Bamboo-like N-doped carbon tubes encapsulated Co2P–Fe2P derived from zeolitic imidazolate framework as an efficient trifunctional electrocatalyst for water splitting and Zn-air batteries

The development of high-performance and stable trifunctional electrocatalysts is a pressing challenge for the practical application of water splitting and regenerative Zn-air batteries. Herein, bamboo-like N-doped carbon tubes encapsulated Co₂P–Fe₂P nanoparticles (CoFe-PN/C) was fabricated via a facile template-sacrificial approach by using CoZn-ZIF trapping Fe³⁺ (CoFeZn/C) as the precursor. The incorporation of Fe³⁺ was achieved by the one-pot synthesis approach during crystallization of ZIF, which led to the generation of the unique bamboo-like tube structure under the condition of simultaneous phosphating and carbonization. Benefiting from the large surface area, the optimized electronic structure of active sites and the unique bamboo-like nanotube, the resultant CoFe-PN/C can be used as the trifunctional electrocatalyst possessing a small overpotential at 10 mA cm⁻² for the HER (178 mV) and OER (300 mV), as well as a high half-wave potential of 0.884 V for ORR (40 mV more positive than that of commercial 20 wt% Pt/C). Moreover, the self-designed CoFe-PN/C||CoFe-PN/C alkaline electrolyzer driving 50 mA cm⁻² only need operating potential of 1.84 V and the maximum discharge power density of the CoFe-PN/C-assembled ZABs could achieve 152.0 mW cm⁻², superior to those of Pt/RuO₂ couple. This work will facilitate the development and application of trifunctional electrocatalysts based on bi-transition metallic phosphides for energy conversion and storage technology.     

Deep surface reconstruction of Co-based cocatalyst on Ti-doped α-Fe2O3 photoanode for highly efficient water oxidation

Transition metal-based cocatalysts play important roles in promoting the surface kinetics of hematite (α-Fe₂O₃) photoanode. However, their performances are restricted by the shallow reconstruction process for generating highly efficient metal oxyhydroxides, where the oxygen evolution reaction (OER) occurs. Therefore, a Brnsted base-regulated strategy is developed to promote the in situ surface reconstruction of cocatalysts on Ti-doped α-Fe₂O₃ (Ti–Fe₂O₃) under photoelectrochemical conditions. After deep surface reconstruction by electrochemical activation, the CoWO₄ cocatalyst decorated Ti–Fe₂O₃ photoanode (a-CoWO₄/Ti–Fe₂O₃) delivers a photocurrent density of 0.88 mA cm^?2 at 1.23 V_RHE, which is about 3.0 times of activated Ti–Fe₂O₃ (a-Ti-Fe₂O₃) and 1.5 times of activated CoO_x/Ti–Fe₂O₃. Tungstate promotes the surface reconstruction of cobalt-based cocatalyst, resulting in a significant increase in bulk charge separation efficiency (η_sep) and surface charge injection efficiency (η_inj). Moreover, the type-II heterojunction between CoWO₄-derived CoOOH and a-Ti-Fe₂O₃ drives the rapid separation and transfer of photogenerated electron-hole pairs, and enhances the performance of Ti–Fe₂O₃ photoanode.     

Effect of Co2O3 as sintering aid on perovskite BaCe0.8Y0.2O3-δ proton conductive membrane for hydrogen separation

BaCe_0.8Y_0.2O_3-δ proton conductor powder was prepared by sol-gel method, and the effects of sintering temperature and sintering aids addition on the mechanical properties and hydrogen permeability of BaCe_0.8Y_0.2O_3-δ proton conductor were investigated. XRD tests showed that when the addition of sintering aid Co₂O₃ reached 5%, the BaCe_0.8Y_0.2O_3-δ proton conductor still showed a good perovskite phase. The sintering temperature of the sample with sintering aid is significantly lower than that of the blank sample. SEM shows that the addition of Co₂O₃, the proton conductor grains are closely arranged, the mechanical properties are increased, and the hydrogen permeability is significantly improved.     

Experimental investigation and model development for thermal conductivity of α-Al2O3-glycerol nanofluids

In order to investigate the effect of nanoparticle volume fraction, nanoparticle size and temperature on the thermal conductivity of glycerol based alumina (α-Al₂O₃) nanofluids, a set of experiments were carried out for temperature ranging from 20 °C to 45 °C. The nanofluids contained α-Al₂O₃ nanoparticles of three different sizes (31 nm, 55 nm and 134 nm) were prepared by two-step method at volume fractions ranging from 0.5% to 4%. The experimental results show that α-Al₂O₃-glycerol nanofluids have substantially higher thermal conductivity than the base fluid and the maximum enhancement of the relative thermal conductivity was 19.5% for the case of 31 nm at 4% volume fraction. The data analyses indicated that the volume fraction and size of the nanoparticles have significant effects on the thermal conductivity ratio (TCR) of Al₂O₃-glycerol nanofluids, while the temperature has almost no significant effect on the data for range of this study. At room temperature, the effective thermal conductivity remains almost constant for 50 h at 4% volume fractions. The comparison of the obtained experimental data and predictions from some existing theoretical and empirical models reveals that the thermal conductivity ratio and its trend could not be accurately explained by the models in open literature. Consequently, a new empirical correlation based on the experimental data has been developed in this study.     

Effect of La2O3 replacement on γ-Al2O3 supported nickel catalysts for acetic acid steam reforming

The effect of replacement of γ-Al₂O₃ by La₂O₃ was studied on Ni catalysts for hydrogen production via acetic acid steam reforming. The La/(La + Al) weight ratio ranged from 0 to 1 in the catalyst support prepared by co-precipitation method. Over the Ni/La-3Al catalyst (the La/(La + Al) weight ratio at 0.25), the carbon conversion and hydrogen yield reached 100% and 72.72%, respectively, which was obviously higher than other catalysts at 700 °C, S/C = 1 and LHSV = 10 h^?1. The effect of S/C, LHSV and stability test were studied in detail over Ni/La-3Al catalyst, whose high activity maintained for more than 30 h.     

Ni/Y2O3–ZrO2 catalyst for hydrogen production through the glycerol steam reforming reaction

In the study presented herein, the catalytic activity and stability of a Ni catalyst supported on Y₂O₃–ZrO₂ was examined for the first time in the glycerol steam reforming reaction and compared with a Ni/ZrO₂. The addition of Y₂O₃ stabilized the ZrO₂ tetragonal phase, increased the O₂ storage capacity of the support and the medium strength acid sites of the catalyst, and although the Ni/Zr catalyst had a higher concentration of basic sites, the Ni/YZr presented more stable monodentate carbonates. Moreover, the Ni/YZr had substantially higher Ni surface concentration and smaller Ni particles. These properties influence the gaseous products’ distribution by increasing the H₂ yield and selectivity and preventing the transformation of CO₂ to CO, by inhibiting the reverse water gas shift (RWGS) reaction from taking place. For both catalysts the main liquid products identified were allyl alcohol, acetaldehyde, acetone, acrolein, acetic acid and acetol; these were subsequently quantified. The time-on-stream experiments showed that the Ni/YZr was more stable during reaction and had a higher H₂ yield after 20 h (2.17 in comparison to 1.50 mol H₂/mol C₃H₈O₃, for the Ni/Zr). Extensive investigation of the carbon deposits showed that although lower amounts of coke were deposited on the Ni/Zr catalyst, these structures were more graphitic in nature and had fewer defects, which means they were harder to oxidize. Moreover, transmission electron microscopy (TEM) analysis showed that sintering of Ni nanoparticles during the reaction was significant for the Ni/Zr catalyst, as the mean particle diameter increased from an initial value of 48.2 to 67.9 nm, while it was almost absent on the Ni/YZr catalyst (the mean particle diameter increased from 42.1 to 47.4 nm).     

Cu supported on ZnAl-LDHs precursor prepared by in-situ synthesis method on γ-Al2O3 as catalytic material with high catalytic activity for methanol steam reforming

A novel catalyst precursor ZnAl-LDHs/γ-Al₂O₃ was prepared by in-situ synthesis method, and the copper was supported on calcined hydrotalcite catalyst precursor by wet impregnation. The correlation between the structure and the catalytic activity for methanol steam reforming was studied by XRD, SEM, TPR, chemisorption N₂O, IR and N₂ adsorption techniques. The results showed that the ZnAl-LDHs was successfully synthesized by in-situ synthesis method on γ-Al₂O₃ and the copper mass fraction had a great effect on the interactions between support and copper species. Furthermore, the catalyst reducibility and copper surface area evidently influenced catalytic activity for methanol steam reforming. The 10% Cu/γ-Al@MMO exhibited the best catalytic activity, that was, the methanol conversion was 99.98% and the CO concentration was only 0.92% at 300 °C in hydrogen production by methanol steam reforming.     

Preparation and characterization of α-Fe2O3 supported clay as a novel photocatalyst for hydrogen evolution

Improvement in the hydrogen evolution is reported over α-Fe₂O₃ supported on Algerian natural clay. The hetero-system is prepared by impregnation and calcination at 450 °C. It was characterized by X-ray diffraction, SEM analysis, FTIR spectroscopy and photo electrochemistry. The hematite Fe₂O₃ crystallizes in the corundum structure and exhibits n-type conductivity with a flat band potential of −0.88 V_SCE. Hence, the photo electrons located in Fe₂O₃-CB (−1 V_SCE) have high ability to reduce water into hydrogen. α-Fe₂O₃ gets effectively dispersed in the clay and the photoactivity increases with increasing its content. SO₃²⁻, working as hole scavenger, provides an absolute protection against the photo corrosion and favors the charges separation. The best performance of H₂ evolution occurs at alkaline pH on 10% Fe₂O₃/clay with a liberation rate 0.121 μmol/mg/min and a quantum efficiency of 1.2%.     

Catalytic steam reforming of biomass-derived acetic acid over modified Ni/γ-Al2O3 for sustainable hydrogen production

In order to obtain sustainable H₂, the catalytic steam reforming of acetic acid derived from biomass was performed by using the catalysts modified with basic promoters (Mg, La, Cu, and K). La and K increased the total basicity of Ni/γ-Al₂O₃ by 30.6% and 93.4%, respectively, which could induce ketonization, producing acetone. In contrast, Mg reduced the number of middle and strong basic sites by 17.2% and improved the number of weak basic sites by 5% for Ni/γ-Al₂O₃, which promoted the steam reforming of acetic acid (ca. 100% of H₂ and carbon selectivity at even 450 °C) without ketonization. Moreover, the amount of carbon deposited on Ni/Mg/γ-Al₂O₃ was 55.1% less than that deposited on Ni/γ-Al₂O₃. When Cu was employed, the conversion was ca. 60% with less than 70% of H₂ selectivity, at all temperatures considered herein.     

Opposite effects of self-growth amorphous carbon and carbon nanotubes on the reforming of toluene with Ni/α-Al2O3 for hydrogen production

Ni-based catalysts are prone to be deactivated by carbon deposition. This study aims to investigate the influence mechanism of different types of carbon deposition on the activity of Ni/α-Al₂O₃ catalyst at various steam-to-carbon (S/C) ratios during steam reforming of toluene for hydrogen production. At a low S/C ratio of 1, the catalytic activity of Ni/α-Al₂O₃ was inhibited due to the covering and blocking of Ni active sites by the formation of amorphous carbon on the Ni surface. While at a high S/C ratio of 3, more than 80 wt% of carbon deposition was found to be self-growth carbon nanotubes (CNTs) with an average diameter of around 15 nm. The activity of Ni/α-Al₂O₃ in steam reforming of toluene was unusually promoted, which can be attributed to the tip-growth mechanism of CNTs, whereby the Ni particles migrated to the tip or the surface of CNTs, resulting in the improved active site dispersion.     

Enhanced photocurrent by MOFs layer on Ti-doped α-Fe2O3 for PEC water oxidation

Low photocurrent density of hematite (α-Fe₂O₃) originating from the inherent defects usually hinders its application in photoelectrochemical (PEC) water oxidation. In this paper, the synergetic effect of increase of oxygen vacancies and in-situ constructing heterojunction by coating MOFs on the α-Fe₂O₃ nanoarrays gives rise to the boosted photocurrent of α-Fe₂O₃ from 0.25 mA/cm² to 2.1 mA/cm² at 1.23 V (vs. RHE). The results showed that the appropriate energy band structure engineered by the presence of MOFs layer not only facilitated the PEC water oxidation, but also enhanced the light absorption performance. With inducing oxygen vacancies in further, the intrinsic conductivity of photoanode can be well ameliorated. The value of carrier density is improved one order higher to promote charge transfer between the interfaces and raise the carrier separation efficiency as a result.     

High purity hydrogen production via aqueous phase reforming of xylose over small Pt nanoparticles on a γ-Al2O3 support

In this study, aqueous phase reforming (APR) of xylose was conducted over highly dispersed Pt nanoparticles supported on a γ-Al₂O₃ support (Pt-SNP). Formation of small Pt nanoparticles was confirmed by X-ray diffraction and transmission electron microscopy, which revealed that most of the particles ranged between 0.8 and 1.6 nm in size and the average particle size was 1.3 nm. Temperature-programmed reduction analysis indicated that these small Pt nanoparticles were highly reducible under the reducing environment compared to the commercial Pt/γ-Al₂O₃ catalysts (Pt-commercial). The catalytic activities of both Pt-SNP and Pt-commercial catalysts were examined in a semi-batch autoclave reactor system for the APR of xylose. It was found that Pt-SNP showed higher carbon to gas conversion with high hydrogen selectivity than Pt-commercial. This was likely due to the increased density of edge sites in the Pt-SNP catalyst that facilitated the cleavage of the C–C bonds rather than the C–O bonds, leading to greater hydrogen production. Furthermore, the Pt-SNP catalyst showed better carbon deposit resistance as compared to Pt-commercial. The amount of carbon deposition on the Pt-SNP catalyst surface and the organic carbon species dissolved in the post-reaction xylose solution were significantly lower compared to that of Pt-commercial. Finally, high purity hydrogen production was achieved using a continuous fixed-bed hybrid reactor including an aqueous phase reformer and a home-made Pd/Ta dense metallic composite membrane. A stable hydrogen gas production (99.999%) was obtained over the Pt-SNP catalyst, which demonstrated the success of a potentially commercial APR reactor system that continuously converted the aqueous xylose solution to hydrogen with high purity.     

Coke-resistance enhancement of mesoporous γ-Al2O3 and MgO-supported Ni-based catalysts for sustainable hydrogen generation via steam reforming of acetic acid

Highly ordered mesoporous γ-Al₂O₃ particles and MgO materials were synthesized by evaporation induced self-assembly (EISA) and template-free hydrothermal co-precipitation routes, respectively. Ni, Ni–MgO, and Ni–La₂O₃-containing catalysts were prepared using a wet-impregnation method. The synthesized catalysts were characterized by N₂ adsorption–desorption, XRD, SEM-EDS, DRIFTS, XPS, TGA-DTA, and Raman spectroscopy analysis. The mesoporous γ-Al₂O₃ catalyst support exhibited a high surface area of 245 m²/g and average pore volume of 0.481 cm³/g. The DRIFTS results indicate the existence of large Lewis's acid regions in the pure γ-Al₂O₃ and metal-containing catalysts. Catalytic activity tests of pure materials and metal-containing catalysts were carried out at the reaction temperature of 750 °C and a feed molar ratio of AA/H₂O/Ar:1/2.5/2 over 3 h. Complete conversion of acetic acid and 81.75% hydrogen selectivity were obtained over the catalyst 5Ni@γ-Al₂O₃. The temperature and feed molar ratio had a noticeable impact on H₂ selectivity and acetic acid conversion. Increasing the water proportion in the feed composition from 2.5 to 10 considerably improved the catalytic activity by increasing hydrogen selectivity from 81.75% to 91%. Although the Ni-based γ-Al₂O₃-supported catalysts exhibited higher activity performance compared to the Ni-based MgO-supported catalysts, they were not as resistant to coke formation as were MgO-supported catalysts. The introduction of MgO and La₂O₃ into the Ni@γ-Al₂O₃ and Ni@MgO catalysts' structures played a significant role in lowering the carbon formation (from 37.15% to 17.6%–12.44% and 12.17%, respectively) and improving the thermal stability of the catalysts by decreasing the agglomeration of acidic sites and reinforcing the adsorption of CO₂ on the catalysts' surfaces. Therefore, coke deposition was reduced, and catalyst lifetime was improved.     

Fast hydrogen diffusion along Σ13 grain boundary of α-Al2O3 and its suppression by the dopant Cr: A first-principles study

To acquire knowledge of the effect of chromium dopant bringing on hydrogen diffusion along grain boundaries (GBs) of α-Al₂O₃, the energetics and mobility of hydrogen along Σ13 GB with and without Cr dopant have been studied via the first-principles calculations with the projector-augmented wave method. The energy barriers for hydrogen diffusion before and after Cr doped on Al-terminated Σ13 GB are determined to be 0.69 eV and 1.09 eV, respectively, which is smaller than or close to the hydrogen bulk diffusion with an activation energy of 1.10 eV. The results suggest that before doping Cr atoms, there is a rapid and easy diffusion channel for hydrogen along the Σ13 GB. However, the calculations show the segregation of Cr atoms to the GB is energetic favorable with a segregation energy of ?0.39 eV/atom, and the existence of Cr can suppress hydrogen diffusion along the Al-terminated Σ13 GB.     

Improved low-temperature activity of Ni–Ce/γ-Al2O3 catalyst with layer structural precursor prepared by cold plasma for CO2 methanation

Ni–Ce/γ-Al₂O₃ catalyst (Ni–Ce-LDH-P) derived from LDHs was synthesized on γ-Al₂O₃. Plasma technology was employed to its preparation process. Impregnation method and thermal calcination and reduction technology were used to prepare reference catalysts (Ni–Ce-LDH-C, Ni–Ce-P and Ni–Ce-C). CO₂ methanation was chosen as the probe reaction. XRD, BET, SEM, TEM and CO₂-TPD were used to characterize the microstructure and properties of catalyst. Experimental results showed that Ni–Ce-LDH-P catalyst with smaller Ni size, better Ni dispersion and higher alkalinity exhibited outstanding low-temperature activity at range of 200–350 °C. Characterization results showed that the precursor of Ni–Ce-LDH-P catalyst presented in lamellar shape, inferring the formation of chemical bonds among Ni, Ce and Al (from γ-Al₂O₃). It is the chemical bonds that improved the dispersion of Ni crystal and the interaction between Ni and γ-Al₂O₃. Meanwhile, the plasma technology with relatively low temperature prevented the sintering and agglomeration of Ni during the preparation process. Therefore, the excellent performance of Ni–Ce-LDH-P catalyst should be ascribed to the synergy of the unique lamellar structure and the special characteristics of “high energy at relatively low temperature” of plasma technology.     

Effect of rGO on Fe2O3–TiO2 composite incorporated NiP coating for boosting hydrogen evolution reaction in alkaline solution

Fe₂O₃–TiO₂ composite incorporated NiP coating is a known promising catalytic coating for electrocatalytic Hydrogen Evolution Reaction (HER). It is explored in the present study that the activity of the coating can be enhanced by incorporation of rGO. The Fe₂O₃–TiO₂/rGO, electrocatalyst is synthesized by a facile hydrothermal method. Various compositions of the Fe₂O₃–TiO₂/rGO incorporated NiP coatings on mild steel substrate are developed by a chemical reduction method. The developed Fe₂O₃–TiO₂/rGO composite coating exhibits effective hydrogen evolution reaction activity with a Tafel slope of 98 mV dec⁻¹ and a low overpotential of 96 mV at a current density of 10 mA cm⁻². The hydrogen evolution reaction mechanism comprises of Volmer (adsorption of Hydrogen atom) followed by Heyrovskii (reduction to H₂). The enhanced catalytic activity by the incorporation of rGO into the coating is due to three dimensional projections of nano Fe₂O₃–TiO₂ on the folded surface of rGO. It effectively enhances the electrochemically active surface area of the coated electrode. The electrode is highly stable during alkaline HER. These results reveal that Fe₂O₃–TiO₂/rGO can be treated as an effective electrocatalyst during HER from alkaline solutions. The conclusions pave the way for exploration of new similar catalysts for other applications.     

Improved uniformity of Fe3O4 nanoparticles on Fe–N–C nanosheets derived from a 2D covalent organic polymer for oxygen reduction

Developing high-performance non-precious metal-based electrocatalysts for oxygen reduction reaction (ORR) is an urgent demand. In this study, we prepared highly efficient Fe₃O₄-nanoparticles-decorated Fe–N–C nanosheets (Fe₃O₄/CCOP_HM-F127) from 2D covalent organic polymer (COP) for ORR via a facile impregnation method. The introduced anionic surfactant, i.e. F127, can effectively improve the distribution and size uniformity of Fe₃O₄ nanoparticles. The onset potential of Fe₃O₄/COP_HM-F127 is 1.0 V, which is equivalent to that of commercial Pt/C. Moreover, the half-wave potential of Fe₃O₄/COP_HM-F127 can reach up to 0.87 V, which is better than that of commercial Pt/C. Fe₃O₄/COP_HM-F127 also exhibits excellent durability and methanol tolerance during the electrocatalytic process.     

Cobalt doping of α-Fe/Al2O3 catalysts for the production of hydrogen and high-quality carbon nanotubes by thermal decomposition of methane

Fe–Co/Al₂O₃ catalysts were developed and tested in the catalytic decomposition of methane (CDM) for the synthesis of multi-wall carbon nanotubes (MWCNT) and the CO₂-free hydrogen production. While Fe (54.5–66.7 mol.%) is the main active phase for the carbon formation on the catalyst, Co acts as dopant aiming to improve its overall catalytic behaviour. Catalysts with Co contents of up to 18.2 M% showed the presence of α-Fe and Fe–Co crystallites with different size and lattice parameter. Fe_1-xCo_x alloy with bcc crystal system was identified only for Co contents of 14.0% and above, and presented a lattice constant lower than α-Fe, which would modify the carbon diffusion of the metal particle during the MWCNT growth. Co inhibited the Fe₃C formation during CDM resulting in higher carbon formations and longer activity times. This phase, shown in undoped catalysts, favored the presence of bamboo-type carbon nanotubes.     

Improved charge transfer and morphology on Ti-modified Cu/γ-Al2O3/Al catalyst enhance the activity for methanol steam reforming

The metal-oxide interaction has been considered as an effective factor for catalytic performance in methanol steam reforming. In this work, Ti modified Cu/γ-Al₂O₃/Al catalyst was prepared by anodization technology. It is found that the addition of Ti can largely increase the surface area of the carrier and thus improve the dispersion of copper. The co-existence of Ti⁴⁺ and Ti³⁺ makes the charge transfer between Cu and Ti easier, which improves the redox performance of copper. The DFT calculations reveal that Ti also enhance the adsorption capacity of water and methanol on the surface of the catalysts. Besides, Ti also reduce the acid density on the carrier, inhibit methanol dehydration reaction and thereby reduce the selectivity of the DME. The optimal catalyst CuTi_1.9/γ-Al₂O₃/Al achieves nearly 100% conversion at 275 °C, while the methanol conversion of Cu/γ-Al₂O₃/Al is 82%. And the H₂ output of CuTi_1.9/γ-Al₂O₃/Al reached 69.17 mol/(kg_cat·h) at 300 °C.     

Synthesis and characterization of nano-sized γ-Al2O3 for investigation the effect of temperature on catalytic dehydration of methanol to dimethyl ether

The new high surface area and high active nano-sized porous γ-Al₂O₃ catalyst was produced by a co-precipitation method. The synthesized catalyst was characterized by X-ray diffraction, Fourier transform infrared, NH₃-temperature programmed desorption, and Brunauer-Emmett-Teller techniques. The results of characterization tests showed excellent textural and acidic properties of the synthesized catalyst for the methanol dehydration reaction. Catalytic dehydration of methanol to dimethyl ether was performed in an adiabatic fixed bed reactor using the new nano-sized catalyst at different operating temperatures. The results showed that the highest methanol conversion occurs in the temperature range of 300–350°C. Finally, a new correlation was developed to predict methanol conversion from operating temperature.