Nanoscale
·
2024
·Vol. 16
·期 27
·12992-12999
·
IF 5.8
Huiling Zhu,Xiangran Xu,Yongchao Wang,Jian Ding,Xinru Yu,Xiaoyi Liu,Zhaowu Zeng,Huan Wang,Zhen Li,Yang Wang
The photocatalytic conversion of nitrogen into high-value ammonia products holds tremendous potential in the global nitrogen cycle. However, the activation of N2 and competition of hydrogen evolution limit the improvement of nitrogen fixation performance. In this study, we developed a fluorinated TiO2 (F-TiO2) using a hydrothermal-annealing method. The incorporation of F dopants not only enhances the adsorption and activation of N2 through electronic structure regulation, but also facilitates an in situ increase in active sites via the electron repulsion effect between F and Ti atoms. In addition, the presence of F on the surface effectively improved the nitrogen supply problem and optimized the nitrogen fixation selectivity for its hydrophobic modulation. The NH3 yield of the F-TiO2 photocatalyst reached 63.8 μmol h−1 g−1, which was 8.5 times higher than that of pure TiO2. And the selectivity experiment showed that the electronic ratio of NH3 to H2 production reached 0.890. This research offers valuable insights for the design of highly efficient and selective nitrogen-fixing photocatalysts.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2025
·
IF 6.5
Yi Lu,Ahmed Mahmoud Idris,Ping Lu,Xinyan Jiang,Jin Wang,Hao Zheng,Xiandan Liang,Sheng Li,Zhengquan Li
Photocatalytic selective oxidation represents a sustainable approach for valuable chemical transformations, yet achieving high yield and selectivity of products remains a significant challenge. In this work, we demonstrate that electronic structure modulation of CsCuCl 3 halide perovskites enables highly selective photocatalytic oxidation of toluene to benzaldehyde (BD). By strategically doping Zn into CsCuCl 3 , we achieved control over the electronic modulation of catalytic sites, leading to a remarkable BD yield of 4.08 mmol g −1 h −1 with 85.4 % selectivity under visible light irradiation. Mechanistic investigations revealed that Zn doping creates an optimal electronic structure, which simultaneously facilitates O 2 activation to form superoxide radicals and promotes selective C–H bond activation of toluene. Density functional theory calculations showed that Zn doping induces charge redistribution at Cu and Cl sites, optimizing surface energetics for both O 2 and toluene adsorption while lowering kinetic barriers for the rate-determining steps. The enhanced charge carrier separation efficiency, confirmed by spectroscopic and electrochemical analyses, further contributes to the superior catalytic performance. This work establishes electronic structure engineering as a powerful strategy for developing high-performance single-component photocatalysts and provides new insights into the selective photocatalytic oxidation reactions.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Xuan-Yi Zhu,Shui-Zhong Zhao,Xue-Feng Zhang,Xia Huang,Cheng-Juan Gao,Li-Hong Yu,Zi-Yi Du,Li-Ming Cao,Chun-Ting He
Transition metal phosphides (TMPs) are high-potential catalysts for hydrogen evolution reaction (HER) yet struggle with the long-term maintenance of high activity at ampere-level current densities. Size cutting and heteroatom modification of TMPs are effective ways to improve their surface affinities and catalytic efficiencies, but the particle stabilities and synergistic regulation of band structures at different sites have become huge challenges. Herein, we have successfully synthesized cluster-level sulfur-doped iridium diphosphide (S-IrP2) through a molecular engineering strategy. It requires only low overpotentials of 133.6 ± 1.2 and 217.2 ± 2.6 mV to drive industrial current densities of 1.0 and 2.0 A·cm–2, respectively, being one of the best alkaline HER catalyst. Moreover, it showed almost no activity loss over 20,000 cycles and exhibited a remarkable charge transfer amount that exceeds those of reported TMPs. The electronic tailoring of IrP2 by sulfur atoms enables simultaneous shifting of the d-band and f-band centers of Ir and the p-band center of P, which co-optimizes the H and OH adsorption to lowering the H migration and H2 formation barriers. This work demonstrates that the molecular confinement synthesis holds tremendous prospects for architecting ultrafine metallic compounds with re-definable active surfaces.
研究领域:
材料科学
·
电化学
·
能源催化
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2023
·
IF 7.2
Nan Lu,Bin Liu,Zhengxin Peng,Jing Sui,Xiaofan Zhang,Yuting Ma,Renhong Li,Xiaoqing Yan
Rational design and fabrication of catalysts with excellent efficiency, high selectivity and outstanding stability is of great significance for the practical application of formic acid dehydrogenation into hydrogen gas. Herein, Pd catalysts with a narrow size distribution around 2.2 nm are deposited on the porous chitosan microspheres, which are produced by the polycondensation with Schiff base linkage. The Pd–N bond configuration is formed upon the abundant amino-group on the chitosan backbone with the surface anchoring Pd nanocluster. The surface charge is redistributed to generate high-valence Pd δ+ species due to the ligand-to-metal charge transfer between Pd and N, thus greatly improving the catalytic performance of formic acid dehydrogenation at room temperature and maintaining outstanding stability during 15 consecutive reaction cycles. The present work paves the way to the rational synthesis of Pd-based catalysts with tunable electronic states for practical purposes.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Haoran Jiang,Yong Xiao,Zhirang Liu,Zichen Wang,Bojian Wei,Qiliang Wei,Niancai Cheng
The development of high-performance electrocatalysts for hydrogen evolution reaction (HER) in different pH conditions is pivotal in producing green hydrogen, but remains challenging. Herein, we regulate the p-d orbitals hybridization between B and Pt for effective and durable HER at all pH ranges by controlling the inserted B atom. Consequently, the optimized B-doped Pt catalysts with 20 at.% B content (Pt80B20/C) has the highest HER performance, with only 7 mV overpotential in acidic conditions, 37 mV in alkaline media, and 47 mV in neutral media, more remarkably, have negligible attenuation during electrolysis up to 100 h, which is superior to commercial Pt/C catalysts. Theoretical calculations revealed that by inserting appropriate B atoms in the interstitial vacancies of Pt, the electronic structure of Pt is suitable for providing appropriate hydrogen intermediates (H*) adsorption/desorption strength, resulting in superior acid HER electrocatalyst performance. Besides, a strong electronic interaction existed between Pt and inserted-B atoms leaving Pt sites in an electron deficiency state, which facilitates the bond cleavage of the H-OH of H 2 O, hence accelerating water dissociation and promoting neutral/alkaline HER dynamics.
研究领域:
材料科学
·
电化学
·
能源催化
·
纳米科技
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Simeng Wu,Yanxiang Wang,Jiangyiming Jiang,Yibo Li,Dongming Liu
Atomic doping engineering represents a forefront in enhancing electromagnetic wave (EMW) dissipation by modulating electromagnetic response-related physical properties. Despite advantages in defect polarization, its limitations in precisely tailoring conductive/interfacial polarization loss often compromise the EMW absorption. This work proposes a loss pathway self-compensating strategy based on bimetallic catalytic theory and atomic doping effect, specifically involving the in-situ growth of carbon nanotubes encapsulating Cu-doped CoSe 2 on a carbon fiber framework. Deliberately introduced Cu, as a dual-effect electronic structure modulator, facilitates the controllability of carbon nanotubes and localized charge rearrangement in CoSe 2 , achieving dynamic synergistic regulation of conductive and defect polarization loss. The multi-dimensional coupling architecture further optimizes interfacial polarization loss and impedance matching. The perfected samples exhibit brilliant EMW absorption performance, achieving an extraordinary minimum reflection loss value of − 68.4 dB and an impressive ultra-wide effective absorption bandwidth of 7.11 GHz. Electromagnetic parameter analyses and density functional theory calculations reveal direct and indirect feedback mechanisms of electronic structure on loss pathways. Radar cross-section simulations and marine corrosion tests confirm the suitability of sample for marine defence. This work presents a strategy leveraging electronic structure modulation to circumvent loss pathway compromises, supplying a new inspiration for designing advanced EMW absorbing materials.
研究领域:
材料科学
·
电磁学
·
催化理论
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Junfeng Qin,Shijie Hu,Xiaohua Zhang,Min Hong,Cuicui Du,Jinhua Chen
Although Metal-organic frameworks (MOFs) have attracted extensive attention in energy-related fields, the direct application of MOF as bifunctional electrocatalysts for overall water electrolysis still remains a challenging topic. Herein, nickel foam (NF) self-supported hydrangea shaped NiRu bimetallic MOFs (NiRu-PTA/NF) prepared by a simple one-step hydrothermal method was directly used as bifunctional electrocatalyst, and exhibited highly-efficient hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic performances for alkaline freshwater/seawater overall splitting owing to the large active surface area, abundant active sites and high intrinsic activity attributed to the unique morphology, enriched oxygen vacancies and modulated electronic structure of the catalyst. Specifically, NiRu-PTA/NF needed only 16 mV overpotential to drive a HER current density of 10 mA cm −2 and 298 mV overpotential to drive a OER current density of 20 mA cm −2 in alkaline freshwater, much lower than those of Ni-PTA/NF ( η 10,HER = 162 mV, η 20,OER = 372 mV) and Ru-PTA/NF ( η 10,HER = 36 mV, η 20,OER = 335 mV). Furthermore, a two-electrode configured water electrolysis cell assembled with NiRu-PTA/NF as both cathode and anode required a very low cell voltage of 1.54 V to achieve an electrolytic current density of 10 mA cm −2 and were operated continuously for 200 h at various current densities including 10, 100 and 200 mA cm −2 . Additionally, the NiRu-PTA/NF-assembled electrolysis cell also displayed excellent seawater electrolysis performance. This study proposes an available strategy to design highly-efficient bifunctional catalysts for overall freshwater/seawater electrolysis based on electronic structure and oxygen vacancy modulation between bimetallic centers of MOFs, and extends their promising application prospects for industrially clean hydrogen production.
研究领域:
材料科学
·
能源化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2024
·
IF 15.8
Haijian Huang,Hao Feng,Ziyu He,Yanan Huang,Jiawei Xu,Chengzhi Hu,Zhangxian Chen,Zeheng Yang,Weixin Zhang
Enhancing proton storage in the zinc-ion battery cathode material of MnO2 holds promise in promoting its electrochemical performance by mitigating the intense Coulombic interaction between divalent zinc ions and the host structure. However, challenges persist in addressing the structural instability caused by Jahn–Teller effects and accurately modulating H+ intercalation in MnO2. Herein, the doping of high-electronegativity Sb with fully occupied d-orbital in MnO2 is reported. The Sb doping strategy engenders the formation of Mn–O–Sb path in the structure with a strong dipole polarization field, which facilitates the delocalization of eg orbital electron in Mn and thus mitigates the Jahn–Teller effects. Simultaneously, adjusting the level of Sb doping in MnO2 leads to modulation of the p-band center of O, optimizing its interaction with hydrogen and thereby enhancing proton storage. Consequently, MnO2 doped with 6% Sb exhibits commendable performance in both rate capability and cycling endurance, delivering 113 mAh g–1 at 2 A g–1 after 2000 cycles. This investigation underscores the crucial role of electronic structural engineering in elevating the electrochemical performance of cathode materials for zinc-ion batteries.
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
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2022
·
IF 9.965
Lei Hu,Liujun Jin,Tingyu Zhang,Jianhua Zhang,Jinghui He,Dongyun Chen,Najun Li,Qingfeng Xu,Jianmei Lu
The electronic modulation and morphology control of electrocatalysts are effective strategies to improve their catalytic performance. Herein, MoO 2 -MoO 3 /Ni 2 P nanoflowers were fabricated on the skeleton of conductive nickel foam as an electrocatalyst with enhanced performance via a universal hydrothermal and phosphating method. The introduction of P and Mo into the nickel-based catalyst through the co-doping strategy effectively adjusted the electronic structure of the Ni active sites, thereby significantly improving the performance of the catalyst. Particularly, the introduction of Mo allowed adjusting the morphology of the material, thereby increasing the electrochemical active area and promoting the exposure of more active sites. This strategy for improving the electrocatalyst’s performance in urea-assisted water splitting will provide a new concept for the simultaneous mitigation of the energy crisis and environmental contamination.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2022
·Vol. 26
·期 7
·e202200489
·
IF 2.551
Wenlin Zhang,Tingting He,Shimeng Liu,Lu-Hua Zhang,Fengshou Yu
Graphical Cobalt phthalocyanine was supported on N-doped MXene via axial coordination and π-π stacking. The formed axial coordination configuration N−Co−N 4 can effectively break the planar structure of Co-N 4 and enhance the oxygen reduction performance with an E 1/2 of 0.863 V, which is better than the 20 wt.% Pt/C catalyst of 0.85 V. The precise control of electronic configurations of catalytic sites via molecular engineering is significantly desirable for boosting electrocatalytic activity. We reported a new-type composite electrocatalyst with cobalt phthalocyanine supported on N-doped MXene nanosheets (N-MXene/CoPc) through a self-assembly process. Beneficial from the joint action of N sites participation and axial coordination, N-MXene/CoPc exhibits a high ORR activity with positive onset potential (E onset =0.98 V vs. RHE) and half-wave potential (E 1/2 =0.863 V), which is superior over the pristine CoPc (E 1/2 =0.72 V) and the composite with undoped MXene as support (MXene/CoPc, E 1/2 =0.771 V). Additionally, N-MXene/CoPc exhibits an excellent durability with only 8.5 % attenuation after 25000 s of continuous i-t test, while a more obvious decay 18.6 % for 20 wt.% Pt/C. This work not merely reported a robust ORR catalyst, but more provides a reasonable design strategy for nonnoble-metal catalysts through catalyst-support interactions.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·Vol. 33
·期 46
·2300625
·
IF 19
Jingqi Chi,Lili Guo,Jiayu Mao,Tong Cui,Jiawei Zhu,Yanan Xia,Jianping Lai,Lei Wang
The electrocatalytic production of hydrogen from seawater provides a low-cost way to realize energy conversion, but is restricted by high potential for seawater electrolysis and the chlorine oxidation reaction (ClOR) at the anode. Here, the self-growth of Mo-doped Ni 2 P nanosheet arrays with rich P vacancies on molybdenum-nickel foam (MNF) (Mo-Ni 2 P v @MNF) is reported as bifunctional catalyst for Cl-free hydrogen production by coupling hydrogen evolution reaction (HER) with hydrazine oxidation reaction (HzOR) in seawater. Impressively, the Mo-Ni 2 P v @MNF electrode as bifunctional catalyst has an excellent activity for overall hydrazine splitting (OHzS) with an ultralow voltage of only 571 mV at 1000 mA cm −2 and can maintain stability for an ultra-long time of 1000 h at 100 mA cm −2 . Moreover, integration of OHzS into self-assembled hydrazine fuel cells (DHzFC) or solar cells can enable the self-powered H 2 production. The industrial hydrazine sewage as feed for the above eletrolysis system can be degraded to ≈5 ppb rapidly. Density functional thoery calculations demonstrate that the electronic structure modulation induced by P vacancies and Mo doping can not only achieve thermoneutral ΔG H* for hydrogen evolution reaction but also enhance dehydrogenation kinetics from *N 2 H 4 to *NHNH 2 for HzOR, achieving enhanced dehydrogenation kinetics.
研究领域:
材料科学
·
电催化
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2023
·Vol. 25
·期 31
·4480-4486
·
IF 3.1
Yangyang Wang,Xin Wen,Xiaojing Dong,Chen Xu,Wenguang Ma,Yiqiang Sun,Bo Xu,Cuncheng Li
The development of a bifunctional ruthenium-based electrocatalyst that can efficiently and economically drive both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) remains challenging because ruthenium species can undergo severe agglomeration during preparation which can significantly reduce the catalytic activity. Constructing supported metal catalysts can not only improve the stability of Ru but also improve the catalytic performance by adjusting the electronic structure, which is an effective way to solve the current challenges. In this paper, Ru-loaded MoO2/MoO3 heterostructures (Ru–MoOx) with oxygen vacancies were successfully synthesized by controlling the annealing temperature. This special structure can effectively tune the electronic structure, enhance the electrical conductivity and increase the active sites, thus improving the catalytic activity of the catalyst. Performance studies have shown that Ru–MoOx exhibits excellent HER and OER performance in alkaline media. And it is not surprising that the overall water decomposition performance of Ru–MoOx is also excellent, requiring only a cell voltage of 1.54 V to reach 10 mA cm−2.
研究领域:
材料科学
·
电化学
✓ 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）