Chemistry-An Asian Journal
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2020
·Vol. 15
·期 24
·4280-4285
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IF 4.056
Zhipeng Sun,Lei Sheng,Hao Gong,Li Song,Xiaolong Jiang,Shengyao Wang,Xianguang Meng,Tao Wang,Jianping He
In this work, a series of gold-supported titanium oxide composites have been prepared and high selectivity (over 90%) of hydrogen peroxide is achieved. For the first time, electrochemical impedance spectroscopy and electron spin resonance analysis demonstrate that high charge transfer impedance of the catalyst can suppress the decomposition of OOH* intermediates thus promoting the two-electron process of the oxygen reduction reaction.
研究领域:
电催化
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材料科学
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能源化学
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纳米材料
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环境化学
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DOI
高影响因子
ACS Applied Materials & Interfaces
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2026
·Vol. 18
·期 31
·42780-42788
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IF 7.8
Zou Lie,Huang Xiao-Yan,Zhang Yi,A Yao-Lin,Xu Qing-Chi,Chen Bing-Hui,Liu Jinxuan,Zhang Hua,Li Jian-Feng
Understanding the molecular origins of oxygen reduction reaction (ORR) activity on Pt-based catalysts is essential for the rational design of high-performance electrocatalysts. Herein, by combining electrochemical measurements with in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), we systematically investigate the ORR pathway on Pt-based alloy nanocatalysts incorporating different transition metals to elucidate how surface oxygenated intermediates dictate ORR activity. Among the catalysts examined, PtNi exhibited higher activity than PtFe, PtCo, and commercial Pt/C, underscoring the pronounced sensitivity of intrinsic ORR activity to alloy composition. Potential-dependent in situ Raman spectra, corroborated by isotopic labeling, directly identified *OOH as a key ORR intermediate and established a clear correlation between its vibrational frequency and catalytic activity. The results suggest that Ni alloying may modify the electronic environment of Pt, thereby weakening the Pt-O interaction, optimizing the adsorption state of the kinetically relevant *OOH intermediate, and consequently promoting ORR kinetics. This study establishes an effective spectroscopic platform for probing ORR intermediates on realistic electrocatalyst surfaces and offers molecular-level understanding of the activity enhancement in Pt-based alloy catalysts.
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DOI
PubMed
高影响因子
ACS Earth and Space Chemistry
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2023
·
IF 3.4
Hao Tian,Xue-Bin Zhang,Yin-Ping Li,Qing He,Na-Na Tian,Song-Hai Wu,Xu Han
Although inorganic Fe(IV)═O oxo and Fe(III)-OOH peroxo have attracted more attention in aqueous environments, direct evidence for the characterization and identification of those oxidizing species is still lacking. In this study, the doped Cu/Co increases the reactivity of ferrihydrite/hematite in oxidizing As(III) by S(IV)-O2 under alkaline and dark conditions. Quenching experiments exclude the contributions of ·OH, O2•–, SO3•–, SO4•–, SO5•–, HSO5–, and H2O2 and confirm that peroxo and oxo are primary oxidizing species in As(III) oxidation. Electrochemical analyses indicate that Fe(IV)═O oxo and Fe(III)-OOH peroxo are primarily located on the surface of ferrihydrite and hematite. Selective oxidation of methyl phenyl sulfoxide and methyl phenyl sulfide to the corresponding oxidation products further reveals the presence of ≡Fe(IV)═O oxo on both ferrihydrite and hematite, and the doped Cu/Co significantly decreases the produced ≡Fe(IV)═O oxo on ferrihydrite, while increases the produced ≡Fe(IV)═O oxo on hematite. Meanwhile, selective oxidation of benzyl alcohol to benzaldehyde indicates the presence of ≡Fe(III)-OOH peroxo on both ferrihydrite and hematite, and the doped Cu/Co apparently increases the produced ≡Fe(III)-OOH peroxo on ferrihydrite and hematite. Raman analysis further reveals the presence of ≡Fe(IV)═O oxo and ≡Fe(III)-OOH peroxo on pure and metal-doped ferrihydrite/hematite, which also confirms that the doped Cu/Co decreases the produced ≡Fe(IV)═O oxo on ferrihydrite and increases ≡Fe(IV)═O oxo on hematite, while apparently increasing ≡Fe(III)-OOH peroxo on both ferrihydrite and hematite. This study enriches our understanding on the oxidizing species in the S(IV)-mediated oxidation processes under alkaline conditions, providing new insight on the oxidation reactivity of surface peroxo and oxo species mediated by the doped metal ions.
研究领域:
环境科学
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化学
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产品关联
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2026
·
IF 3.6
Yue Gui,Jincheng Liu,Ping Yang,Jingxian Zhu,Yiran Xu,Jing Wang,Xin Dong,Tongming Sun,Yanfeng Tang,Minmin Wang
This study successfully fabricated a freestanding ZnO@(NiFe)OOH nano-heterostructure array electrocatalyst with high hydrophilicity for efficient electrocatalytic nitrate reduction to ammonia (NO 3 RR) in neutral media. The material integrates the large specific surface area of one-dimensional ZnO nanoarrays with the electronic modulation capability of heterogeneous interfaces, which significantly enhances nitrate adsorption and activation, promotes proton supply, and effectively suppresses the hydrogen evolution side reaction. The highly hydrophilic surface further accelerates electrolyte diffusion, nitrate ion transport, and product desorption. In a neutral electrolyte of 0.1 M PBS containing 0.15 M KNO 3 at a potential of −1.0 V (vs. RHE), the catalyst achieves an ammonia production rate of 4.86 mg·h −1 ·cm −2 with a Faradaic efficiency of 85.58%, while generating minimal byproducts, demonstrating excellent catalytic selectivity and stability. This work provides a new strategy for the structural design and performance enhancement of NO 3 RR electrocatalysts, which holds significance for advancing green ammonia synthesis and enabling efficient conversion of nitrate in water pollution control. Graphical A self-supported ZnO@(NiFe)OOH core-shell array enables efficient nitrate-to-ammonia conversion. The ZnO core accelerates NO 3 -diffusion and prevents active site coverage while enhancing conductivity and stability. The (NiFe)OOH shell facilitates intermediate conversion and suppresses hydrogen evolution by weakening H+ adsorption. Its surface hydroxyl groups promote water dissociation, ensuring a local proton supply. In neutral media, this design achieves superior performance: at −1.0 V vs RHE in 0.15 M KNO 3 , it delivers an NH3 yield of 4.86 mg h −1 cm −2 and a faradaic efficiency of 85.58%.
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Yuqing Li,Suhang Meng,Chunhe Cao,Yi Li
The electronic structure of metal oxides plays an important role in determining their catalytic activity, but how to regulate this structure to overcome inherent limitations in electron transfer efficiency and spin state configuration remains a significant challenge. Herein, we designed a Ni-doped Co 3 O 4 nanorod, where Ni occupied at the octahedral site can effectively facilitate the spin-state transition of Co 3+ from a low-spin to a high-spin state, inducing an electronic structure reconstruction in Co 3 O 4 . This not only increases the e g filling of Co 3+ but also generates additional electronic states, benefiting water purification process. As expected, the obtained Ni-Co 3 O 4 -4 catalyst exhibits excellent catalytic performance in electro-Fenton like (EF-like) system, achieving a ciprofloxacin (CIP) removal efficiency of 94.3%, with a rate constant ( k ) 1.69 times higher than that of Co 3 O 4 . In situ Raman spectra confirmed that the charge rearrangement between Ni and Co 3 O 4 facilitated the formation of the key *OOH intermediate, promoting the production of superoxide radicals (·O 2 - ). Additionally, the developed Ni-Co 3 O 4 -4 system can operate continuously for 600 min in a continuous-flow reactor. This work deepens the comprehensive understanding of the relationship between electrocatalytic activity and the spin configuration of Co ions, offering an effective design strategy for spinel compound catalysts aimed at environmental remediation.
研究领域:
环境科学
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催化材料
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电化学
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DOI
高影响因子
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
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2020
·Vol. 22
·期 22
·12456-12464
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IF 3.43
Xiang-Ming Wang,Song-Hai Wu,Hai-Tao Ren,Peng-Yue Zhu,Cong Wang,Yong Liu,Shi-Wei Sun,Xiao-Cong Zhang,Yi-Ying Lin,Zi-He Meng,Shao-Yi Jia,Xu Han
Bi2+xWO6 is a cost-effective and environmentally friendly photocatalyst that shows high reactivity in the oxidation of various contaminants under visible light. However, under alkaline conditions, the reactive oxidative species in the Bi2+xWO6 system are still not clear yet. In this study, it is observed that the oxidation rates of As(III) increase with increasing pH values in the Bi2.15WO6 system. Photoluminescence and the Mott–Schottky analyses confirm that OH− promotes the separation and transfer of photogenerated electron–hole pairs over Bi2.15WO6, thus facilitating the oxidation of As(III). Electron spin resonance spectra analysis and quenching experiments rule out contributions of •OH, O2˙−, 1O2 and superoxo species to As(III) oxidation and indicate that surface –OOH and/or H2O2 are indeed the predominant species under alkaline conditions. The improved production of H2O2 by H-donors such as glucose and phenol, as well as the UV-vis diffuse reflectance and Raman analyses, further confirms the formation of surface –OOH on Bi2.15WO6 under alkaline conditions. In the dark, the significant higher oxidation rate of As(III) by H2O2–Bi2.15WO6 than that by H2O2 alone reveals that surface −OOH, instead of H2O2, plays an important role in As(III) oxidation. This study enriches our understanding of the diversity of reactive oxygen species (ROS) in the Bi2.15WO6 system and gives new insight into the mechanism involved in the oxidation of As(III) under alkaline conditions.
研究领域:
环境科学
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光催化
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材料科学
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
·
IF 22.1
Lina Yan,Chao Wang,Yueshuai Wang,Yahui Wang,Zhaozhao Wang,Lirong Zheng,Yue Lu,Ruzhi Wang,Ge Chen
Electrochemical production of hydrogen peroxide (H 2 O 2 ) is a sustainable and environmentally benign process. The electrochemical oxygen reduction process (ORR) via a two electron pathway (2e - ORR) offers a practical method for on-site H 2 O 2 generation. As an earth-abundant catalyst, the cobalt-nitrogen coordinated systems integrated into the carbon matrix (Co-NC) has caused wide attention for its high activity in 2e - ORR. Even though most of the reported Co-NC catalysts have classical planar Co-N 4 coordination, axial coordination engineering has recently emerged as an effective way to control the active sites in the axial direction by using different coordination ligands. The structure-function link between the Co-N configuration of non-planar coordination and 2e - ORR activity is, however, not fully understood. An axial-N coordinated Co-N 5 motif embedded in hierarchically porous graphite-3R carbon (Co-N 5 C) was effectively synthesized using a template-sacrificing method. The Co-N 5 C has a high selectivity for 2e - ORR and a high H 2 O 2 molar production rate of up to 6.78 mol peroxide/g catalyst /h in acidic media, both of which are better than its Co-N 4 counterpart. DFT analyses demonstrate that axial-N ligands regulated the d -band center of the Co atom in the Co-N 5 C catalyst, inducing a shift in Δ G *OOH near the Sabatier volcano plot's peak (Δ G *OOH = 4.22 eV). This optimized the binding of the *OOH intermediate and then enhanced the protonation of *OOH to produce H 2 O 2 more efficiently.
研究领域:
材料科学
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电化学
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催化科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
·
IF 20.2
Xin Xiao,Yan Wei,Shaowei Song,Brian McElhenny,Fanghao Zhang,Xingxing Jiang,Yang Zhang,Shuo Chen,Mingkui Wang,Yan Shen,Zhifeng Ren
Exploiting highly efficient oxygen-evolving electrocatalysts is crucial for hydrogen production through seawater electrolysis. Here, a hierarchical structure of boron-doped (Ni,Fe)OOH grown on Ni 3 N nanosheets supported on nickel foam [denoted as B-(Ni,Fe)OOH/Ni 3 N/NF] is fabricated. Benefiting from the formation of abundant active sites and the reduced free energy barrier of the rate-determining step caused by B doping, the obtained B-(Ni,Fe)OOH/Ni 3 N/NF exhibits extraordinary electrocatalytic activity for oxygen evolution reaction, requiring overpotentials of only 283 mV and 309 mV to achieve a current density of 1000 mA cm −2 in alkaline pure water and seawater media, respectively, as well as superior stability. When driven by a commercial Si solar cell, the electrolyzer using B-(Ni,Fe)OOH/Ni 3 N/NF as the anode and a previously reported Ru/(Fe,Ni)(OH) 2 /NF as the cathode can achieve a high current of over 1000 mA in alkaline seawater media. This shows the great potential in applying a photovoltaic-driven electrolyzer toward large-scale hydrogen production in seawater electrolysis.
研究领域:
材料科学
·
能源化学
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DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Rongbin Lin,Xiaoliang Zhang,Hai Li,Jinchun Tu,Cong Li,Zaowen Zhao,Weiwei Li,Lei Ding
Seawater electrolysis offers a viable strategy for the large-scale production of clean hydrogen. However, the oxygen evolution reaction (OER) catalysts is often compromised by the competitive chloride evolution reaction and the associated corrosion in seawater environments. Herein, we present a novel NiFe-S aerogel (AG) electrocatalyst featuring a porous 3D-network structure and a core–shell architecture. This catalyst demonstrates outstanding OER performance, achieving a low overpotential of 260 mV at 100 mA cm −2 , a Tafel slope of 55 mV dec -1 , and remarkable stability exceeding 500 h at 500 mA cm −2 in alkaline natural seawater. Through combined experimental and computational analyses, we discovered that the self-reconstructed crystalline-amorphous (Ni,Fe)OOH/NiFeS 2 heterojunction is pivotal to the outstanding performance of the NiFe-S AG electrocatalyst. The unique heterostructure facilitates electron transfer and down shifts the d-band center of the active sites, optimizing the adsorption strength of oxygen-containing intermediate species. Moreover, the stability is augmented by increased Fe and Ni vacancy formation energies, and higher affinity for OH – over Cl - , hence attenuating the corrosion from Cl - and suppressing the leaching of active sties. This work highlights the significance of the crystalline-amorphous heterojunction in aerogel catalyst and offers new insights into the design of efficient electrocatalysts for seawater oxidation.
研究领域:
材料科学
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电化学
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能源技术
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产品关联
DOI
高影响因子
Small
·
2024
·
IF 13
Wen Zhang,Jianyang Gao,Qinzhen Gong,Fusheng Liu,Yang Zhang,Guang-Rui Xu,Zexing Wu,Lei Wang
Seawater electrolysis is the most promising technology for hydrogen production, in which surface reconstruction on the interface of electrode/electrolyte plays a crucial role in activating the catalytic reactions with a low activation energy barrier. Herein, an efficient Mo modifying NiCoMo prickly flower clusters electrocatalyst supported on nickel foam (Mo-doped Ni/Co-OOH prickly flower clusters) is obtained, which serves as an eminently active and durable catalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) due to the surface reconstruction during the alkaline seawater electrolysis with ultralow overpotentials. It just requires a cell voltage of 1.52 V to achieve the current density of 10 mA cm −2 for water electrolysis along with robust durability over 30 h. Mo doping effectively regulates the surface reconstruction of Ni/Co-OOH, which facilitates the adsorption of oxygen-containing intermediates on the active center, and the nonhomogeneous interface induces charge rearrangement for the catalytic process to improve efficiency, providing a new strategy for revealing the seawater electrolytic mechanism.
研究领域:
材料科学
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电化学
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可再生能源
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DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2017
·Vol. 19
·期 24
·5809-5817
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IF 9.125
Haidong Yang,Yu Long,Yan Zhu,Ziming Zhao,Ping Ma,Jun Jin,Jiantai Ma
The exploration of highly efficient nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER) is of great importance for potential applications in sustainable energy conversion. Recently, the layered metal hydroxide (LMH) family is receiving extensive research attention owing to its unique structural properties. However, the gained electrocatalytic performance of LMH-based catalysts for the OER is still far from the state-of-the-art requirements because of its finite number and poor reactivity of exposed active sites. In response, we synthesized crystal lattice distorted ultrathin cobalt hydroxide (denoted as CLD-u-Co(OH)2) nanosheets with a great number of efficient catalytic active sites through the introduction of Ga into ultrathin Co(OH)2, followed by a selective removal of Ga, denoted as the “introduction @ removal” process. As a result, the crystal lattice distortion confined inside CLD-u-Co(OH)2 generates abundant elongated Co–OOH bonds on exposed (10) facets serving as efficient catalytic active sites for the OER. Besides, the optimized amount of “introduction @ removal” of Ga (4 at%) allows for an exquisite balance between distortion engineering and electrical conductivity, synergistically. The as-prepared CLD-u-Co(OH)2 achieves an overpotential of 265 mV at a current density of 10 mA cm−−2, an unexpectedly small Tafel slope of 47 mV dec−−1, and a long-term stability (beyond 20 h) in basic media. It is mainly attributed to abundant catalytic active sites, robust reactivity per site, and good electrical conductivity. Furthermore, the green and sustainable engineering of crystal lattice distortion to improve the intrinsic electrocatalytic activity of CLD-u-Co(OH)2 nanosheets presented in this work may provide a promising strategy to design and synthesize newly highly efficient LMH-based electrocatalysts for the OER.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Ruilin Liu,Chao Wang,Yong Yan,Ruzhi Wang,Ge Chen
The direct hydrogen peroxide (H2O2) product from H2 and O2 is a promising anthraquinone replacement because it is environmentally friendly and has a high atom efficiency. Experimental and theoretical studies have proven that optimizing the adsorption of the critical intermediate OOH* on the metal site significantly promotes the further protonation of this intermediate and inhibits the O–O bond cleavage, thus enhancing the activity and selectivity. Redistributing the charge density of active sites to tuning the d-band center of the metal could effectively modulate the intermediates adsorption, and thus regulate the catalytic efficiency. Herein, we show that a Lewis acid (ZnCl2 solution) induces abundant oxygen vacancies (Ovs) on the TiO2 surface, which results in a reversal of charge transfer from TiO2–Ov support to the Pd atom, generating an electron-rich Pd configuration. Compared with pristine Pd/TiO2, Pd/TiO2–Ov possesses higher H2O2 selectivity and productivity, with values of 80.7% and 186 mol kgcat–1 h–1, respectively. In addition, Pd/TiO2–Ov maintains stability during the six cycles reaction due to its high resistance to the leaching of Pd species. Theoretical calculations reveal that the reversed charge transfer downshifts the d-band center of Pd, which promotes O2 adsorption on the Pd surface and weakens the OOH* intermediates adsorption. Thus, the energy barrier for the hydrogenation of the OOH* intermediate is significantly decreased, and the O–O band cleavage is inhibited. This study reports a reversal of charge transfer tuning the d-band center of the active site for efficient direct H2O2 synthesis, which may provide insight for designing high-performance catalysts.
研究领域:
化学
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材料科学
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催化
·
环境科学
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产品关联
DOI
高影响因子
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