Catalysis Science & Technology
·
2020
·Vol. 10
·期 15
·5048-5059
·
IF 5.721
Yao-Yao Wang,Zheng Tang,Xue-Yang Ji,Song Wang,Zi-Shuo Yao,Jun Tao
Pt nanoparticles (NPs) can enhance the photocatalytic performance of metal–organic frameworks (MOFs) for hydrogen evolution. However, Pt atoms in the core of Pt NPs cannot be utilized for the hydrogen evolution reaction (HER) and the agglomeration of Pt NPs also reduces the enhancement effect. In this paper, we propose a simple and kinetically modulated post-synthetic strategy to encapsulate low-coordinated and monodispersed Pt clusters (PCs) with a mean size of 1.6 nm into the inner space of NH2-UiO-66 (U6N). The X-ray absorption spectroscopy (XAS) data indicate that the PCs with low coordination numbers and short Pt–Pt bonds possess more unoccupied d orbitals, which enhance the interactions between PCs and the MOF. Consequently, such enhanced interactions result in the acceleration of electron–hole separation that is beneficial to the HER activity of U6N, as confirmed by ultrafast transient absorption spectra. This MOF with encapsulated PCs shows a H2 production efficiency of 36.83 mmol h−1 g−1 and turnover number of 598 h−1 under visible light with photosensitizer erythrosin B and sacrificial agent triethanolamine. The results suggest that such PCs can efficiently boost the photocatalytic HER of U6N, and our strategy may provide a new avenue for fabricating MOFs with excellent catalytic properties.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Hailong Li,Wei Zheng,Jianping Yang,Wenqi Qu,Lijian Leng,Yong Feng,Qingjie Guo,Zequn Yang
Fundamental barriers remaining yet impeding the rational design of metal sulfide (MS)-based sorbents for efficient elemental mercury (Hg 0 ) capture are the lack of a quantitative understanding between the amount of the most active ligands (i.e., under-coordinated sulfur) and the Hg 0 removal performance of MS. The intrinsic diversity and complexity of the sulfur species, which make it difficult to exclusively control the abundance of under-coordinated sulfur in MS while keeping its valence generally unchanged, is the primary challenge to be overcome. A dedicated tin sulfide (SnS x ) nanosheet was thus adopted to this end by adjusting its size and the exposure ratio of edge mono-sulfide. Unlike other methods used for the construction of under-coordinated sulfur, e.g., doping heteroatoms, introducing defects, straining lattice, etc., this novel method achieved the independent adjustment of the abundance of under-coordinated sulfur in MS. A linear relationship was hence established, indicating that, with the molar ratio of under-coordinated sulfur in SnS x increased by 1 %, its Hg 0 capture capacity was enhanced by ∼ 0.9 mg g −1 . This quantitative relationship was further taken as valuable guidance serving the Hg 0 capture performance improvement of SnS x with the co-consideration of its textural properties. The applicability of this quantitative relationship may be further extended across the MS community, saving the time spending in experiments and stepping towards the rational design of MS-based Hg 0 sorbents.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Synthesis
·
2024
·
IF 0
Ma Xianhui,Yang Tong,He Dayin,Gao Xiaoping,Jiang Wei,Li Deming,Sun Yuanhua,Lin Xingen,Xu Jie,Wang Huijuan,Tai Xiaolin,Lin Yue,Yao Tao,Zhou Huang,Wu Yuen
The surface structure of catalysts greatly impacts the performance of the electrochemical CO 2 reduction reaction. However, the reconstruction caused by applied potential can affect the surface structure and is difficult to control. Here, inspired by drug capsules with extended-release structures, we construct a water-soluble carbonate shell on metal oxide catalysts. The shell acts as a protective coating, effectively slowing down the surface evolution process of the catalyst from high to low valence state under the applied electric field. Therefore, by tuning the shell thickness and dissolution rates, the surface reconstruction can be regulated, steering it towards the formation of an abundant low-coordinated structure. This strategy could promote the generation of Cu(0) with rich grain boundaries and small particles. The C 2+ Faradaic efficiency was 82.8 ± 2.2% with a current density of 2.0 A cm −2 , exceeding the performance of conventional CuO catalysts. Ex situ and in situ characterizations indicate that these generated surface structures enhance *CO intermediate stabilization and C–C coupling. Our approach for regulating surface reconstruction can be applied to other catalysts, such as ZnO, In 2 O 3 , SnO 2 and Bi 2 O 3 , elevating their selectivity towards CO and formate.
研究领域:
材料科学
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电化学
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催化反应
✓ 已验证
产品关联
DOI
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Shan Wang,Chong Lin,Xuetong Zhang,Ye Tan,Bin Xiao,Yepeng Zeng,Jingyang Tian,Minghui Cao,Yuanping Jiang,Min Li
Monometallic nickel–organic frameworks based on a carboxylated ligand [2,6-naphthalenedicarboxylic acid (Ni-NDC)] have abundant and uniformly distributed single-atom Ni sites, enabling superior oxygen evolution reaction (OER) activity. In theory, most of the Ni atoms inside Ni-NDC microcrystals are coordinatively saturated except for the surface. Therefore, there are no accessible low-coordination atoms (LCAs) as electrocatalytic sites for the OER. One effective way is to expose more LCAs by preparing self-supporting Ni-NDC nanoarrays (Ni-NDC NAs) with hierarchical secondary structural units. Another effective method is to create more internal LCAs by removing partial ligands or coordination atoms attached to the Ni atoms. Herein, by combining the two strategies, we engineered LCAs in the interior and exterior of Ni-NDC to synergistically accelerate the OER. In brief, ultrathick “brick-like” Ni-NDC NAs were first prepared with dissolution and coordination effects of NDC on self-sacrificial templates of “agaric-like” nickel hydroxide nanoarrays [Ni(OH)2 NAs]. Subsequently, dual-coordinated NDC was partially replaced by monocoordinated 2-naphthoic acid (NA). The Ni-NDC NAs were further tailed into ultrathin “liner leaf-like” nanoneedle arrays (LCAs-Ni-NDC NAs). As a consequence, the LCAs-Ni-NDC NAs have more internal and external LCAs, which can deliver an OER performance that is superior to that of Ni-NDC NAs.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Peiyi Ji,Xinchen Han,Zonglin Li,Qingxiao Zhang,Weihua Cheng,Jie Sheng,Runze Fan,Qingliang Liao,Chenhao Zhang,Hui Li
Catalytic hydrogenation of aromatic nitro-compounds to corresponding aromatic amines is an environmental-friendly transformation for the production of dyes and pigments in industrial. Herein, an efficient low-coordinated Pt derived from Ni-Pt alloy archored on silica has been fabricated via dealloying process. Transmission electron microscopy (TEM) analysis confirmed an equivalent metal particle size to the reference dense Pt. Additionally, the characterizations revealed that the generation of unsaturated coordination in the resultant material leads to enhanced active surface area, increased fraction of low-coordinated and electron-enriched Pt. The as-prepared low-coordinated Pt catalyst was applied for liquid-phase m-dinitrobenzene (m-DNB) hydrogenation. Under the reaction conditions of ambient temperature, atmospheric pressure and m-DNB/Pt molar ratio of 140, both the m-DNB conversion and the selectivity to m-phenylenediamine (m-PDA) reached 99% within 2 h, superior to those observed over the reference dense Pt and the reported Pt-based catalysts. The enhanced catalytic properties were attributed to the promotional effect of unsaturated coordinated structure, which provided more Pt active sites with low coordination number and high electron density. This study demonstrates the importance of unsaturated coordination in metallic catalysts and establishes a powerful protocol for the design of an effective metal catalyst for the hydrogenation of a range of nitroaromatic compounds.
研究领域:
催化化学
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环境科学
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材料科学
✓ 已验证
DOI
高影响因子
Nanoscale
·
2019
·Vol. 11
·期 37
·17301-17307
·
IF 6.97
Sai Luo,Yang Ou,Lei Li,Junjie Li,Xingqiao Wu,Yi Jiang,Mingxi Gao,Xiaofang Yang,Hui Zhang,Deren Yang
Although tremendous efforts have been devoted to exploring non-Pt based electrocatalysts toward the oxygen reduction reaction (ORR), achievements in both catalytic activity and durability are still far from satisfactory. Here, we report a facile approach for the synthesis of intermetallic Pd3Pb ultrathin nanoplate-constructed flowers. Such highly opened hierarchical nanostructures with an ordered phase and low-coordinated edge sites exhibited a substantially enhanced activity toward the ORR. Especially, the intermetallic Pd3Pb nanoflowers achieved a record-breaking mass activity (1.14 mA μgPd−1) in an alkaline solution at 0.9 V vs. a reversible hydrogen electrode among the reported Pd-based ORR electrocatalysts to date, which was 1.8, 3.9 and 11.4 times higher than those of intermetallic Pd3Pb nanocubes, Pd3Pb dendrites and commercial Pt/C, respectively. More importantly, the intermetallic Pd3Pb nanoflowers also showed a higher durability with only 23.7% loss in mass activity after 10 000 cycles compared to the commercial Pt/C (35% loss in mass activity) due to their chemically stable intermetallic structures.
研究领域:
材料科学
·
电化学
·
催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED MATERIALS
·
2022
·Vol. 35
·期 11
·2208672
·
IF 32.086
Lingzheng Bu,Jiashun Liang,Fandi Ning,Ju Huang,Bolong Huang,Mingzi Sun,Changhong Zhan,Yanhang Ma,Xiaochun Zhou,Qing Li,Xiaoqing Huang
Developing high-performance catalysts for fuel cell catalysis is the most critical and challenging step for the commercialization of fuel cell technology. Here 1D trimetallic platinum–iron–cobalt nanosaws (Pt 3 FeCo NSs) with low-coordination features are designed as efficient bifunctional electrocatalysts for practical fuel cell catalysis. The oxygen reduction reaction (ORR) activity of Pt 3 FeCo NSs (10.62 mA cm −2 and 4.66 A mg −1 Pt at 0.90 V) is more than 25-folds higher than that of the commercial Pt/C, even after 30 000 voltage cycles. Density functional theory calculations reveal that the strong inter-d-orbital electron transfer minimizes the ORR barrier with higher selectivity at robust valence states. The volcano correlation between the intrinsic structure featured with low-coordination Pt-sites and corresponding electronic activities is discovered, which guarantees high ORR activities. The Pt 3 FeCo NSs located in the membrane electrode assembly (MEA) also achieve very high peak power density (1800.6 mW cm −2 ) and competitive specific/mass activities (1.79 mA cm −2 and 0.79 A mg −1 Pt at 0.90 V iR -free cell voltage) as well as a long-term lifetime in specific H 2 O 2 medium for proton-exchange-membrane fuel cells, ranking top electrocatalysts reported to date for MEA. This work represents a class of multimetallic Pt-based nanocatalysts for practical fuel cells and beyond.
研究领域:
能源材料科学
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催化化学
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电化学
✓ 已验证
DOI
高影响因子
Energy & Environmental Science
·
2022
·Vol. 15
·期 8
·3246-3256
·
IF 39.714
Qian Liu,Xiaobin Liao,Yuanhao Tang,Jianghao Wang,Xiangzhou Lv,Xuelei Pan,Ruihu Lu,Yan Zhao,Xin-Yao Yu,Hao Bin Wu
Exploring advanced electrocatalysts for the hydrazine oxidation reaction (HzOR) could expedite the applications of direct hydrazine fuel cells (DHzFCs) for zero-carbon economics. Herein, we report a remarkable HzOR electrocatalyst based on low-coordinated Co arrays supported on Cu foam (p-Co/CF). The low-coordinated Co arrays were synthesized by the reduction of the Co(OH)F precursor with H2 plasma to induce numerous few-atom vacancies, producing low-coordinated surface Co atoms as catalytic active sites. The as-prepared p-Co/CF electrode exhibits a low onset potential of −0.15 V (vs. RHE) and a small Tafel slope of 8.83 mV dec−1 in 0.05 M N2H4/1 M KOH electrolyte, which are superior to those of most reported electrocatalysts toward the HzOR. Density functional theory (DFT) calculations have been employed to elucidate the HzOR process on metallic Co catalysts, suggesting that the improved catalytic activity would be attributed to the weakened adsorption of N2H3* on low-coordinated Co sites. Benefited by the superior catalytic activity of p-Co/CF, a prototype DHzFC has been demonstrated to deliver a high open circuit voltage of 1.1 V and a maximal power density of 186 mW cm−2 at ambient temperatures. This work provides guidance for designing high-performance non-noble metal electrocatalysts toward viable direct hydrazine fuel cells.
研究领域:
材料科学
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电化学
·
能源科学
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Zhaohui Wang,Kun Li,Junling Hu,Ang Li,Yang Tang,Yanzhi Sun,Pingyu Wan,Haomin Jiang,Yongmei Chen
H 2 O 2 production in coupled electrochemical systems, where H 2 O 2 is generated through 2e-pathway of water oxidation (2e-WOR) at anode and 2e-pathway of oxygen reduction (2e-ORR) at cathode, offers an advanced alternative to the anthraquinone process. However, the efficiency of such coupled system is often hindered by the limited activity and selectivity of electrocatalysts. Herein, a dual-functional catalyst composed of amorphous TiO 2 embedded in mesoporous carbon hollow spheres (TiO x @MCHS) is reported, which exhibits exceptional electrocatalytic performance for both 2e-WOR and 2e-ORR. By employing TiO x @MCHS-loaded electrodes as both anode and cathode in a membrane-free flow cell with 4 м K 2 CO 3 /KHCO 3 as electrolyte, a rate of 108.3 µmol min −1 cm −2 and a Faradaic efficiency (FE) of ≈145% for H 2 O 2 production are achieved at a voltage of ≈2.5 V under a constant current of 240 mA (anode: 1 cm 2 , cathode: 4 cm 2 ). Experimental and computational results reveal the crucial role of low-coordinated Ti in optimizing the adsorption of intermediates involved in the two electrode reaction pathways, thereby enhancing both activity and selectivity of these processes. This work establishes a new paradigm for the development of advanced electrocatalysts and the design of novel coupled-electrolysis systems, enabling scalable and sustainable H 2 O 2 electrosynthesis.
研究领域:
材料科学
·
电化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2021
·Vol. 32
·期 5
·2106886
·
IF 18.808
Haisheng Gong,Zengxi Wei,Zhichao Gong,Jingjing Liu,Gonglan Ye,Minmin Yan,Juncai Dong,Christopher Allen,Jianbin Liu,Kang Huang,Rui Liu,Guanchao He,Shuangliang Zhao,Huilong Fei
Electrochemical H 2 O 2 production through the 2-electron oxygen reduction reaction (ORR) is a promising alternative to the energy-intensive anthraquinone process. Herein, by simultaneously regulating the coordination number of the atomically dispersed cobalt sites and the nearby oxygen functional groups via a one-step microwave thermal shock, a highly selective and active Co N C electrocatalyst for H 2 O 2 electrosynthesis that exhibits a high H 2 O 2 selectivity (91.3%), outstanding mass activity (44.4 A g −1 at 0.65 V), and large kinetic current density (11.3 mA cm −2 at 0.65 V) in 0.1 m KOH is obtained. In strong contrast to the typical Co N 4 moieties for the 4-electron ORR, the present Co N C catalyst possesses a low-coordinated Co N 2 configuration and abundant epoxide groups, which work in synergy for promoting the 2-electron ORR, as demonstrated by a series of control experiments and theoretical simulations. This study may provide an effective avenue to modulating the composition and structure of electrocatalysts at the atomic scale, leading to the development of new electrocatalysts with unprecedented reactivity.
研究领域:
材料科学
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电化学
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Small
·
2020
·Vol. 16
·期 17
·2000421
·
IF 11.459
Xiaohui Yang,Faling Ling,Xiangrong Zi,Yanwei Wang,Han Zhang,Huijuan Zhang,Miao Zhou,Zaiping Guo,Yu Wang
The electrochemical N 2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber–Bosch process for distributed and modular production of NH 3 . Nevertheless, developing high-efficiency catalysts to simultaneously realize both high activity and selectivity for the development of a sustainable NRR is very critical but extremely challenging. Here, a unique plasma-assisted strategy is developed to synthesize iridium diphosphide nanocrystals with abundant surface step atoms anchored in P,N-codoped porous carbon nanofilms (IrP 2 @PNPC-NF), where the edges of the IrP 2 nanocrystals are extremely irregular, and the ultrathin PNPC-NF possesses a honeycomb-like macroporous structure. These characteristics ensure that IrP 2 @PNPC-NF delivers superior NRR performance with an NH 3 yield rate of 94.0 µg h −1 mg −1 cat. and a faradaic efficiency (FE) of 17.8%. Density functional theory calculations reveal that the unique NRR performance originates from the low-coordinate step atoms on the edges of IrP 2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH 3 formation. More importantly, such a plasma-assisted strategy is general and can be extended to the synthesis of other high-melting-point noble-metal phosphides (OsP 2 @PNPC-NF, Re 3 P 4 @PNPC-NF, etc.) with abundant step atoms at lower temperatures.
研究领域:
材料科学
·
电化学
·
理论计算
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Nano
·
2025
·
IF 16
Kang Lian,Sanshuang Gao,Wenxian Liu,Qian Liu,Yanhong Feng,Jun Luo,Guangzhi Hu,Ke Chu,Dingsheng Wang,Xijun Liu
The combination of CO2 fixation and small organic molecule oxidation offers a promising solution to increasing severe environmental issues and energy crises. Here, low-coordinated NiN3 sites were anchored onto nitrogen-doped ordered mesoporous carbon (Ni-SAs/NOMC), which is capable of efficiently catalyzing the coupled methanol oxidation reaction and CO2 reduction reaction (MOR||CO2RR), thereby reducing the energy required for CO2 conversion and enhancing the economic value of the CO2 electrolytic system. In the membrane electrode assembly electrolyzer-based MOR||CO2RR, Ni-SAs/NOMC achieved Faradaic efficiencies (FEs) of 95.4% for formate at the anode and 96.3% for CO at the cathode. Moreover, at a current density of 0.8 A cm–2, Ni-SAs/NOMC demonstrated stable electrolysis for up to 100 h, with FEs at both the anode and cathode remaining stable at approximately 90%. In situ spectroscopy analyses and theoretical calculations identified the formation of critical intermediate species and the origin of activity improvement, guiding the development of efficient electrosynthesis of valuable chemicals.
研究领域:
能源化学
·
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）