Nature Communications
·
2025
·Vol. 16
·期 1
·1-13
·
IF 15.7
Xu Guangyuan,Peng Xingjie,Wu Chuanqiang,Xi Shibo,Xiang Huixin,Feng Lei,Liu Zhendong,Duan Yi,Gan Lijin,Chen Si,Kong Yuan,Ma Yanzhe,Nie Fujing,Zhao Jie,Hai Xiao,Wei Wei,Zhou Meng,Wang Tianfu,Yao Chuanhao,Zhou Wu,Yan Huan
CO 2 electroreduction to CO promises to give an efficient strategy for CO 2 fixation and transformation. However, current reported active sites fail to deliver sufficient activity with high CO Faradic efficiency (FEco) over a wide range of potential. Here, we show a general synthetic protocol to fabricate a batch of highly pure and active NiN 2 catalysts with precise engineering of the uniform-large ( UL ) vacancy around the active sites, which is accomplished through the ‘pre-deposition + pyrolysis’ of various atomically precise Ni clusters (Ni n ) and in-situ etching of the support by the ‘nano bomb’ (sulfur-ligand in the clusters). The NiN 2 sites with UL vacancies could achieve a high turnover frequency (TOF) of 350000 h −1 with ~100% FEco in a wide potential range of 1500 mV. In-situ infrared spectra and theoretical calculations reveal that a highly pure NiN 2 site with UL vacancy contributes to this remarkable catalytic performance compared to the counterparts. This general synthetic strategy enables us to simultaneously engineer active sites and surrounding vacancies with the employment of atomically precise metal clusters, thereby enhancing catalytic performance for other specific reactions.
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
PubMed
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Shengpeng Mo,Shuangde Li,Jiangjing Zhou,Xin Zhao,Huimin Zhao,Xiaobin Zhou,Yinming Fan,Zongqiang Zhu,Bing Li,Qinglin Xie,Wenzhe Si,Yunfa Chen,Daiqi Ye,Junhua Li
A concentrated solar reaction device has been designed for the solar-driven photothermal CO2 reverse water–gas shift reaction, in which solar-to-chemical conversion efficiency would be up to 26% via a concentrated solar panel. Meanwhile, a special photothermal Ni–C–In catalyst (Ni/C–In2O3) with interstitial C, the In3Ni2 intermetallic compound, and disordered Ni clusters has been synthesized. As a result, the SO2-tolerant Ni/C–In2O3 catalyst exhibits an outstanding solar-driven photothermal catalytic performance (near thermodynamic limitation) with 100% CO selectivity and a 20.96 mmol gcat–1 h–1 CO production rate for solar-driven CO2 hydrogenation under concentrated solar irradiation (around 1521.9 mW/cm2) even sunlight without external heating. The incorporation of interstitial C and exposed Ni clusters in the Ni–C–In intermetallic catalyst could strengthen intensive solar light absorption. Moreover, quasi in situ XPS and DFT theoretical calculation results validate that asymmetric interaction between interstitial C and the Ni-cluster not only effectually regulates the electronic structure of the Ni–C–In intermetallic catalyst but also greatly optimizes the activation of H2 and CO2 molecules and the energy barriers of key reaction dynamics (HCOO* formation and dehydrogenation) in the RWGS reaction. Accordingly, this study provides a promising strategy for the electronic structure modification of photothermal functional catalysts with C modification to boost CO2 hydrogenation, putting forward an important step toward practical solar-to-fuel production with concentrated natural sunlight.
研究领域:
材料科学
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催化化学
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2024
·
IF 15.8
Jinghang Chen,Yuqi Ren,Yiwei Fu,Yitao Si,Jie Huang,Jiancheng Zhou,Maochang Liu,Lunbo Duan,Naixu Li
We report a solvothermal method for the synthesis of an oxygen vacancy-enriched ZrO2 photocatalyst with Co single atoms and Ni clusters immobilized on the surface. This catalyst presents superior performance for the reduction of CO2 in H2O vapor, with a CO yield reaching 663.84 μmol g–1 h–1 and a selectivity of 99.52%. The total solar-to-chemical energy conversion efficiency is up to 0.372‰, which is among the highest reported values. The success, on one hand, depends on the Co single atoms and Ni clusters for both extended spectrum absorption and serving as dual-active centers for CO2 reduction and H2O dissociation, respectively; on the other hand, this is attributed to the enhanced photoelectric and thermal effect induced by concentrated solar irradiation. We demonstrate that an intermediate impurity state is formed by the hybridization of the d-orbital of single-atom Co with the molecular orbital of H2O, enabling visible-light-driven excitation over the catalyst. In addition, Ni clusters play a crucial role in altering the adsorption configuration of CO2, with the localized surface plasmon resonance effect enhancing the activation and dissociation of CO2 induced by visible–near-infrared light. This study provides valuable insights into the synergistic effect of the dual cocatalyst toward both efficient photothermal coupling and surface redox reactions for solar CO2 reduction.
研究领域:
材料科学
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环境科学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Xiangbo Ma,Xiaofeng Xu,Lele Geng,Jinming Si,Zichen Song,Wenqian Wang,Songqi Gu,Shichao Du,Honggang Fu
The Ni-N coordination structure has been shown to be conducive to the electrochemical CO 2 reduction reaction (CO 2 RR) to CO, and this process has been extensively validated. However, the impact of Ni-N coordination structures within Ni-based clusters on CO 2 RR has received relatively limited research attention to date. In this study, catalysts containing Ni single atoms and Ni n clusters (Ni-N/Ni n ) were synthesised, and subsequently, Ni n clusters were transformed into Ni n N x clusters (Ni-N/Ni n N x ) through secondary nitridation. The experimental results, as illustrated by X-ray photoelectron spectra and X-ray absorption fine structure spectra, demonstrate that the Ni-N bond in Ni-N/Ni n N x increased and Ni- N -Ni bonds within atomic clusters were generated, thereby confirming the transformation from Ni n clusters to Ni n N x clusters. Density functional theory calculations show that the Ni n N x clusters have a lower energy barrier for the *CO 2 − + H + → *COOH step compared to Ni n clusters, and promote the entire reaction. Furthermore, in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations collectively indicate that abundant Ni-N coordination structures in clusters effectively reduce the energy barrier of CO 2 + e − → *CO 2 − and facilitate the activation of CO 2 to *CO 2 − across a broader potential window. Ni-N/Ni n N x demonstrates high Faraday efficiency of CO (FE COmax = 98.6 % at −0.4 V vs. RHE), a wider potential window (−0.3 to −0.8 V vs. RHE, FE CO > 90 %) and high CO partial current density (j CO > 100 mA cm −2 ). In comparison with Ni-N/Ni n , the maximum CO partial current density of Ni-N/Ni n N x is enhanced by approximately 4.6 times. These findings offer valuable insights into the structure–activity relationship of Ni-based cluster catalysts and facilitate the development of more advanced atomically cluster catalysts.
研究领域:
材料科学
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电化学
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理论计算
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2022
·
IF 4.598
Yong Yan,Xihao Lin,Weibing Zhang,Xinhua Li
Some metal–organic frameworks (MOFs) cannot be used as electrode materials for lithium-ion batteries because of their inferior intrinsic electrocatalytic activity and poor conductivity. Herein, the application of two nickel (II) cluster-based pillar-layered MOFs, Ni-mba-Na ([Ni 8 (mba) 6 (Cl) 2 Na(OH − ) 3 ] n , H 2 mba is 2-mercaptobenzoic acid) and Ni-mba-K ([Ni 8 (mba) 6 (Cl) 2 K(OH − ) 3 ] n ), as electrode materials are reported. They differ from conductive MOFs because they are insulators with small specific surface areas (<10 m 2 g −1 ) and H 2 mba is an inexpensive chemical raw material. The conductivities of Ni-mba-Na and Ni-mba-K at 30 ℃ are 4.002 × 10 −10 and >10 −11 S cm −1 , respectively. They exhibit excellent lithium storage performance, stability, and high inherent density (1.835 and 1.838 g cm −3 ) and specific capacity (1091.6, and 905.6 mAh/g at the first cycle). Design recommendations for these MOFs are provided based on their structure and performance differences. This paper provides a novel application of non-conductive MOFs in the energy storage field and strategy for design of high-performance electrode materials for lithium-ion batteries.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Jie Fan,Wen-Cui Li,Lei He,Bowen He,Fan Tang,Zhankai Liu,Dongqi Wang,Xi Liu,Liwei Chen,An-Hui Lu
Ni-based catalysts are the most promising candidates for methane dry reforming (MDR) reaction but still suffer from deactivation caused by coke-deposition. Herein, we reported a coke resistance MDR catalyst consisting of cationic Ni clusters (Niδ+, 0 < δ < 2) stabilized over oxygen-functionalized boron nitride. A simple method was developed for the fabrication of highly dispersed cationic Ni clusters on boron nitride. The local coordination modes between nickel and boron nitride determine the formation of cationic Ni clusters. We provided detailed spectroscopy and microscopy characterizations to reveal the structure features of these cationic Ni clusters. The average particle size of these clusters is ∼1.7 nm. There are abundant Nixδ+–O–B interfaces on the cationic Ni clusters, which serve as catalytically active sites. Compared to conventional metallic Ni nanoparticles, the cationic Ni clusters exhibited comparable apparent catalytic activity and reduced carbon deposition, particularly operated at 600 °C where unavoidable coke formation from CH4 cracking and the Boudouard reaction usually tends to occur thermodynamically and kinetically. Based on theoretical and experimental evidence, a dynamic synergistic conversion mechanism for CH4 and CO2 on the Nixδ+–O–B interface has been revealed. The oxygen within the Nixδ+–O–B interface could rapidly convert CHx*(x = 1–3) intermediates forming H2 and CO to avoid carbon deposition. CO2 is efficiently activated at boron sites of the Niδ+–O–B interface to regenerate active oxygen species, thereby boosting the conversion of CH4. These insights may shine light on the development of intrinsic coke-free Ni-based catalysts for methane dry reforming in the near future.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Research
·
2020
·
IF 0
Jiapeng Ji,Ying Sha,Zeheng Li,Xuehui Gao,Teng Zhang,Shiyu Zhou,Tong Qiu,Shaodong Zhou,Liang Zhang,Min Ling,Yanglong Hou,Chengdu Liang
The shuttle effect hinders the practical application of lithium-sulfur (Li-S) batteries due to the poor affinity between a substrate and Li polysulfides (LiPSs) and the sluggish transition of soluble LiPSs to insoluble Li2S or elemental S. Here, we report that Ni hexatomic clusters embedded in a nitrogen-doped three-dimensional (3D) graphene framework (Ni-N/G) possess stronger interaction with soluble polysulfides than that with insoluble polysulfides. The synthetic electrocatalyst deployed in the sulfur cathode plays a multifunctional role: (i) selectively adsorbing the polysulfides dissolved in the electrolyte, (ii) expediting the sluggish liquid-solid phase transformations at the active sites as electrocatalysts, and (iii) accelerating the kinetics of the electrochemical reaction of multielectron sulfur, thereby inhibiting the dissolution of LiPSs. The constructed S@Ni-N/G cathode delivers an areal capacity of 9.43 mAh cm-2 at 0.1 C at S loading of 6.8 mg cm-2, and it exhibits a gravimetric capacity of 1104 mAh g-1 with a capacity fading rate of 0.045% per cycle over 50 cycles at 0.2 C at S loading of 2.0 mg cm-2. This work opens a rational approach to achieve the selective adsorption and expediting of polysulfide transition for the performance enhancement of Li-S batteries.
研究领域:
材料科学
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能源化学
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电化学
✓ 已验证
DOI
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 10
·4823-4832
·
IF 3.5
Haihui Hu,Ke Ma,Yuandong Yang,Na Jin,Linjie Zhang,Jinjie Qian,Lili Han
Hydrogen peroxide (H2O2) electrosynthesis via the two-electron oxygen reduction reaction (2e− ORR) represents a green alternative to the energy-intensive anthraquinone process. However, the practical application of this method is limited by the lack of cost-effective and high-performance electrocatalysts. Reported here is a hybrid catalyst composed of nickel (Ni) clusters immobilized onto the surface of two-dimensional siloxene nanosheets (Ni/siloxene), which exhibits excellent efficiency and selectivity in electrocatalytic oxygen reduction to H2O2 in an alkaline medium, demonstrating a standard 2e− pathway with >95% H2O2 selectivity across a wide potential range. Experimental results disclose that the high performance of Ni/siloxene can be traced to a synergy of the Ni clusters and the oxygen-rich surface of siloxene. Density functional theory (DFT) calculations further reveal a weakened interaction between Ni/siloxene and *OOH and the consequently reduced energy barrier for the *OOH protonation toward H2O2 desorption, thus leading to a high 2e− ORR reactivity and selectivity. This work provides a valuable and practical guidance for designing high-performance 2e− ORR electrocatalysts based on the rational engineering of the metal–support interaction.
研究领域:
材料科学
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电化学
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催化
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纳米技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Yanshuang Gu,Xiaoran Zhang,Lixue Zhou,Peng Yu,Peng Huang,Daming Feng,Chunhua Ge
The urea oxidation reaction (UOR) plays a crucial role in advancing electrochemical energy storage systems and in the remediation of urea-contaminated wastewater. However, progress in UOR technology has been hindered by the lack of efficient, cost-effective catalysts. Herein, a functional UOR electrocatalyst, NiS@PPI-TAPT, was developed through uniformly embedding nickel sulfide (NiS) clusters within a porous perylene-based polyimide framework (PPI-TAPT). The resulting catalyst exhibits hierarchical porosity and a spherical microstructure, which significantly enhance active site accessibility and surface area. Additionally, the conjugated structure of the polyimide framework enables rapid electron transfer, thereby improving UOR performance compared to its naphthalene-based analogue, NiS@PPI-TANT, which shows an uneven distribution of NiS. In an electrolyte solution of 1 M KOH containing 0.33 M urea, NiS@PPI-TAPT achieves a current density of 10 mA cm⁻² at a low potential of 1.39 V vs . RHE, surpassing conventional water oxidation systems (e.g., oxygen evolution reaction). Notably, at a current density of 100 mA cm −2 , the overpotential for UOR is 209 mV lower than that of the OER. Moreover, the catalyst demonstrates exceptional reaction kinetics (Tafel slope: 55 mV dec⁻¹) and minimal charge-transfer resistance, highlighting its energy-efficient in urea oxidation. This work presents a rational strategy for designing high-performance, low-cost UOR electrocatalysts through the integration of metal sulfides with conductive porous organic frameworks.
研究领域:
电化学
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环境催化
·
材料化学
·
能源存储
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废水处理
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纳米催化
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2023
·Vol. 15
·期 37
·15238-15248
·
IF 6.7
Nan Zhang,Gang Li,Zhichao Yu,Zhenguo Tang,Xiaoyan Liu,Congwei Wang,Kaiying Wang
Heterostructure interfacial engineering between photocatalyst and co-catalyst to obtain an optimized electronic structure is a promising approach to improving their performance in the photocatalytic hydrogen evolution reaction (HER). In this work, two-dimensional nanopetal-like ZnIn2S4 (ZIS) with an adequately exposed active (110) edge facet-decorated Ni cluster heterostructure was prepared via chemical bath deposition, followed by photodeposition. In the catalyst preparation, the ZIS microstructure was modulated to sufficiently expose the active sites of the (110) edge for the HER, on which spontaneous interfacial engineering with an additional Ni cluster co-catalyst would be triggered via photodeposition in situ. The hydrogen production rate of the composite photocatalyst was excellent, at up to 26.80 mmol g−1 h−1 under simulated sunlight, which was 15.4 times greater than that of pristine ZIS. The optimized photocatalyst achieved a state-of-the-art apparent quantum yield of 61.68% at a single wavelength of 420 nm. Combined with systematic experimental characterization and density functional theory calculation, it was demonstrated that the separation and migration of charge carriers were significantly enhanced via the Ni cluster-induced interfacial electron redistribution, which contributed to the near-zero Gibbs free energy barrier and favored intermediate (*H) adsorption and desorption behavior, resulting in the superior photocatalytic performance. In summary, this work enables tuning of the interfacial electronic properties via spontaneous photodeposition of metallic cluster co-catalyst on the edge active sites, through which the separation of photogenerated charge carriers and surface redox reactions can be synergistically facilitated.
研究领域:
材料科学
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化学工程
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催化
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纳米技术
·
光化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Science Bulletin
·
2022
·
IF 20.577
Qi Hao,Qi Tang,Hai-Xia Zhong,Jia-Zhi Wang,Dong-Xue Liu,Xin-Bo Zhang
Single-atom catalysts (SACs) have attracted increasing concerns in electrocatalysis because of their maximal metal atom utilization, distinctive electronic properties, and catalytic performance. However, the isolated single sites are disadvantageous for reactions that require simultaneously activating different reactants/intermediates. Fully exposed metal cluster catalyst (FECC), inheriting the merits of SACs and metallic nanoparticles , can synergistically adsorb and activate reactants/intermediates on their multi-atomic sites, demonstrating great promise in electrocatalytic reactions . Here a facile method to regulate the atomic dispersion of Ni species from cluster to single-atom scale for efficient CO 2 reduction was developed. The obtained Ni FECC exhibits high Faradaic efficiency of CO up to 99%, high CO partial current density of 347.2 mA cm −2 , and robust durability under 20 h electrolysis. Theoretical calculations illuminate that the ensemble of multiple Ni atoms regulated by sulfur atoms accelerates the reaction kinetics and thus improves CO production.
研究领域:
电化学
·
催化
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Wenbin Li,Tongmeng Xing,Peng Zhang,Bin Chen,Zhuo Zhang,Baiyang Zhou,Ting Ding,Jing Li,Lunyong Zhang
The photo-assisted enhancement, as well as the multifunctional energy-environment synergy not only demonstrate substantial research significance in electrocatalytic materials but also pose considerable scientific challenges. In this study, we propose a quadruple-functional photo-assisted electrocatalytic (PEC) system for efficient and monitorable polychlorinated biphenyl (PCB-12) dechlorination during alkaline water splitting. The system comprises Ni(OH) 2 S x nanosheets decorated with NiS/Ni 3 S 2 clusters and Ag 2 S large nanoparticles (NPs) embedded with small Ag NPs. This integrated material demonstrates four distinct and efficient functions: 1) water splitting with current density of 1 A/cm 2 at 1.62 V vs RHE; 2) PEC dechlorination and degradation of 10 −4 M PCB-12 within 50 h; 3) facilitation of Cl - capture and hot electron injection from Ag 2 S/Ag hetero-NPs; 4) monitoring of PCB degradation as in-situ surface-enhanced Raman spectroscopy (SERS) substrate. The results indicate that NiS/Ni 3 S 2 is conducive to the retention of H*/OH*, while the H*/OH* on the Ni(OH) 2 S x is prone to desorption, makes the two active sites beneficial for PCB dechlorination and water splitting, respectively. This study provides a novel strategy for the collaborative application of multifunctional photo-electrocatalysts in energy conversion and environmental remediation.
研究领域:
电催化
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环境修复
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能量转换
·
纳米材料
·
光谱学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）