Amount Of Doping Research Articles

SnO2-modified CuMnOx catalysts for humid CO oxidation at low temperature

Low-temperature CO oxidation has been widely applied in environmental pollution control, but challenges remain in CO purification in high-humidity environments. In this study, the CuMnSn8 catalyst exhibited excellent low-temperature CO oxidation performance, achieving complete CO oxidation at temperatures below 55 °C in 85 % relative humidity. A series of characterizations indicated that an appropriate amount of SnO2 doping could promote the formation of more amorphous oxides, increase the oxygen species content, and facilitate the dispersion of Cu and Mn elements. The catalytic active sites for CO oxidation and the influence of SnO2 doping on the CO oxidation mechanism were investigated through in-situ DRIFTS experiments. The results indicated that Sn enhanced the synergistic effect between Cu and Mn, altered the pathway of CO oxidation reaction, generated more easily decomposable bidentate carbonate intermediates. This work provides insight into the design of CO oxidation catalysts with high activity in high humidity.

Room temperature ferromagnetism in undoped and Fe doped Zn3P2 nanoparticles: Structural, optical and magnetic properties

In the current study, the structural, optical, and magnetic characteristics of Fe-doped Zn3P2 nanoparticles prepared by the solid-state reaction technique with various concentrations of Fe (x = 0.00, 0.02, 0.04, 0.06, and 0.08) were investigated. Studies using X-ray diffraction (XRD) verified that all of the produced samples had a tetragonal structure without any other phase, and that the lattice parameters increased (a = 8.090 Å, c = 11.421 Å to a = 8.120 Å, c = 11.499 Å) as the amount of dopant increased. The scanning electron microscopy (SEM) performed on the sample demonstrates that the grain size is almost spherical. The size of agglomerations slightly increases with increasing dopant concentration. The results of an energy dispersive X-ray analysis (EDAX) are almost exactly what was anticipated for the atomic weight ratios. The optical bandgap of the samples went from being 1.406 eV to being 1.453 eV when the dopant concentration was raised. When excited at wavelengths of 210 nm and 240 nm, rather than 307 nm, very intensity Photoluminescence (PL) emission spectra were detected in all of the samples. Vibrating sample magnetometer (VSM) verified that magnetic moment is found to increase (0.08829 emu/g to 0.23125 emu/g) with increase of dopant concentration from 0.02 to 0.08.

Improved thermoelectric properties of Ge2Sb2Te5 films by Bi doping: Experiments and first-principles calculation

The high carrier concentration and low Seebeck coefficient limit the thermoelectric properties of Ge2Sb2Te5 materials. In this paper, Bi-doped Ge2Sb2Te5 thin films with different doping amounts were prepared by magnetron sputtering. The thermoelectric properties of Bi-doped Ge2Sb2Te5 were measured by experiments and predicted by density functional theory and Boltzmann transport theory. The results show that Bi atoms occupy Ge vacancies and bond with Te atoms. The replacement of Ge2+ vacancy with Bi3+ effectively modulates the carrier concentration and improves the Seebeck coefficient. Bi doping increases the degeneracy of the valence band and density of state near the valence band maximum (VBM), and thereby beneficial for the thermoelectric properties of p-type Ge2Sb2Te5, while not desirable for n-type. At 673 K, the power factor of the sample at 20 W doping power reaches 549.56 μWK−2m−1, which is nearly fifteen times that of the intrinsic Ge2Sb2Te5.

Boosting both electronic and ionic conductivities via incorporation of molybdenum for LiFe0.5Mn0.5PO4 cathode in lithium-ion batteries

As the EV and ESS markets expand, there is a growing interest in LiFexMn1-xPO4 (LFMP) cathode materials amidst the increasing demand for LIBs. The LFMP cathode material is cost-effective and structurally stable; however, it has the drawback of low conductivity. Therefore, the development of an LFMP cathode material with high ionic/electronic conductivity is essential for high-stability and high-C-rate LIB applications. We propose a carbon-coated LFMP cathode material with Mo placed at the Fe and Mn sites. The samples were synthesized using a solvothermal method. Mo contributes to enhanced Li-ion diffusion and charge transfer rates. The XRD Rietveld refinement results showed elongated Li–O bonds within the Mo-doped LFMP/C, which accelerated the Li+ ion diffusion. Through SEM, TEM–EDS mapping, and XPS analysis we have confirmed the properties and morphology of the material. The electrochemical evaluation of the material was conducted using galvanostatic charge-discharge, CV, and EIS methods. Based on these tests, Mo incorporation not only increased the capacity but also enhanced the rate performance, reduced the voltage polarization, and improved the lithium-ion diffusion coefficient. Based on the 3.7 V additional plateau, which is attributed to the sluggish kinetics of Mn3+, Mo6+ played a role in enhancing the kinetic behavior of Mn3+. Low-temperature performance tests demonstrated that the Mo-doped samples exhibited high energy density, cycle retention, and superior ionic conductivity. In summary, an appropriate amount of Mo doping is effective for improving the electrochemical performance of LFMP, making it a promising cathode material.

Sulfur-doped Pt/C catalyst for propane dehydrogenation with improved atomic utilization and stability

Atomically well-dispersed platinum catalysts play a vital role in various chemical processes such as direct dehydrogenation of propane (PDH), due to their high performance originated from high atom utilization. However, these catalysts suffer from complex preparation methods, and preparing atomically dispersed Pt-based catalysts with feasible methods remains challenging. Herein, we report a convenient method to prepare efficient atomically dispersed Pt/C catalysts for PDH by sulfur doping into the carbon support by simple cyclohexane impregnation method. The prepared atomically well-dispersed catalysts possess strong interactions between Pt and carbon support, which led to improved exposure of active sites and higher propylene formation rate compared to that without sulfur doping. Sintering of the Pt species was also inhibited and stability was improved by 47%. Propylene selectivity also showed a positive correlation with the amount of sulfur doping. The propane conversion first increased and then decreased, which was due to the loss of sulfur during the reaction that caused the agglomeration of Pt and the evolution of structure. It was found that the maximum catalytic activity appeared with Pt clusters of ∼ 0.71 nm with an average Pt-Pt coordination number of 3.1 and Pt-Pt bond distance of 3.09 Å.

The enhancement of intelligent electric response properties in the Polymer Gel Artificial Muscle (PGAM) by incorporating micro/nanoscaled doping and regulation of Graphene Oxide (GO)

To align with the principles of environmental conservation and sustainable progress, a Polymer Gel Artificial Muscle (PGAM) was designed with a sandwich-like configuration, comprising two non-metallic electrode membranes enclosing an electrically-actuated membrane. This PGAM exhibited promising prospects due to its advantageous features such as lightweight, intelligibility, flexibility, and excellent activity. However, despite the widespread utilization of polymer gels, their investigation into intelligent electric response property remained a significant challenge. This study investigated the intelligent electric response properties of the enhanced PGAM by incorporating micro/nanoscaled doping with varying amounts of Graphene Oxide (GO). A control group consisting of a PGAM without GO was also utilized, allowing for the analysis of the regulatory mechanism behind GO-doped PGAM. The findings indicated that a doping amount of 0.03 wt% of GO resulted in a maximum peak difference of 16.08 mN/g in the output force density of PGAM during multiple cycles, with a maximum change rate of 21.13%. The PGAM demonstrated a maximum output force density of 15.06 mN/g during a single cycle when doped with 0.03 wt% of GO. Furthermore, electrochemical analysis of the PGAM revealed that at the same doping amount of 0.03 wt%, the specific capacitance reached its peak value of 324 nF·cm−2, while the resistance reached its minimum value of 1.61 Ω. In summary, the incorporation of GO doping has been found to enhance the intelligent electric response properties of PGAM, thereby offering a novel approach for the advancement of flexible actuators exhibiting superior intelligent electric response property.

Microstructure and electrochemical properties of Mg/Nb/Zr co-doped LiNi0.94Mn0.04Al0.02O2 cathode materials

The increasing oil scarcity and environmental awareness have accelerated the rise of the new energy vehicle industry, but range and cost issues have hindered the rapid popularization of new energy vehicles. The Co-free Ni-rich layered cathode materials have received a wide attention due to their high energy density, low cost, and stable raw material supply. However, its structure and electrochemical stability still need to be further improved. In this study, the electrochemical properties of LiNi0·94Mn0·04Al0·02O2 (NMA), a Co-free Ni-rich layered cathode material, have been improved by co-doping of Mg, Nb, and Zr. Also, the effects of co-doping on the crystal structure, morphology and electrochemical properties of NMA cathode materials were investigated, too. The results show that the NMA material (NMA-333) with 0.9 mol% doping amount has the best electrochemical performance. The discharge-specific capacity in the first cycle at 1 C was 199.6 mAh g−1, and the capacity retention after 200 cycles reached 73.94 %, which is nearly 24 % higher than that of the original material (NMA-1.03). Meanwhile, the NMA-333 material has a relatively better rate performance, with a discharge-specific capacity of 125.2 mAh g−1 at 10 C. Moreover, the structure and morphology of the modified material were represented by SEM, TEM, XRD, and XPS. And the results showed that the co-doping modification could refine the primary particles of the NMA material, reduce the lithium-nickel mixing, and increase the lattice spacing. The XPS, SEM, and XRD of the post-cycle electrodes further showed that co-doping had stabilized the crystal structure, inhibited the generation and expansion of microcracks, and reduced the occurrence of harmful side reactions, thus improving the cycling performance of the NMA materials at high voltage. The method could be a feasible way to improve the electrochemical performance of layered high-nickel cobalt-free cathode materials.

The Effect of Bi0.5Li0.5ZrO3-SrSnO3 Composite Doping on the Construction of Polymorphic Phase Boundaries and Enhanced Electrical Properties of K0.45Na0.55Nb0.965Sb0.035O3 Piezoelectric Ceramics

In this experiment, a new lead-free piezoelectric ceramics (1−x)K0.45Na0.55Nb0.965Sb0.035O3−x(0.9Bi0.5Li0.5ZrO3−0.1SrSnO3) were prepared by the conventional solid-phase method, and the effects of the doping amount of 0.9Bi0.5Li0.5ZrO3−0.1SrSnO3 on the K0.45Na0.55Nb0.965Sb0.035O3 ceramics on the crystal structure, microstructure, microscopic structure and electrical properties. All the doping ions entered the KNN lattice and formed a dense solid solution with a single-phase structure, and the phase structure of the ceramics coexisted from orthorhombic (O) to orthorhombic-tetragonal (O-T) phases in the range of 0 ≤ x ≤ 0.03, and transitioned to rhombohedral-tetragonal (R-T) phase coexistence when 0.035 ≤ x ≤ 0.05. The electrical properties of the ceramics were analyzed and the polymorphic phase boundary (PPB) region was obtained at x = 0.035 and had the best overall properties: d 33 = 324pC/N, k p = 49%, ε r = 1479, tanδ = 3.21%, P r = 31.98 μC/cm2, E c = 16.83 kV cm−1 and T C = 293°C. By The microstructural analysis of the ceramics showed that the appropriate amount of compound doping of the second element enhances the denseness of the ceramics as well as makes the grains uniformly distributed. These results indicate that the ceramics of this system have great prospects for future applications in the field of lead-free piezoelectric ceramics.

Zn2+ doped Ni3(NO3)2(OH)4 nanoflower spheres for electrochemical applications

In this present work, Ni3(NO3)2(OH)4 doped with Zn2+ ions are prepared by a solvothermal method using Ni(NO3)2·6H2O, Zn(NO3)2·6H2O, C16H33(CH3)3NBr (CTAB) and C2H5OH as raw materials. Characterization methods such as X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) are used to analyze the materials. Cyclic voltammetry (CV) and galvanostatic charge–discharge curves (GCD) are employed to compare the electrochemical performance of materials with different doping amounts. The electrochemical test results show that doping with Zn2+ significantly enhances the poor electrical conductivity of Ni3(NO3)2(OH)4. Electrochemical tests reveal that the doping amount of 0.4 mmol has the best electrochemical performance with a mass-specific capacitance of 1832 F·g−1 at a current density of 1 A·g−1 in the three-electrode system which is much higher than that of undoping sample (771 F·g−1). Additionally, the assembled NiZn-0.4//AC asymmetric supercapacitor device (ASC) has an energy density of 61.9 Wh·kg−1 at a power density of 747.8 W·kg−1. The Coulombic efficiency retention of the ASC device remains at 98 % after 2000 galvanostatic charge–discharge circles, and the specific capacitance retention is 91 % of the initial value. The doping of Zn2+ provides a valuable approach for enhancing the conductivity and specific capacitance of nickel-based supercapacitor electrode materials.

Enhanced co-production of high-quality syngas and highly-concentrated hydrogen via chemical looping steam methane reforming over Ni-substituted La0.6Ce0.4MnO3 oxygen carriers

Chemical looping steam methane reforming (CLSMR) is increasingly attracting more and more attention as a promising technology for co-production of syngas and hydrogen. However, low reactivity, poor selectivity and weak resistance to carbon deposition of oxygen carriers (OCs) probably discourage further commercial application of CLSMR. With this background, a novel strategy of incorporating Ce and Ni into LaMnO3 is advised to promote lattice oxygen migration rate and improve syngas selectivity. The redox activity and cycle stability of La0.6Ce0.4Mn1−xNixO3 for CLSMR are explored in a fixed-bed reactor coupling with various characterization methods. The characterization results show that La0.6Ce0.4Mn1−xNixO3 OCs still maintain the standard perovskite structures and well-ordered skeleton. The introduction of Ce3+ induces large amounts of oxygen vacancies on the surface of OCs and improve the syngas selectivity of methane reforming, leading to higher oxygen mobility and lower carbon deposition. Meanwhile, the experimental results also confirm that the doping of Ni into La0.6Ce0.4MnO3 can greatly improve the oxygen-donation ability and effectively provide more active sites for reaction with methane. While excessive Ni in perovskite will enhance the methane dissociation, which is the main reason of carbon deposits. The proper amount of Ni doping can well match the methane activation rate to migration rate of bulk lattice oxygen that is feasible to realize the balance between productivity and efficiency. In addition, the reduced metal elements along with great amounts of oxygen vacancies together contribute to more active sites for the following steam splitting which avails to produce high-purity H2. La0.6Ce0.4Mn0.7Ni0.3O3 oxygen carrier eventually achieve syngas yield of 2.8 mmol/g H2 and 1.4 mmol/g CO that is closed to the ideal value without obvious carbon deposition, and pure H2 yield of 3.8 mmol/g, exhibiting the best redox performance and good regenerability. Meanwhile, La0.6Ce0.4Mn0.7Ni0.3O3 can still maintain high redox activity and basic perovskite structure after 15 cyclic redox tests, illustrating a desirable stability and reliability. In summary, this study offers a valuable and effective strategy to tackle with the bottleneck of CLSMR, paving the way of doping transition metal as a pathway of modulating reaction performance and stability of OCs in chemical looping processes.

Effects of Dy doping amount and sintering process on the structure and dielectric properties of Sr1-3x/2DyxTiO3 ceramics

Effects of Dy doping amount and sintering process on the structure and dielectric properties of Sr1-3x/2DyxTiO3 ceramics

Efficient photoelectrocatalytic reduction of CO2 to formate via Bi-doped InOCl nanosheets

Converting CO2 into useful substances is an important approach to address the challenge of reducing CO2 emissions and combating climate change. Compared with the traditional process, photoelectrocatalytic CO2 reduction has great potential to solve the problem of CO2 emission. In this work, Bi-doped InOCl cathode catalysts were prepared by a two-step calcination process, and they demonstrated efficient catalytic activity for the reduction of CO2 to formate. The inclusion of bismuth (Bi) in InOCl resulted in improved catalytic performance compared to the native InOCl catalyst. Specifically, the highest formate selectivity can be observed at −0.9 V vs RHE with a Faraday efficiency of 89.9% and the product rate of 101.41 μmol h–1cm–2 when the Bi doping amount is 5%, representing approximately 2 and 3 times the values obtained with native InOCl, respectively. The experimental results indicate that Bi doping promotes the formation of {001} crystalline surfaces in InOCl, while increasing the specific surface area and the availability of more active sites for CO2 reduction. This work holds significant potential for further advancements in the field of photoelectrocatalytic reduction of CO2.

Fluence profiling at JSI TRIGA reactor irradiation facility

We present an analysis of the fluence profile at the JSI TRIGA neutron reactor facility in Ljubljana. For the study, multi-pad Low-Gain Avalanche Diodes (LGADs) are used. The deactivation of acceptor doping in the gain layer implant due to the irradiation, typical of LGAD devices, is exploited to map the fluence profile inside the irradiation channels. The amount of active doping of the LGAD gain layer is extracted via capacitance–voltage measurements for each pad before and after irradiation to a fluence of 1.5 × 1015neq/cm2, where neq stands for 1 MeV equivalent neutron count, providing a precise and prompt measurement of the fluence distribution over the LGAD sensor. Experimental results are compared to neutron fluence expectations calculated with Monte Carlo techniques.

Smart nanoarchitectonics of epoxy coating: Preparation, release behavior and self-healing performance based on mesoporous silica nano-containers loaded with DMTD inhibitors

Self-healing coatings doped by nano-containers loaded with inhibitors have shown remarkable anti-corrosion efficiency and durability in extending metal life and slowing down coating failure. However, low loading capacity of corrosion inhibitors in nano-containers is a problem plaguing the further development and application of smart coatings. In this study, mesoporous silica with large pore sizes (MSN) was synthesized using the soft template method which significantly increased the loading capacity of the corrosion inhibitor, and a smart self-healing composite coating was designed, which could protect carbon steel from corrosion and provide durable protection for it. Specifically, the composite coating (EP/DMTD@MSN-PAA) was prepared by incorporating mesoporous silica nano-containers embedded with 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecules into the epoxy resin coating. The results of BET test showed that the prepared MSNs had high specific surface area (734.97 m2/g) and large pore volume (0.85 cm3/g). The thermogravimetric (TG) analysis showed 35.7% of loading amount of corrosion inhibitors in the nano-materials. Response release experiments showed that the DMTD@MSN-PAA had of acid-response release characteristics. When pH value of the system decreased from 7 to 3, the release amount of the DMTD molecules increased from 40.3% to 93.7%. The contact angle test showed that the epoxy resin (EP) coating had a contact angle value of 57.7°, while those of the composite coatings doped with 1 wt%, 3 wt% and 6 wt% DMTD@MSN-PAA (EP/DMTD@MSN-PAA) were 65.1°, 75.2° and 67.2°, respectively. These results indicated that the composite coatings had better hydrophobicity compared to the EP coating, and were conducive to prolonging the coating service time. The anti-corrosion performances of both the EP and the composite coatings with different doping amounts of DMTD@MSN-PAA were evaluated by EIS measurements. The Rct value of the EP coating decreased from 190.3 to 25.1 Ω · cm2 within the time of 48 h of immersion in 3.5 wt% NaCl solution, while ones of the EP/DMTD@MSN-PAA coatings doped with 1 wt%, 3 wt% and 6 wt% of DMTD@MSN-PAA increased from 303.1, 720.7.7, 523.4–1426.4, 2113.8, 1066.3 Ω · cm2, respectively. In addition, the corrosion resistance of the EP and composite coatings were further evaluated by etching experiments. The results showed that after 35 d of immersion, compared with that of the EP coating, surface corrosion degree of the composite coatings was lower, and the scaling off speed of the coatings slowed down, which further proved that the composite coating had strong corrosion resistance and special self-healing characteristics.

The Cu/TiO2 adsorbent modified by Ce-doping removes trace phosphorus impurities from circular hydrogen of a polysilicon chemical vapor deposition furnace

There is an urgent need for efficient and cost-effective adsorbents for the removal of trace hydrogen phosphide (PH3) from the circular hydrogen systems in the polysilicon chemical vapor deposition furnaces. In this study, a straightforward and cost-effective method was used to synthesize a highly efficient adsorbent (Cex-Cuy/TiO2) for PH3 removal using TiO2 as the carrier and CuO as the active substance. Experimental findings demonstrated that optimal Ce doping amounts (nCu:nCe = 20:1) markedly enhanced the adsorbent's performance, with an adsorption capacity reaching as high as 149.14 mg g−1. Material characterization results indicated that Ce positively influenced the uniform dispersion of Cu on the TiO2 surface, and Ce doping increased the adsorbed oxygen content of the adsorbent, consequently enhancing its oxidation performance. The investigation of the reaction mechanism and causes of adsorbent deactivation revealed that the depletion of active substances (CuO) in the adsorbent and the accumulation of products such as Cu3P and phosphates are the primary factors contributing to its deactivation. Furthermore, high-temperature calcination could restore the activity of the adsorbent, indicating its great potential for engineering applications.

N-doped Cu2O with the tunable Cu0 and Cu+ sites for selective CO2 electrochemical reduction to ethylene

The electrochemical carbon dioxide reduction reaction (CO2RR) to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming. However, the selective CO2 reduction to C2 products remains challenge. Cu-based catalyst with the specific Cu0 and Cu+ sites is important to generate C2 products. This work used nitrogen (N) to tune amounts of Cu0 and Cu+ sites in Cu2O catalysts and improve C2-product conversion. The controllable Cu0/Cu+ ratio of Cu2O catalyst from 0.16 to 15.19 was achieved by adjusting the N doping amount using NH3/Ar plasma treatment. The major theme of this work was clarifying a volcano curve of the ethylene Faraday efficiency as a function of the Cu0/Cu+ ratio. The optimal Cu0/Cu+ ratio was determined as 0.43 for selective electroreduction CO2 to ethylene. X-ray spectroscopy and density functional theory (DFT) calculations were employed to elucidate that the strong interaction between N and Cu increased the binding energy of NCu bond and stabilize Cu+, resulting in a 92.3% reduction in the potential energy change for *CO-*CO dimerization. This study is inspiring in designing high performance electrocatalysts for CO2 conversion.

Ti-Doped Co-Free Li1.2Mn0.6Ni0.2O2 Cathode Materials with Enhanced Electrochemical Performance for Lithium-Ion Batteries

Cobalt-free manganese-based lithium-rich layered oxides (LLOs) have garnered research attention as prospective lithium-ion cathode materials owing to their large specific capacity and low price. However, their large-scale application is hindered by their low Coulombic efficiency, poor cycling performance, voltage attenuation, and structural phase transition. To address these issues, the LLO structure is modified via Ti doping at the manganese site herein. Ti-doped Li1.2Mn0.6−xTixNi0.2O2 (x = 0, 0.03, 0.05, 0.10, and 0.15) is prepared using the high-temperature solid-state method. The Ti-doped Li1.2Mn0.6Ni0.2O2 is calculated via first principles. The results show that Ti4+ doping improves the cycle stability and rate performance of Li1.2Mn0.6Ni0.2O2. Electrochemical test results show that the sample exhibits enhanced electrochemical performance when the Ti doping amount is 0.05. The discharge specific capacity at 0.1C is 210.4 mAh·g−1, which reaches 191.1 mAh·g−1 after 100 cycles, with a capacity retention rate of 90.7%. This study proves the feasibility of using cheap cobalt-free LLOs as cathode materials for LIBs and provides a novel system for exploiting low-cost and high-performance cathode materials.

A quadruple transition metal dichalcogenide for variously synergetic electron behaviors during photocatalytic carbon dioxide reduction

A quadruple 2H transition metal dichalcogenide of platinum doped molybdenum selenide sulfide (MoSSe) has been achieved. The critical doping amount of Pt is estimated to be approximately 0.9 a.t.% to prevent the formation of a heterogeneous phase. It has been observed that the excess Pt beyond this critical doping level cannot be settled into the lattice of MoSSe but forms an independent metal phase of Pt nanoparticles, composing a heterostructure with MoSSe, in which the behavior of photogenerated electrons will be predominantly governed by metal Pt and transported along the pathways for gas production in the photocatalytic CO2 reduction. However, as long as Pt can be located in the lattice of MoSSe, the elemental variety of Pt doped MoSSe has provided various active sites during the photocatalytic CO2 reduction process, favoring the localized coupling of matching intermediates, consequently enhancing the production of high value-added liquid products. In essence, the successful integration of Pt into the 2H MoSSe lattice opens up diverse active sites, optimizing the photocatalytic performance on the selectivity of liquid production reduced from CO2.

Synthesized trimanganese tetraoxide functionalized zinc oxide hierarchical structures with abundant oxygen vacancies for ppb-level volatile organic compounds detection

Hierarchical heterostructures have been proven to be the great material structures for the fabrication of gas sensors, due to they high surface area, well-aligned porosity and synergy effect. Here, ZnO hierarchical structures with various amount of Mn dopant were synthesized through a simple one-step solution route followed by annealing treatment. The characterization results demonstrated that Mn dopant existed in the forms of Mn3O4 nanoparticles and lattice Mn2+ ions. The as-synthesized Mn3O4/ZnO hierarchical structures with abundant oxygen vacancies (MnxZnO with x values of 0, 0.25, 0.5, 1 and 3) were used as the sensing materials toward volatile organic compounds (VOCs) detection, illustrating that the introduction of Mn dopant can significantly improve the gas sensing performance. Especially, under optimal working temperature, Mn0.5ZnO hierarchical structures-based gas sensor exhibits the highest responses, fast response/recovery speed (2/9 s), a low detection limit (150 ppb), good selectivity and long-term stability toward acetone. In addition, the enhanced gas sensing mechanisms were explained by large surface area, oxygen vacancies and p-n heterojunction, boosting the surface reactions, which was further verified through DFT calculations. This work also confirmed that Mn element could be a promising dopant in metal oxides for high-performance VOCs gas sensors.

Mechanistic study of chemical looping partial oxidation of methane over Ce2(SO4)3/MgO with CoO modification

Chemical looping partial oxidation of methane (CLPOM) to syngas provides an exceptional opportunity for methane utilization. However, it is still urgent to obtain efficient oxygen carrier (OC) and clarify its microscopic mechanism. In this work, CoO and MgO modified Ce2(SO4)3 OC are optimized based on various preparation methods and different CoO and Ce2(SO4)3 doping amount. Considering the conversion rate (XCH4), selectivities of CO (SCO) and H2 (SH2), H2/CO molar ratio, when the doping amount of CoO, Ce2(SO4)3 and MgO is 20 wt%, 30 wt% and 50 wt% respectively, the OC prepared by mechanical ball milling method has a better thermodynamic and kinetic properties in chemical looping reaction. Compared with literature, this OC has a larger XCH4. In multiple cycles, XCH4 is still higher than 90%, SCO and SH2 remain above 95%. Density functional theory calculation reveal that the Co doping reduces the energy barrier (Eb) of rate-limiting step by 24.3% and lowers the migration Eb of lattice oxygen by 78.2%. The OC with oxygen vacancy can further reduce the Eb of rate-limiting step, but the Eb basically remains unchanged when the oxygen vacancy (Ov) concentration is greater than 1.96%. Because of the high Eb of CO2 formation and low Eb of syngas formation, the syngas demonstrates high selectivity and does not produce CO2 in experiment. Meanwhile, the doping of CoO and MgO reduces carbon deposition, refines the nano-particles of OC, increases the specific surface area (SSA), and enhances resistance to sintering and aggregation. The unique pore structure also provides a favorable microenvironment for the reaction. These findings demonstrate that CoO and MgO modified Ce2(SO4)3 OC have the potential for application in CLPOM, and these basic insights can also be applied to other chemical looping systems.