finding aligns with our recent observation of CoFe 2 O 4 supported Pt SACs. By contrast, the MSI in Pt nanoparticle catalyst was barely affected by the water treatment, giving rise to almost unchanged catalytic performance. This work highlights the critical role of metal size in determining the MSI modulation, offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.
研究领域:
催化化学
·
材料科学
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产品关联
DOI
高影响因子
Nanoscale
·
2025
·
IF 5.1
Runxin Li,Yangyang Dong,Heng Xu,Yifei Yuan,Jie Xu
High-valent metal single atoms generally exhibit exceptional electrocatalytic activity because of their rapid electron-transfer kinetics. However, their synthesis remains a formidable challenge owing to intrinsic instability under typical preparation conditions. Herein, atomically dispersed Ir3+ single atoms were successfully stabilized on a NiS2 matrix via a substitutional replacement of Ni lattice sites by Ir, followed by coordination with adjacent S atoms. The resulting catalyst delivers outstanding oxygen evolution reaction (OER) performance, achieving a current density of 10 mA cm−2 at an overpotential of only 190 mV. Density-functional theory calculations reveal that the high oxidation state of Ir upshifts the Ni d-band center toward the Fermi level, thereby strengthening OOH* adsorption and accelerating the OER kinetics. This work not only provides a robust strategy for constructing high-valent single-atom catalysts but also highlights the pivotal role of sulfide supports in stabilizing high oxidation states for advanced electrocatalysis.
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DOI
PubMed
高影响因子
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