APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Lili Huang,Shengpeng Mo,Xin Zhao,Jiangjing Zhou,Xiaobin Zhou,Yanan Zhang,Yinming Fan,Qinglin Xie,Bing Li,Junhua Li
Herein, a core-shell structured Co 3 S 4 /NC@ZnS/NC heterojunction has been constructed via elaborately synthesizing metal-organic framework (MOF)-on-MOF precursors (ZIF-67@ZIF-8) and following controlled carbonization-sulfidation processes. The developed Co 3 S 4 /NC@ZnS/NC achieves higher performances for CO 2 photoreduction with water vapor towards CO (28.44 μmol g −1 h −1 ), CH 4 (1.93 μmol g −1 h −1 ) and C 2 H 4 (12.23 μmol g −1 h −1 ) in a continuous-flow condition under visible-light irradiation, which are significantly superior than those of Co 3 S 4 /NC and ZnS/NC. 13 CO 2 isotope tracer analysis verifies that CO, CH 4 and C 2 H 4 originate from the carbon source of CO 2 . Experiments and DFT calculations confirm that constructing an electron transport layer (ZnS/NC) in Co 3 S 4 /NC@ZnS/NC can contribute to a feasible channel for the enhanced separation and transfer of charge carriers. In heterojunction , non-bonding Co and Zn atomic pairs as adsorption sites synergistically participate in the CO 2 activation through the unique electron transport channel and acquire the lower energy barriers of COOH* formation. Moreover, in situ DRIFTS reveals the key intermediates and possible conversion pathways to main products. This work presents an attractive strategy to construct dual MOFs-derived metal sulfide heterojunctions for high-performance CO 2 conversion.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
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2025
·
IF 6.5
Ziheng Zhen,Antai Li,Tiantian Xiao,Maoshuai Li,Jing Lv,Shouying Huang,Yue Wang,Xinbin Ma
Bimetallic catalyst with dual-atom pairs has drawn much attention in heterogeneous catalysis due to their unique synergistic effects. In this work, we prepared a series CeO 2 supported Cu-Pt dual sites catalysts and found the optimized one of 2Cu0.025Pt/CeO 2 exhibited excellent performance in the hydrogenation of methyl acetate (MA). Its product yield of ethanol was as 4 times as that of 2Cu/CeO 2 catalyst under the same reaction conditions, with only 0.025 wt% Pt addition. Combined with various characterizations and contrast samples, it is demonstrated that the post-deposited trace Pt species preferentially located besides the copper atoms and formed Cu-Pt atomic pairs. But when further increasing the loading of Pt, the aggregation of Cu happened, leading to a rapid decrease of activity. To reveal the role of Cu-Pt atom pairs in the hydrogenation of carbon–oxygen bonds reactions, we conducted chemisorption experiments and DFT simulations. It is suggested that Cu-Pt atomic pairs significantly enhanced the adsorption and activation capability of both the MA and H 2 molecules during the reaction. These insights may provide synthesis and design strategy for high-performance dual-atom sites catalysts for the carbon–oxygen bonds hydrogenation reactions.
研究领域:
催化化学
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材料科学
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理论计算
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Nano Materials
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2024
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IF 5.3
Tian Qin,Lina Li,Xiaoke Mu,Xi Liu,Liwei Chen
When the size of metallic nanocatalysts is reduced to clusters or even single atoms, they can exhibit unique catalytic activity. Understanding the local atomic structure of these highly dispersed metal species is crucial for comprehending changes in catalytic behavior. In recent years, researchers have developed the electron pair distribution function (ePDF) method, which has been utilized to study the atomic short-order arrangement of various materials. However, this technique has not yet been applied to the local structure study of supported metallic nanocatalysts to complement other characterization results. In this study, we introduced the ePDF method to investigate nanocarbon-supported Pt materials, which have potential applications as an oxygen reduction reaction catalyst. We demonstrate that with differential pair distribution function and independent component analysis, ePDF can probe the local structure of supported metal species, even the single atoms, in microregions. This technique was further extended to in situ experiments, indicating its semiquantitative capacity of studying structural evolution. The ePDF method is expected to complement electron microscopy and extended X-ray absorption fine structure, providing deeper insights into the structure–performance relationship of catalysts.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
·
IF 15.7
Chen Yuanxing,Qin Ying,Liu Mingwang,Yang Wenhong,Qiu Yiwei,Li Wen,Zheng Lirong,Gu Wenling,Zhu Chengzhou,Hu Liuyong
Energy level mismatches between semiconductors and cocatalysts often induce carrier recombination, limiting photocatalytic and photoelectrochemical (PEC) efficiency. Here, we integrate Pt nanocluster-Fe single-atom pairs with CuO to regulate both solid-solid and solid-liquid interfaces in PEC systems. Experimental and theoretical analyses reveal that an Ohmic contact at the CuO/Pt interface accelerates electron extraction, while Pt-to-Fe charge transfer enhances oxygen reduction at Fe sites, collectively boosting reaction kinetics. Leveraging this, we construct a PEC biosensor exploiting chelating effect of glyphosate on CuO to impede electron transfer, achieving a detection limit of 0.41 ng/mL. This interface engineering strategy advances cocatalyst design for enhanced energy conversion and sensing applications by simultaneously addressing carrier dynamics and interfacial reaction barriers.
研究领域:
材料科学
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光催化
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生物传感
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Energy Chemistry
·
2023
·
IF 13.1
Qingchun Zhang,Di Liu,Yaping Zhang,Zhiliang Guo,Minpeng Chen,Yuyun Chen,Bo Jin,Yingze Song,Hui Pan
The development of highly active, selective, and stable electrocatalysts can facilitate the effective implementation of electrocatalytic CO 2 conversion into fuels or chemicals for mitigating the energy crisis and climate problems. Therefore, it is necessary to achieve the goal through reasonable material design based on the actuality of the operational active site at the molecular scale. Inspired by the stimulating synergistic effect of coupled heteronuclear metal atoms, a novel Ni-Co atomic pairs configuration (denoted as NiN 3 ©CoN 3 -NC) active site was theoretically screened out for improving electrochemical CO 2 reduction reaction (CO 2 RR). The structure of NiN 3 ©CoN 3 -NC was finely regulated by adjusting Zn content in the precursors Zn/Co/Ni-zeolite imidazolate frameworks (Zn/Co/Ni-ZIFs) and pyrolysis temperature. The structural features of NiN 3 ©CoN 3 -NC were systematically confirmed by aberration-corrected HAADF-STEM coupled with 3D atom-overlapping Gaussian-function fitting mapping, XAFS, and XRD. The results of theoretical calculations reveal that the synergistic effect of Ni-Co atomic pairs can effectively promote the *COOH intermediate formation and thus the overall CO 2 RR kinetic was improved, and also restrained the competitive hydrogen evolution reaction. Due to the attributes of Ni-Co atomic pairs configuration, the developed NiN 3 ©CoN 3 -NC with superior catalytic activity, selectivity, and durability, with a high turnover frequency of 2265 h −1 at −1.1 V (vs . RHE) and maximum Faradaic efficiency of 97.7% for CO production. This work demonstrates the great potential of DACs as highly efficient catalysts for CO 2 RR, provides a useful strategy to design heteronuclear DACs, exploits the synergistic effect of multiple metal sites to facilitate complex CO 2 RR catalytic reactions, and inspires more efforts to develop the potential of DACs in various fields.
研究领域:
材料科学
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环境科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2020
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IF 16.683
Hongguan Li,Jing Wang,Ruijuan Qi,Yongfeng Hu,Jing Zhang,Hongbin Zhao,Jiujun Zhang,Yufeng Zhao
Charge and spin manipulations of electrons are considered to be of great significance in boosting the catalytic activity of M N C electrocatalysts. However, to the best of our knowledge, most current studies focus only on the charge engineering, the interplay between spin and charge is not well understood, and the simultaneous manipulation of both charge and spin remains challenging. Herein, we show that the cooperative interplay between charge itineration and spin-polarization of electrons has a profound impact on the catalytic behavior through density functional theory (DFT) calculations for the first time. Following this concept, we report a Fe-Ni atomic pair as a superior bifunctional catalyst for high performance ORR and OER, with a very small potential difference (ΔE) of 0.691 V. We confirm that the coexistence of Fe 3d itinerant charge and moderate spin polarization (magnetic moment: 1.48 μ B ) is responsible for the superior functional catalytic activity for the Fe Ni atomic pairs.
研究领域:
电催化
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材料化学
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物理化学
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纳米催化
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能源材料
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计算化学
✓ 已验证
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-15
·
IF 14.7
Yao Zhibo,Cheng Hao,Xu Yifei,Zhan Xinyu,Hong Song,Tan Xinyi,Wu Tai-Sing,Xiong Pei,Soo Yun-Liang,Li Molly Meng-Jung,Hao Leiduan,Xu Liang,Robertson Alex W.,Xu Bingjun,Yang Ming,Sun Zhenyu
The electrocatalytic reduction of CO 2 to CO is slowed by the energy cost of the hydrogenation step that yields adsorbed *COOH intermediate. Here, we report a hydrogen radical (H•)-transfer mechanism that aids this hydrogenation step, enabled by constructing Ni-partnered hetero-diatomic pairs, and thereby greatly enhancing CO 2 -to-CO conversion kinetics. The partner metal to the Ni (denoted as M) catalyzes the Volmer step of the water/proton reduction to generate adsorbed *H, turning to H•, which reduces CO 2 to carboxyl radicals (•COOH). The Ni partner then subsequently adsorbs the •COOH in an exothermic reaction, negating the usual high energy-penalty for the electrochemical hydrogenation of CO 2 . Tuning the H adsorption strength of the M site (with Cd, Pt, or Pd) allows for the optimization of H• formation, culminating in a markedly improved CO 2 reduction rate toward CO production, offering 97.1% faradaic efficiency (FE) in aqueous electrolyte and up to 100.0% FE in an ionic liquid solution.
研究领域:
电化学
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催化
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Science Bulletin
·
2025
·
IF 21.1
Tongtong Yang,Heng Liu,Hengjie Liu,Weiyi Zhao,Jiawei Ge,Wenhui Wang,Shuai Yang,Meijian Tang,Kai Wei,Kangcheng Wang,Zeming Qi,Xian Wang,Hao Li,Junjie Ge
Single-atom catalysts (SACs) challenge conventional multi-site catalysis by enabling oxidative processes like H 2 and CO oxidation. However, we herein present that the completely isolated SACs are inactive, while spatially adjacent single-atom pairs (interatomic distance < 4 Å) work cooperatively as the true active sites. Rh atomic densities were precisely tuned between 0.1 wt%–17.5 wt% via graphene quantum dots confinement. Mathematical modeling quantifies the scaling of active pairs versus electrochemical performance, rationalizing activity dependence on atomic proximity. 18 O isotope labeling and in situ synchrotron infrared spectroscopy analyses identified a new reaction mechanism, with water bifunctional dissociation enabled on sub-4 Å Rh pairs, and acts as the rate-determining step towards both CO and H 2 oxidation. While H 2 O enters the COOR process as a reactant and enters the HOR process as a molecular catalyst. Our findings redefine bifunctional catalysis, merging single-atom precision with nanoparticle-like cooperativity for efficient energy conversion systems.
研究领域:
材料科学
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催化
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电化学
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能量转换
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纳米技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-12
·
IF 14.7
Wei Shengjie,Ma Wenjie,Sun Minmin,Xiang Pan,Tian Ziqi,Mao Lanqun,Gao Lizeng,Li Yadong
Constructing atom-pair engineering and improving the activity of metal single-atom nanozyme (SAzyme) is significant but challenging. Herein, we design the atom-pair engineering of Zn-SA/CNCl SAzyme by simultaneously constructing Zn-N 4 sites as catalytic sites and Zn-N 4 Cl 1 sites as catalytic regulator. The Zn-N 4 Cl 1 catalytic regulators effectively boost the peroxidase-like activities of Zn-N 4 catalytic sites, resulting in a 346-fold, 1496-fold, and 133-fold increase in the maximal reaction velocity, the catalytic constant and the catalytic efficiency, compared to Zn-SA/CN SAzyme without the Zn-N 4 Cl 1 catalytic regulator. The Zn-SA/CNCl SAzyme with excellent peroxidase-like activity effectively inhibits tumor cell growth in vitro and in vivo. The density functional theory (DFT) calculations reveal that the Zn-N 4 Cl 1 catalytic regulators facilitate the adsorption of * H 2 O 2 and re-exposure of Zn-N 4 catalytic sites, and thus improve the reaction rate. This work provides a rational and effective strategy for improving the peroxidase-like activity of metal SAzyme by atom-pair engineering.
研究领域:
材料科学
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催化
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纳米技术
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生物化学
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理论化学
✓ 已验证
DOI
高影响因子
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