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SENSORS AND ACTUATORS B-CHEMICAL · 2022 · IF 9.221

Room temperature detection of low-concentration H2S based on CuO functionalized ZnFe2O4 porous spheres

Hao Zhang,Siyuan Gao,Zeyao Feng,Zhen Sun,Xianwen Yan,Zhenhua Li,Xueli Yang,Guofeng Pan,Ye Yuan,Lanlan Guo

Room temperature H 2 S gas sensor with low detection limit is necessary for practical application. In this work, ZnFe 2 O 4 was synthesized through a simple solvothermal method, and then CuO was decorated onto the surface of ZnFe 2 O 4 via a modified metal organic framework synthesis method . After a series of characterization methods, it was found that CuO/ZnFe 2 O 4 had porous nanosphere morphology. Gas sensing measurements indicating that the synthesized CuO/ZnFe 2 O 4 porous spheres exhibited excellent H 2 S sensing performance under room temperature, including high sensitivity under low concentration (less than 10 ppm), excellent selectivity, low limit of detection (0.1 ppm), good repeatability, and fast response/recovery time. The sensing mechanism was discussed in detail, which is mainly contributed to the sensitization effect of CuO. This work provides a new strategy for constructing room temperature H 2 S gas sensor based on ZnFe 2 O 4 .

研究领域: 材料科学 · 传感器技术
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Nafion-Mediated Proton Transfer Facilitates the Electroreduction of SO2 to H2S

Hui Liu,Zhujiang Wang,Hao Chen,Yushan Tu,Jun Wu,Fenghua Shen,Xudong Liu,Yingxue Fu,Lin Wu,Jiaqi Long,Kaisong Xiang

The electrocatalytic reduction of SO2 to produce H2S is a critical approach for achieving the efficient utilization of sulfur resources. At the core of this approach for commercial applications lies the imperative need to elevate current density. However, the challenges posed by high current density manifest in the rapid depletion of protons, leading to a decrease in SO2 partial pressure, consequently hampering the generation and separation of H2S. Here, we demonstrate an effective solution to alleviate the problem of insufficient supply of protons by employing Nafion polymer as the proton conductor to modified Cu catalysts surface, creating a proton-enriched layer to boost H2S generation. It was observed that Nafion shortens the hydrogen bonds with water molecules in the electrolyte via its sulfonic acid groups, benefiting the proton transfer and consequently increasing the proton density on the electrode surface by 5-fold. With the Nafion-modified catalyst, the H2S partial current density and separation efficiency reached 205.9 mA·cm–2 (1.01 mmol·cm–2·h–1) and 87.8%, which were 1.34 and 1.22 times that on unmodified Cu, respectively. This work highlights the practicality of fabricating a proton conductor via ionic polymer for the control over product selectivity in pH-sensitive reactions under high current density.

CAS / MDL: 31175-20-9
研究领域: 电化学 · 材料科学 · 催化 · 环境化学
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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Molecular traps and exposed Mo sites induced by oxygen knockout enhanced H2S sensing of MoO3 nanoflowers

Xiang Li,Huimin Yang,Qirui Wu,Chaoqi Zhu,Jiahong Tang,Chaofan Ma,Lu Tang,Huiyu Su,Xiaoxia Wang,Changsheng Xie,Dawen Zeng

Limited by the dense arrangement of oxygen atoms in the outer layer, the active Mo sites of MoO 3 ultrathin nanoflowers are shielded by oxygen, making it difficult for efficient gas adsorption. Here, oxygen atoms on the surface of MoO 3 nanoflowers (MoO 3 NFs) were knocked out based on a simple hydrogenation strategy to obtain MoO 3 defective nanoflowers (MoO 3 DNFs) with abundant molecular traps and exposed Mo sites. Notably, the response of MoO 3 DNFs-10 to 2 ppm H 2 S is 3 times that of MoO 3 NFs. Oxygen atom knockout was verified based on Laser Raman Spectroscopy, Photoluminescence (PL), UV–Visible Spectroscopy (UV–Vis), and X-ray photoelectron energy Spectroscopy (XPS), while calculations based on density functional theory (DFT) were used to reveal the sensing enhancement of molecular traps and exposed Mo sites. On the one hand, molecular traps can effectively trap H 2 S molecules to facilitate further adsorption. On the other hand, exposed Mo sites have higher charge activity and exhibit higher adsorption capacity for H 2 S gas. This work breaks through the limitations of the traditional oxygen vacancy model and innovatively discusses the synergistic effect of molecular traps and exposed Mo sites on enhanced sensing, which can provide a reference for the gas sensing by metal oxide semiconductors.

研究领域: 材料科学 · 传感器技术
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

One-step synthesis of flower-like MgO/Carbon materials for efficient H2S oxidation at room temperature

Kunlin Li,Xueyan Chen,Jianghao Zhang,Min Chen,Xiaoxiao Qin,Fei Wang,Kai Li,Jinhou Fang,Changbin Zhang

Regenerable materials with abundant basic sites and sulfur storage space are highly desirable for the removal of H 2 S. In this work, we synthesized a flower-like MgO/Carbon material by one-step carbonization of magnesium gluconate and applied it for H 2 S oxidation at room temperature. The results demonstrate that the high content of MgO and super-hydrophilic surface of the MgO/Carbon provide abundant basic sites for the adsorption and dissociation of H 2 S. Moreover, carbon defects and a well‐developed pore structure offer active sites for the desulfurization reaction and large space for storage of sulfur products. Consequently, the MgO/Carbon materials exhibit excellent H 2 S oxidation performance, which is far superior to that of commercial activated carbon. In addition, the MgO/Carbon materials show extraordinary regeneration capacity and maintain their high performance even after 5 cycles of desulfurization/regeneration. Furthermore, mechanisms for the H 2 S oxidation process, deactivation and regeneration are proposed based on the experimental and characterization results. Considering the simple preparation process, excellent desulfurization and regeneration performance of as-prepared MgO/Carbon material, our findings provide a new strategy for the design of efficient desulfurizers.

研究领域: 材料科学 · 环境科学
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SENSORS AND ACTUATORS B-CHEMICAL · 2022 · IF 9.221

A room-temperature ppb-level H2S sensor based on MoO3/CuO/g-C3N4 via a simple synthesis

Cheng Feng,Congting Zhang,Chang Xu,Shuang Lin,Baohua Zhang,Huanxing Wu,Zheng Zhang,Xinming Guo,Haineng Bai,Fuqiang Guo

The detection of H 2 S for biomarkers or special occasions often requires a lower detection limit. In this work, the ppb-level H 2 S sensor based on MoO 3 /CuO/g-C 3 N 4 (MCC) was presented by a simple method. The characterized results show that MCC-2 possesses a larger specific surface area, and has more adsorbed oxygen and oxygen vacancy compared to MoO 3 and MoO 3 /CuO. The gas-sensitive test results show that the response of the MCC-2 sensor to 1000 ppb H 2 S is up to 8.24 at room temperature , which is 1.31 times of MoO 3 /CuO (6.28). More importantly, the theoretical detection limit of the MCC-2 sensor is as low as 1.1 ppb, which is the lowest in the recent H 2 S sensor. In addition, the MCC-2 sensor has reliable repeatability, excellent selectivity to H 2 S, and still maintains a high response after continuous test for 5 weeks. Simultaneously, the MCC-2 sensor also keeps an outstanding response at high relative humidity. The excellent gas sensing properties are due to the larger specific surface area that can enable more gases to be adsorbed on the material surface. In addition, the oxygen vacancy reduces the energy required to adsorb the target gas and the formed heterojunctions by MoO 3 /CuO/g-C 3 N 4 expedite carrier migration.

研究领域: 材料科学 · 环境科学 · 化学
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JOURNAL OF MOLECULAR STRUCTURE · 2021 · IF 3.196

A simple and efficient fluorescent probe for rapidly detecting H2S in GBC - SD cells based on 1,8 - naphthalimide - ebselen

Chenglu Zhang,Lu Zhang,Yuqing Li,Zhixuan Ren,Lu Li,Yanpeng Zhang,Yizheng Li,Cui Liu

A novel 1,8 - naphthalimide - ebselen fluorescent probe BPHN was synthesized. BPHN has great fluorescence properties: high quantum yield (0.5932), large Stokes shift (125 nm) and remarkable stability at wide pH range (5–11). The results of fluorescence spectroscopy experiments show that BPHN can recognize H 2 S selectively and sensitively. BPHN exhibits low LOD (0.129 μM) and fast response (90 s). The potential of BPHN as a biosensor for H 2 S was demonstrated by imaging of exogenous H 2 S in living cells. BPHN can also detect H 2 S qualitatively and quantitatively in actual water samples.

研究领域: 生物化学 · 医学检测 · 分析化学
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CERAMICS INTERNATIONAL · 2023 · IF 5.2

Porous-Pt-CuO-driven electrochemical biosensor for tracking of endogenous H2S biomessenger molecules

Xiao Zhang,Qianhui Wei,Hongbin Zhao,Feng Wei,Tengfei Li

Hydrogen sulfide (H 2 S) is considered to be the third endogenous gas messenger after nitric oxide and carbon monoxide , and is closely related to physiological and pathological functions of human being. Rapid and real-time monitoring of endogenous H 2 S production in living cells is of great significance for clinical diagnoses of related disease and in-depth investigation of pathological processes. The application of electrochemical sensors has become a promising method to achieve real-time H 2 S monitoring comparing to other methods. Up to now, low-cost, and highly sensitive electrocatalysts for H 2 S detection are conspicuously scarce. Herein, we developed a high-efficient method to construct a H 2 S electrochemical sensor, which configure dissolved–H 2 S–sensitive electrochemical sensor using porous Pt-modified copper oxide (Pt–CuO) as electrocatalyst. The obtained sensor possessed remarkable H 2 S detection performance, achieving the detection limit of 0.5 ppm and apparent selectivity toward various gases (e.g., ammonia, nitrogen dioxide , and carbon dioxide). The electrochemical sensor was also applied for monitoring H 2 S released from mesenchymal stem cells. The enhanced sensing performance was attributed to: (1) electrocatalytic reaction between CuO and [H 2 S] (H 2 S and HS − ) was observed in the cyclic voltammetry curves with oxidation current peaks; (2) Pt catalytic activity promoted electron transfer during the detection process and further decreasing Pt–CuO resistance; and (3) enhanced diffusion of detection molecules/ions, which increased the reactivity sites through forming cross porous structures using sodium carbonate as sacrifice template. The proposed Pt–CuO-based electrochemical sensor shows great potential for applications in clinical diagnoses, and provides effective means to understand the role of H 2 S in biological processes.

研究领域: 生物医学工程 · 分析化学 · 生物化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

Self-assembly tourmaline@BiFeO3 composites with enhanced polarization for dual-selective C3H6O and H2S detection

Xiaojie Li,Fanhao Jia,Na Luo,Haijie Cai,Jianguo Chen,Wei Ren,Jinrong Cheng,Jiaqiang Xu

Ferroelectric oxides with great polarization have attracted much attention due to the polarization modulated carrier behaviors causing high gas sensitivity in detecting hazardous toxic gases. In this work, tourmaline@BiFeO 3 (T@BFO) composites were fabricated by the sol-gel method based on the electrostatic self-assembly strategy for the C 3 H 6 O and H 2 S detection. It is found that BFO nanoparticles are uniformly distributed on tourmaline due to the strong electrostatic field of tourmaline. In comparison with pure BFO, the T@BFO composites showed an improved gas sensitivity. More importantly, the sensor based on 3.0-T@BFO can effectively detect C 3 H 6 O at 150 °C and H 2 S at 210 °C in limits of detection as low as 50 and 7 ppb, respectively. The results exhibit that 3.0-T@BFO composites have lower activation energies (E act ) of C 3 H 6 O at 150 °C and H 2 S at 210 °C, which endow 3.0-T@BFO with dual-selectivity for C 3 H 6 O and H 2 S. The Ex-situ XPS and density functional theory calculations further reveal that tourmaline activates the sensing site of BFO to achieve selective adsorption of C 3 H 6 O at Bi, Fe, and oxygen vacancies sites and H 2 S at surface lattice oxygens, Fe and oxygen vacancies sites. These results provide an efficient strategy to design practice multifunctional and highly sensitive gas sensors for detecting hazardous toxic gases.

研究领域: 材料科学 · 传感器技术 · 化学
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Prepared gold-modified hollow nanosphere Co3O4/rGO composites for low concentration H2S gas detection

Lihong Liu,Ming Yang,Bo Li,Duo zhang,Lihua Huo

In this paper, Au-modified Co 3 O 4 hollow nanospheres/graphene composites (Au-Co 3 O 4 /rGO) were synthesized for the first time through a novel “one-pot cooking” method at ambient temperature. The hollow nanospheres exhibited a particle size of approximately 10–15 nm, while the modified Au nanoparticles were about 4–5 nm in diameter. A high-efficiency and high response H 2 S gas sensor was constructed based on Au-Co 3 O 4 /rGO ternary composites. The effects of different Au modifying mass ratios on the H 2 S gas-sensitive performance of the composites were systematically investigated. At an operational temperature of 92 °C, the Au-Co 3 O 4 /rGO sensor, incorporating an Au loading mass ratio of 1.3 wt%, exhibited a response value of 175.4 for H 2 S at 100 ppm, a recovery time of 30 s, and a detection limit reaching as low as 10 ppb. This response was tripled compared to the undoped Co 3 O 4 /rGO sensor. At the same time, the H 2 S sensing mechanism by Au-Co 3 O 4 /rGO was discussed in detail.

研究领域: 材料科学 · 传感器技术 · 纳米科技
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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2024 · IF 10.8

The Impact of Bisphenol A on the Anaerobic Sulfur Transformation: Promoting Sulfur Flow and Toxic H2S Production

Qizi Fu,Chenxi Li,Zirui Liu,Xingyu Ma,Yunhao Xu,Yan Wang,Xuran Liu,Dongbo Wang

Bisphenol A (BPA), as a typical leachable additive from microplastics and one of the most productive bulk chemicals, is widely distributed in sediments, sewers, and wastewater treatment plants, where active sulfur cycling takes place. However, the effect of BPA on sulfur transformation, particularly toxic H2S production, has been previously overlooked. This work found that BPA at environmentally relevant levels (i.e., 50–200 mg/kg total suspended solids, TSS) promoted the release of soluble sulfur compounds and increased H2S gas production by 14.3–31.9%. The tryptophan-like proteins of microbe extracellular polymeric substances (EPSs) can spontaneously adsorb BPA, which is an enthalpy-driven reaction (ΔH = −513.5 kJ mol–1, ΔS = −1.60 kJ mol–1K –1, and ΔG = −19.52 kJ mol–1 at 35 °C). This binding changed the composition and structure of EPSs, which improved the direct electron transfer capacity of EPSs, thereby promoting the bioprocesses of organic sulfur hydrolysis and sulfate reduction. In addition, BPA presence enriched the functional microbes (e.g., Desulfovibrio and Desulfuromonas) responsible for organic sulfur mineralization and inorganic sulfate reduction and increased the abundance of related genes involved in ATP-binding cassette transporters and sulfur metabolism (e.g., Sat and AspB), which promoted anaerobic sulfur transformation. This work deepens our understanding of the interaction between BPA and sulfur transformation occurring in anaerobic environments.

CAS / MDL: 80-05-7
研究领域: 环境科学 · 微生物学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

Highly effective direct conversion of H2S into COx-free H2 and S at low temperature over novel MoxC@ZrO2 microwave catalysts

Jun Zhu,Jun Chen,Jianan Chen,Jicheng Zhou,Wentao Xu

Direct decomposition of H 2 S into H 2 and S is an attractive alternative to the Claus process, because CO x -free H 2 and S can be simultaneously recovered from an abundant and toxic waste gas, which has huge social economic and ecological environmental benefits. However, it is still a great challenge to achieve the direct H 2 S decomposition reaction with high efficiency due to the thermal equilibrium limitation. Herein, a core-shell structured Mo x C@ZrO 2 was developed as novel microwave catalyst for microwave catalytic H 2 S decomposition. More specifically, the H 2 S conversion over Mo x C@ZrO 2 catalyst is as high as 99.9% at 650 °C, which immensely surpasses the H 2 S equilibrium conversion (6.1% at 650 °C). This study provides an effective strategy for the design of highly active microwave catalysts, and supplies a strategy for efficiently catalytic decomposition of H 2 S waste and recovering high-value hydrogen and sulfur at lower reaction temperatures.

研究领域: 化学工程 · 环境科学
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CRYSTENGCOMM · 2022 ·Vol. 24 ·期 22 ·4021-4029 · IF 3.756

Novel SnO2(ZnO:Sn)m superlattice nanoparticles for ultra-low ppb-level H2S detection

Jianan Huang,Bojia Xu,Binghui Ge,Yi Xu,Baobao Cao

Novel zero-dimensional SnO2(ZnO:Sn)m superlattice nanoparticles were synthesized by a simple method of annealing ZnO nanoparticles precoated with a sol–gel Sn–Zn–O precursor. The annealing temperature and duration were systematically evaluated, and the optimum condition was confirmed as 900 °C for 45 min to obtain ideally fully developed layered structures. Cs-corrected scanning transmission electron microscopy (STEM) revealed that the SnO2(ZnO:Sn)m was composed of alternate stacking of a Sn–O octahedral layer and Sn-doped ZnO slab, which resulted from the anisotropic diffusion of Sn atoms in the ZnO basal plane. A gas sensor based on the SnO2(ZnO:Sn)m superlattice nanoparticles exhibited a superior selectivity towards the poisonous gas of hydrogen sulphide (H2S) among six different types of gases (ethanol, H2, CO, NO2, NH3 and H2S), and an extreme low H2S detection limit of 5 ppb at the working temperature of 400 °C, which was about 3–5 orders lower than that of most ZnO-based H2S gas sensors in the literature. The drastic enhancement of the sensing properties of the SnO2(ZnO:Sn)m superlattice nanoparticles was believed to originate from its unique layered structure, which forms a microcirculation of electrons between the Sn–O atomic layers and Sn-doped ZnO slabs with different work functions, thus greatly accelerating the adsorption and desorption rate of gas molecules and increasing the sensor sensitivity. These new SnO2(ZnO:Sn)m superlattice nanoparticles were demonstrated to be a competitive H2S sensing material candidate for practical application. In addition, the facile superlattice nanoparticles fabrication method presented here could be extended to synthesize other ZnO-based superlattice material systems.

研究领域: 材料科学 · 传感器技术 · 纳米技术
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