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Cu1In2Zr4-O-C catalysts with Cu2In alloy structure were prepared by using the sol–gel method. Cu1In2Zr4-O-PC and Cu1In2Zr4-O-CP catalysts were obtained from plasma-modified Cu1In2Zr4-O-C before and after calcination, respectively. Under the conditions of reaction temperature 270°C, reaction pressure 2 MPa, CO2/H2 = 1/3, and GHSV = 12,000 mL/(g h), Cu1In2Zr4-O-PC catalyst has a high CO2 conversion of 13.3%, methanol selectivity of 74.3%, and CH3OH space-time yield of 3.26 mmol/gcat/h. The characterization results of X-ray diffraction (XRD), scanning electron microscopy (SEM), and temperature-programmed reduction chemisorption (H2-TPR) showed that the plasma-modified catalyst had a low crystallinity, small particle size, good dispersion, and excellent reduction performance, leading to a better activity and selectivity. Through plasma modification, the strong interaction between Cu and In in Cu1In2Zr4-O-CP catalyst, the shift of Cu 2p orbital binding energy to a lower position, and the decrease in reduction temperature all indicate that the reduction ability of Cu1In2Zr4-O-CP catalyst is enhanced, and the CO2 hydrogenation activity is improved.

Oxidative steam reforming of ethanol (OSRE) to produce hydrogen has been investigated over a series of supported PtRu catalysts, with different supports. Bimetallic PtRu-based catalysts were prepared by the impregnation method using H2PtCl6 and RuCl3 as precursors. Six supports (reducible oxides of ZrO2, CeO2, and Co3O4, and irreducible oxides of ZnO, Al2O3, and NiO) were chosen to fabricate bimetallic catalysts. The catalytic performance of the OSRE reaction in the series of PtRu-based samples was evaluated using a fixed-bed flow reactor under atmospheric pressure. In front reaction, the catalyst was pre-activated by reduction under 200°C for 3 h. The gas hourly space velocity was adjusted at 66,000 h−1, and the optimal molar ratios of the H2O/EtOH and O2/EtOH feeds were 4.9 and 0.44, respectively. The results indicated that the PtRu supported on the ZrO2 and CeO2 exhibited superior catalytic performance in the OSRE reaction under a low temperature (a TR of approximately 320°C) for producing the main products of H2 and CO2 with lower CO and CH4 by-products. Also, it was quite stable during a long time evaluation; the maximum YH2 maintained at 4.5–4.2, and the CO distribution approached 3.3–3.5 mol% around 84 h test at 340°C over the PtRu/ZrO2 catalyst.

Chitin and chitosan are abundant unique sources of biologically-fixed nitrogen mainly derived from residues of the fishery productive chain. Their high potential as nitrogen-based highly added-value platform molecules is still largely unexploited and a catalytic way for their valorization would be strongly desirable within a biorefinery concept. Here we report our results obtained with a series of heterogeneous catalysts in the depolymerization of chitosan and chitin to acetylglucosamine. Copper catalysts supported on SiO2, SiO2–Al2O3, SiO2-ZrO2, ZrO2 and the corresponding bare oxides/mixed oxides were tested, together with a sulfated zirconia system (ZrO2-SO3H) that revealed to be extremely selective towards glucosamine, both for chitosan and chitin, thus giving pretty high yields with respect to the values reported so far (44% and 21%, respectively). The use of a heterogeneous catalyst alone, without the need of any additives or the combination with a mineral acid, makes these results remarkable.

Catalysts based on molybdenum carbide or nitride nanoparticles (2–5 nm) supported on titania were prepared by wet impregnation followed by a thermal treatment under alkane (methane or ethane)/hydrogen or nitrogen/hydrogen mixture, respectively. The samples were characterized by elemental analysis, volumetric adsorption of nitrogen, X-ray diffraction, and aberration-corrected transmission electron microscopy. They were evaluated for the hydrogenation of CO2 in the 2–3 MPa and 200–300°C ranges using a gas-phase flow fixed bed reactor. CO, methane, methanol, and ethane (in fraction-decreasing order) were formed on carbides, whereas CO, methanol, and methane were formed on nitrides. The carbide and nitride phase stoichiometries were tuned by varying the preparation conditions, leading to C/Mo and N/Mo atomic ratios of 0.2–1.8 and 0.5–0.7, respectively. The carbide activity increased for lower carburizing alkane concentration and temperature, i.e., lower C/Mo ratio. Enhanced carbide performances were obtained with pure anatase titania support as compared to P25 (anatase/rutile) titania or zirconia, with a methanol selectivity up to 11% at 250°C. The nitride catalysts appeared less active but reached a methanol selectivity of 16% at 250°C.

Direct observation of the surface-enhanced Raman scattering (SERS) of molecules adsorbed on nano-sized zirconia (ZrO2) substrates was first reported without the need for the addition of metal particles. It was found that ZrO2 nanoparticles can exhibit unprecedented Raman signal enhancements on the order of 103 for the probe molecule 4-mercaptobenzoic acid (4-MBA). The dramatic effect of the calcination temperature on the ZrO2 nanoparticles was also investigated. The ZrO2 nanoparticles with the particle diameter of 10.5 nm, which were prepared by calcination at a temperature of 500°C, have the highest SERS activity. A comparison between the experimental and calculation results indicates that charge transfer (CT) effects dominate the surface enhancement. The plentiful surface state of ZrO2 active substrate that is beneficial to CT resonance occurs between molecules and ZrO2 to produce a SERS effect. The CT process depends, to a large extent, on the intrinsic properties of the modifying molecules and the surface properties of the ZrO2. This is a new SERS phenomenon for ZrO2 that will expand the application of ZrO2 to microanalysis and is beneficial for studying the basic properties of both ZrO2 and SERS.

Zr2MoP2O12/ZrO2 composites were successfully synthesized by the solid state method in attempt to fabricate the near-zero thermal expansion ceramics. The phase composition, micromorphology and thermal expansion behavior of the Zr2MoP2O12/ZrO2 composites with different mass ratios were investigated using X-ray diffraction, scanning electron microscopy and thermal mechanical analysis. Results indicate that Zr2MoP2O12/ZrO2 composites can be prepared by pre-sintering at 500°C for 3 h and then sintering at 1050°C for 6 h. The resulting Zr2MoP2O12/ZrO2 composites consisted of orthorhombic Zr2MoP2O12 and monoclinic ZrO2. With increasing content of Zr2MoP2O12, the Zr2MoP2O12/ZrO2 ceramics became more compact and the coefficient of thermal expansion decreased gradually. Zr2MoP2O12/ZrO2 composites show an adjustable coefficient of thermal expansion (CTE) from 5.57 × 10−6 K−1 to −5.73 × 10−6 K−1 by changing the mass ratio of Zr2MoP2O12 and ZrO2. The Zr2MoP2O12/ZrO2 composite with a mass ratio of 2:1 showed near zero thermal expansion, and the average linear thermal expansion coefficient is measured to be 0.0065 × 10−6 K−1 in the temperature range from 25 to 700°C.

In the present work, the activity of Ce and Er-doped ZrO2 nanopowders for sun-driven photocatalytic water oxidation has been investigated. ZrO2 powders with tunable amounts of tetragonal, monoclinic and cubic polymorphs have been synthesized by introducing Ce and Er (from 0.5 to 10 mol % on an oxide basis) through hydrothermal method. The aim of this work is to investigate the role of rare earth (RE) ions rich of electrons (Er3+) and with entirely empty levels (Ce4+) in the ZrO2 matrix for the sun-driven photocatalytic water oxidation reaction. The samples have been characterized by means of UV-Vis spectroscopy, X-Ray diffraction (XRD), N2 adsorption, X-ray photoelectron spectrophotometry (XPS) and transmission electronic microscopy (TEM) with energy dispersive spectroscopy (EDS). With respect to the bare ZrO2 mainly containing monoclinic (m-) phase, an increasing amount of rare-earth (RE) dopant was found to improve the specific BET surface area and to stabilize the tetragonal (t-) or cubic (c-) polymorphs of ZrO2 at room temperature. XRD data confirmed that dopants were mainly inserted in the t-ZrO2 phase. The photocatalytic O2 evolution from water under AM 1.5 G simulated sunlight illumination of the prepared samples have been correlated with their optical, structural and chemical properties. The effect of the dopant concentration on the chemical-physical and photocatalytic properties of the Er- and Ce-doped ZrO2 materials was elucidated. The samples with 5% of RE oxide were the most active, i.e., three times more than pure zirconia. Their superior photocatalytic activity was found to be mainly correlated to two factors: (i) an optimal surface concentration of RE ions of about 3.7%, which increased charge carriers separation in the photocatalysts surface due more superficial defects of the t-ZrO2 and a higher surface area, thus enhancing the reaction kinetics, (ii) a controlled amount of monoclinic vs. tetragonal (or cubic) polymorphs of zirconia with an optimum ratio of about 70/30 of t-ZrO2/m-ZrO2. Instead, the increased ability of the RE-doped ZrO2 to harvest visible light was found to have a secondary role on the photocatalytic activity of the Ce-doped ZrO2 material.

Zr2WP2O12/ZrO2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr2WP2O12/ZrO2 composites with different mass ratio. Relative densities of all the resulting Zr2WP2O12/ZrO2 samples were also tested by Archimedes' methods. The obtained Zr2WP2O12/ZrO2 composites were comprised of orthorhombic Zr2WP2O12 and monoclinic ZrO2. As the increase of the Zr2WP2O12, the relative densities of Zr2WP2O12/ZrO2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr2WP2O12/ZrO2 composites can be tailored from 4.1 × 10−6 K−1 to −3.3 × 10−6 K−1 by changing the content of Zr2WP2O12. The 2:1 Zr2WP2O12/ZrO2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of −0.09 × 10−6 K−1. These adjustable and near zero expansion ceramic composites will have great potential application in many fields.

Cu 1 In 2 Zr 4 -O-C catalysts with Cu 2 In alloy structure were prepared by using the sol-gel method. Cu 1 In 2 Zr 4 -O-PC and Cu 1 In 2 Zr 4 -O-CP catalysts were obtained from plasma-modified Cu 1 In 2 Zr 4 -O-C before and after calcination, respectively. Under the conditions of reaction temperature 270°C, reaction pressure 2 MPa, CO 2 /H 2 = 1/3, and GHSV = 12,000 mL/(g h), Cu 1 In 2 Zr 4 -O-PC catalyst has a high CO 2 conversion of 13.3%, methanol selectivity of 74.3%, and CH 3 OH space-time yield of 3.26 mmol/gcat/h. The characterization results of X-ray diffraction (XRD), scanning electron microscopy (SEM), and temperature-programmed reduction chemisorption (H 2 -TPR) showed that the plasma-modified catalyst had a low crystallinity, small particle size, good dispersion, and excellent reduction performance, leading to a better activity and selectivity. Through plasma modification, the strong interaction between Cu and In in Cu 1 In 2 Zr 4 -O-CP catalyst, the shift of Cu 2p orbital binding energy to a lower position, and the decrease in reduction temperature all indicate that the reduction ability of Cu 1 In 2 Zr 4 -O-CP catalyst is enhanced, and the CO 2 hydrogenation activity is improved., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Song, Gao, Yang, Cao, Liu and Xu.)

Oxidative steam reforming of ethanol (OSRE) to produce hydrogen has been investigated over a series of supported PtRu catalysts, with different supports. Bimetallic PtRu-based catalysts were prepared by the impregnation method using H 2 PtCl 6 and RuCl 3 as precursors. Six supports (reducible oxides of ZrO 2 , CeO 2 , and Co 3 O 4 , and irreducible oxides of ZnO, Al 2 O 3 , and NiO) were chosen to fabricate bimetallic catalysts. The catalytic performance of the OSRE reaction in the series of PtRu-based samples was evaluated using a fixed-bed flow reactor under atmospheric pressure. In front reaction, the catalyst was pre-activated by reduction under 200°C for 3 h. The gas hourly space velocity was adjusted at 66,000 h -1 , and the optimal molar ratios of the H 2 O/EtOH and O 2 /EtOH feeds were 4.9 and 0.44, respectively. The results indicated that the PtRu supported on the ZrO 2 and CeO 2 exhibited superior catalytic performance in the OSRE reaction under a low temperature (a T R of approximately 320°C) for producing the main products of H 2 and CO 2 with lower CO and CH 4 by-products. Also, it was quite stable during a long time evaluation; the maximum Y H2 maintained at 4.5-4.2, and the CO distribution approached 3.3-3.5 mol% around 84 h test at 340°C over the PtRu/ZrO 2 catalyst., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Tang, Liu, Yu and Wang.)

Chitin and chitosan are abundant unique sources of biologically-fixed nitrogen mainly derived from residues of the fishery productive chain. Their high potential as nitrogen-based highly added-value platform molecules is still largely unexploited and a catalytic way for their valorization would be strongly desirable within a biorefinery concept. Here we report our results obtained with a series of heterogeneous catalysts in the depolymerization of chitosan and chitin to acetylglucosamine. Copper catalysts supported on SiO 2 , SiO 2 -Al 2 O 3 , SiO 2 -ZrO 2 , ZrO 2 and the corresponding bare oxides/mixed oxides were tested, together with a sulfated zirconia system (ZrO 2 -SO 3 H) that revealed to be extremely selective towards glucosamine, both for chitosan and chitin, thus giving pretty high yields with respect to the values reported so far (44% and 21%, respectively). The use of a heterogeneous catalyst alone, without the need of any additives or the combination with a mineral acid, makes these results remarkable., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Pappalardo, Remadi, Cipolla, Scotti, Ravasio and Zaccheria.)

Catalysts based on molybdenum carbide or nitride nanoparticles (2-5 nm) supported on titania were prepared by wet impregnation followed by a thermal treatment under alkane (methane or ethane)/hydrogen or nitrogen/hydrogen mixture, respectively. The samples were characterized by elemental analysis, volumetric adsorption of nitrogen, X-ray diffraction, and aberration-corrected transmission electron microscopy. They were evaluated for the hydrogenation of CO 2 in the 2-3 MPa and 200-300°C ranges using a gas-phase flow fixed bed reactor. CO, methane, methanol, and ethane (in fraction-decreasing order) were formed on carbides, whereas CO, methanol, and methane were formed on nitrides. The carbide and nitride phase stoichiometries were tuned by varying the preparation conditions, leading to C/Mo and N/Mo atomic ratios of 0.2-1.8 and 0.5-0.7, respectively. The carbide activity increased for lower carburizing alkane concentration and temperature, i.e., lower C/Mo ratio. Enhanced carbide performances were obtained with pure anatase titania support as compared to P25 (anatase/rutile) titania or zirconia, with a methanol selectivity up to 11% at 250°C. The nitride catalysts appeared less active but reached a methanol selectivity of 16% at 250°C., (Copyright © 2020 Abou Hamdan, Nassereddine, Checa, Jahjah, Pinel, Piccolo and Perret.)

A series of gold catalysts supported on pure CeO 2 , ZrO 2 , and two different Ce-Zr mixed oxides have been prepared and tested in the 5-hydroxymethyl-2-furfural oxidation reaction. All catalysts show high catalytic activity (100% conversion) and important selectivity (27-41%) to the desired product i.e., 2,5-furandicarboxylic acid at low base concentration. Products selectivity changes with the support nature as expected, however, the observed trend cannot be related neither to gold particle size, nor to catalyst reducibility and oxygen mobility. An important relation between the FDCA selectivity and the support textural properties is observed, conducing to the general requirement for optimal pore size for this reaction., (Copyright © 2020 Megías-Sayago, Bonincontro, Lolli, Ivanova, Albonetti, Cavani and Odriozola.)

Direct observation of the surface-enhanced Raman scattering (SERS) of molecules adsorbed on nano-sized zirconia (ZrO 2 ) substrates was first reported without the need for the addition of metal particles. It was found that ZrO 2 nanoparticles can exhibit unprecedented Raman signal enhancements on the order of 10 3 for the probe molecule 4-mercaptobenzoic acid (4-MBA). The dramatic effect of the calcination temperature on the ZrO 2 nanoparticles was also investigated. The ZrO 2 nanoparticles with the particle diameter of 10.5 nm, which were prepared by calcination at a temperature of 500°C, have the highest SERS activity. A comparison between the experimental and calculation results indicates that charge transfer (CT) effects dominate the surface enhancement. The plentiful surface state of ZrO 2 active substrate that is beneficial to CT resonance occurs between molecules and ZrO 2 to produce a SERS effect. The CT process depends, to a large extent, on the intrinsic properties of the modifying molecules and the surface properties of the ZrO 2 . This is a new SERS phenomenon for ZrO 2 that will expand the application of ZrO 2 to microanalysis and is beneficial for studying the basic properties of both ZrO 2 and SERS.

In the present work, the activity of Ce and Er-doped ZrO 2 nanopowders for sun-driven photocatalytic water oxidation has been investigated. ZrO 2 powders with tunable amounts of tetragonal, monoclinic and cubic polymorphs have been synthesized by introducing Ce and Er (from 0.5 to 10 mol % on an oxide basis) through hydrothermal method. The aim of this work is to investigate the role of rare earth (RE) ions rich of electrons (Er 3+ ) and with entirely empty levels (Ce 4+ ) in the ZrO 2 matrix for the sun-driven photocatalytic water oxidation reaction. The samples have been characterized by means of UV-Vis spectroscopy, X-Ray diffraction (XRD), N 2 adsorption, X-ray photoelectron spectrophotometry (XPS) and transmission electronic microscopy (TEM) with energy dispersive spectroscopy (EDS). With respect to the bare ZrO 2 mainly containing monoclinic (m-) phase, an increasing amount of rare-earth (RE) dopant was found to improve the specific BET surface area and to stabilize the tetragonal (t-) or cubic (c-) polymorphs of ZrO 2 at room temperature. XRD data confirmed that dopants were mainly inserted in the t-ZrO 2 phase. The photocatalytic O 2 evolution from water under AM 1.5 G simulated sunlight illumination of the prepared samples have been correlated with their optical, structural and chemical properties. The effect of the dopant concentration on the chemical-physical and photocatalytic properties of the Er- and Ce-doped ZrO 2 materials was elucidated. The samples with 5% of RE oxide were the most active, i.e., three times more than pure zirconia. Their superior photocatalytic activity was found to be mainly correlated to two factors: (i) an optimal surface concentration of RE ions of about 3.7%, which increased charge carriers separation in the photocatalysts surface due more superficial defects of the t-ZrO 2 and a higher surface area, thus enhancing the reaction kinetics, (ii) a controlled amount of monoclinic vs. tetragonal (or cubic) polymorphs of zirconia with an optimum ratio of about 70/30 of t-ZrO 2 /m-ZrO 2 . Instead, the increased ability of the RE-doped ZrO 2 to harvest visible light was found to have a secondary role on the photocatalytic activity of the Ce-doped ZrO 2 material.

Zr 2 MoP 2 O 12 /ZrO 2 composites were successfully synthesized by the solid state method in attempt to fabricate the near-zero thermal expansion ceramics. The phase composition, micromorphology and thermal expansion behavior of the Zr 2 MoP 2 O 12 /ZrO 2 composites with different mass ratios were investigated using X-ray diffraction, scanning electron microscopy and thermal mechanical analysis. Results indicate that Zr 2 MoP 2 O 12 /ZrO 2 composites can be prepared by pre-sintering at 500°C for 3 h and then sintering at 1050°C for 6 h. The resulting Zr 2 MoP 2 O 12 /ZrO 2 composites consisted of orthorhombic Zr 2 MoP 2 O 12 and monoclinic ZrO 2 . With increasing content of Zr 2 MoP 2 O 12 , the Zr 2 MoP 2 O 12 /ZrO 2 ceramics became more compact and the coefficient of thermal expansion decreased gradually. Zr 2 MoP 2 O 12 /ZrO 2 composites show an adjustable coefficient of thermal expansion (CTE) from 5.57 × 10 -6 K -1 to -5.73 × 10 -6 K -1 by changing the mass ratio of Zr 2 MoP 2 O 12 and ZrO 2 . The Zr 2 MoP 2 O 12 /ZrO 2 composite with a mass ratio of 2:1 showed near zero thermal expansion, and the average linear thermal expansion coefficient is measured to be 0.0065 × 10 -6 K -1 in the temperature range from 25 to 700°C.

Zr 2 WP 2 O 12 /ZrO 2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr 2 WP 2 O 12 /ZrO 2 composites with different mass ratio. Relative densities of all the resulting Zr 2 WP 2 O 12 /ZrO 2 samples were also tested by Archimedes' methods. The obtained Zr 2 WP 2 O 12 /ZrO 2 composites were comprised of orthorhombic Zr 2 WP 2 O 12 and monoclinic ZrO 2 . As the increase of the Zr 2 WP 2 O 12 , the relative densities of Zr 2 WP 2 O 12 /ZrO 2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr 2 WP 2 O 12 /ZrO 2 composites can be tailored from 4.1 × 10 -6 K -1 to -3.3 × 10 -6 K -1 by changing the content of Zr 2 WP 2 O 12 . The 2:1 Zr 2 WP 2 O 12 /ZrO 2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of -0.09 × 10 -6 K -1 . These adjustable and near zero expansion ceramic composites will have great potential application in many fields.