Innovative application of magnetically modified bovine horn as a natural keratin resource in the role of value-added organocatalyst

This study presents the conversion of bovine horn powder (BHP) as an available and low-cost waste material to a value-added highly recyclable catalyst. This green catalyst was prepared through the immobilization of BHP, as a natural keratin resource, on the magnetic Fe₃O₄ nanoparticles. The successful preparation of the catalyst was fully investigated using Fourier transform infrared, X-ray diffraction, and energy-dispersive X-ray spectroscopies as well as field emission scanning electron microscopy, vibrating sample magnetometry, and thermogravimetry. The catalytic efficiency of the prepared magnetic organocatalyst was evaluated in the synthesis of a large series of amide derivatives through the solvent-free transamidation reaction of different amides and amines with yields of 75–96%.

The conversion of bovine horn powder as an available and low-cost waste material to a value-added recyclable organocatalyst for transamidation reaction.     

One-pot synthesis of amides via the oxidative amidation of aldehydes and amines catalyzed by a copper-MOF

An efficient method for the oxidative amidation of aldehydes with primary aromatic and aliphatic amines has been developed for the synthesis of a wide variety of amides using inexpensive Cu₂(BDC)₂DABCO (Cu-metal–organic framework [MOF]) as a recyclable heterogeneous catalyst, and N-chlorosuccinimide and aqueous tert-butyl hydroperoxide as oxidants in acetonitrile. This amidation reaction is operationally straightforward and provides secondary amides in good yields in most cases, utilizing inexpensive and readily available reagents under mild conditions.

A method for oxidative amidation of aldehydes with primary amines was developed to synthesise a variety of amides using Cu₂(BDC)₂DABCO (Cu-MOF) as a recyclable heterogeneous catalyst, and N-chlorosuccinimide and aqueous tert-butyl hydroperoxide as oxidants in acetonitrile.     

Fragmentation pattern of amides by EI and HRESI: study of protonation sites using DFT-3LYP data

Amides are important natural products which occur in a few plant families. Piplartine and piperine, major amides in Piper tuberculatum and P. nigrum, respectively, have shown a typical N–CO cleavage when analyzed by EI-MS or HRESI-MS. In this study several synthetic analogs of piplartine and piperine were subjected to both types of mass spectrometric analysis in order to identify structural features influencing fragmentation. Most of the amides showed an intense signal of the protonated molecule [M + H]⁺ when subjected to both HRESI-MS and EI-MS conditions, with a common outcome being the cleavage of the amide bond (N–CO). This results in the loss of the neutral amine or lactam and the formation of aryl acylium cations. The mechanism of N–CO bond cleavage persists in α,β-unsaturated amides because of the stability caused by extended conjugation. Computational methods determined that the protonation of the piperamides and their derivatives takes place preferentially at the amide nitrogen supporting the dominant the N–CO bond cleavage.

The N–CO cleavage of α,β-unsaturated piperamides under EI and ESI is supported by computational studies.     

Development of a thermally stable Pt catalyst by redispersion between CeO2 and Al2O3

For catalytic systems consisting of Pt as the active component and CeO₂–Al₂O₃ as the support material, the metal–support interaction between the Pt and CeO₂ components is widely applied to inhibit aggregation of Pt species and thus enhance the thermal stability of the catalyst. In this work, a highly thermostable Pt catalyst was prepared by modifying the synthesis procedure for conventional Pt/CeO₂/Al₂O₃ (Pt/Ce/Al) catalyst, that is, the CeO₂ component was introduced after deposition of Pt on Al₂O₃. The obtained CeO₂/Pt/Al₂O₃ (Ce/Pt/Al) catalyst exhibits significantly different aging behavior. During the hydrothermal aging process, redispersion of Pt species from the surface of Al₂O₃ to the surface of CeO₂ occurs, resulting in a stronger metal–support interaction between Pt and CeO₂. Thus, the formed Pt–O–Ce bond could act as an anchor to retard aggregation of Pt species and help Pt species stay at a more oxidative state. Consequently, excellent reduction capability and superior three-way catalytic performance are acquired by Ce/Pt/Al-a after hydrothermal aging treatment.

Ce/Pt/Al undergoes redispersion of Pt upon hydrothermal aging, resulting in higher dispersion and consequently superior three-way catalytic performance of Ce/Pt/Al-a.     

Metal-free site-selective C–H cyanoalkylation of 8-aminoquinoline and aniline-derived amides with azobisisobutyronitrile

Using K₂S₂O₈, an efficient and metal-free site-selective C–H cyanoalkylation of 8-aminoquinoline and aniline-derived amides with AIBN (azobisisobutyronitrile) was developed. Without any catalyst, various substrates and functional groups were compatible to afford corresponding products in moderate to high yields. A mechanism study displayed that a radical–radical coupling process was involved via the N-centered radical generation and delocalization of aryl amides.

An efficient metal-free cyanoalkylation of 8-aminoquinoline and aniline-derived amides was achieved in the presence of K₂S₂O₈. The method showed good substrate tolerance and also suitable for bromination and dimerization reactions.     

Comparison on the immersion corrosion and electrochemical corrosion resistance of WC–Al2O3 composites and WC–Co cemented carbide in NaCl solution

WC–15 wt% Al₂O₃ composites were prepared via hot pressing sintering technology. The corrosion behaviors of WC–Al₂O₃ composites and traditional WC–Co cemented carbide in NaCl solution were studied by immersion corrosion and electrochemical technique. The impedance value of the WC–Al₂O₃ composite increased more rapidly than WC–Co cemented carbide during the 24 hours, which indicated that WC–Al₂O₃ composites had a more compact passivation film than WC–Co cemented carbide. The results confirmed that the corrosion resistance of WC–Al₂O₃ composites was higher than that of WC–Co cemented carbide in NaCl solution. The corrosion mechanisms of WC–Al₂O₃ composites and WC–Co cemented carbide in NaCl solution were also revealed by SEM, EDS, XPS and Raman. The corrosion products of WC–Al₂O₃ composites mainly contain WO₃, while for WC–Co cemented carbide they are Co(OH)₂, Co₃O₄ and WO₃. The different corrosion mechanism of the two materials is attributed to the Al₂O₃ phase instead of the Co binder, which avoids the galvanic corrosion between the WC phase and the Co binder.

WC–Al₂O₃ composites possess higher corrosion resistance compared with WC–Co cemented carbide. The main corrosion mechanism for WC–Al₂O₃ composites is the oxidation of the WC phase.     

A new bifunctional heterogeneous nanocatalyst for one-pot reduction-Schiff base condensation and reduction–carbonylation of nitroarenes

In this work, synthesis of Pd–NHC-γ-Fe₂O₃-n-butyl-SO₃H and its activity as a bifunctional heterogeneous nanocatalyst containing Pd–NHC and acidic functional groups, are described. This newly synthesized nanomagnetic catalyst is fully characterized by different methods such as FT-IR, XPS, TEM, VSM, ICP and TG analysis. At first, the catalytic activity of Pd–NHC-γ-Fe₂O₃-n-butyl-SO₃H is evaluated for the reduction of nitroarenes in aqueous media using NaBH₄ as a clean source of hydrogen generation at ambient temperature. Using the promising results obtained from the nitroarene reduction, this catalytic system is used for two one-pot protocols including reduction-Schiff base condensation and reduction–carbonylation of various nitroarenes. In these reactions the in situ formed amines are further reacted with aldehydes to yield imines or carbonylated to amides. The desired products are obtained in good to high yields in the presence of Pd–NHC-γ-Fe₂O₃-n-butyl-SO₃H as a bifunctional catalyst. The catalyst is reused with the aid of a magnetic bar for up to six consecutive cycles without any drastic loss of its catalytic activity.

This paper presents synthesis of Pd–NHC-γ-Fe₂O₃-n-butyl-SO₃H and its activity as bifunctional heterogeneous nanocatalyst containing Pd–NHC and acidic functional groups.     

Effect of Re promoter on the structure and catalytic performance of Ni–Re/Al2O3 catalysts for the reductive amination of monoethanolamine

In this paper, Ni/Al₂O₃ catalysts (15 wt% Ni) with different Re loadings were prepared to investigate the effect of Re on the structure and catalytic performance of Ni–Re/Al₂O₃ catalysts for the reductive amination of monoethanolamine. Reaction results reveal that the conversion and ethylenediamine selectivity increase significantly with increasing Re loading up to 2 wt%. Ni–Re/Al₂O₃ catalysts show excellent stability during the reductive amination reaction. The characterization of XRD, DR UV-Vis spectroscopy, H₂-TPR, and acidity–basicity measurements indicates that addition of Re improves the Ni dispersion, proportion of octahedral Ni²⁺ species, reducibility, and acid strength for Ni–Re/Al₂O₃ catalysts. The Ni15 and Ni15–Re2 catalysts were chosen for in-depth study. The results from SEM-BSE, TEM, and CO-TPD indicate that smaller Ni⁰ particle size and higher Ni⁰ surface area are obtained in the reduced Ni–Re/Al₂O₃ catalysts. Results from in situ XPS and STEM-EDX line scan suggest that Re species show a mixture of various valances and have a tendency to aggregate on the surface of Ni⁰ particles. During reaction, the Ni⁰ particles on the Al₂O₃ support are stabilized and the sintering process is effectively suppressed by the incorporation of Re. It could be concluded that sufficient Ni⁰ sites, the collaborative effect of Ni–Re, and brilliant stability contribute to the excellent catalytic performance of Ni–Re/Al₂O₃ catalysts for the reductive amination of monoethanolamine.

Re promoters improve the catalyst performance and stability of Ni–Re/Al₂O₃ catalysts for the reductive amination of monoethanolamine.     

Recycling the CoMo/Al2O3 catalyst for effectively hydro-upgrading shale oil with high sulfur content and viscosity

Hydrotreatment is an effective upgrading technology for removing contaminants and saturating double bonds. Still, few studies have reported the hydro-upgrading of shale oil, with unusually high sulfur (13200 ppm) content, using the CoMo/Al₂O₃ catalyst. Here we report an extensive study on the upgrading of shale oil by hydrotreatment in a stirred batch autoclave reactor (500 ml) for sulfur removal and viscosity reduction. From a preliminary optimization of the reaction factors, the best-operating conditions were 400 °C, an initial H₂-pressure of 5 MPa, and an agitation rate of 800 rpm, a catalyst-to-oil ratio of 0.1, and a reaction time of 1 h. We could achieve a sulfur removal efficiency of 87.1% and 88.2% viscosity reduction under the optimal conditions. After that, the spent CoMo/Al₂O₃ was repeatedly used for subsequent upgrading tests without any form of pre-treatment. The results showed an increase in the sulfur removal efficiency with an increase in the number of catalyst runs. Ultimately, 99.5–99.9% sulfur removal from the shale oil was achieved by recycling the spent material. Both the fresh and the spent CoMo/Al₂O₃ were characterized and analyzed to ascertain their transformation levels by XRD, TEM, TG, XPS, TPD and N₂ adsorption analysis. The increasing HDS efficiency is attributed to the continuing rise in the sulfidation degree of the catalyst in the sulfur-rich shale oil. The light fraction component in the liquid products (IBP–180 °C) was 30–37 vol% higher than in the fresh shale oil. The product oil can meet the sulfur content requirement of the national standard marine fuel (GB17411-2015/XG1-2018) of China.

The CoMo/Al₂O₃ catalyst was used to upgrade shale oil. Sulfur removal was increased on the spent catalyst. The transition of oxidic Mo-species into active phase MoS₂ was observed with recycling. The high sulfidation degree of the CoMo/Al₂O₃ suppressed deactivation by coking.     

The influence of composition on the functionality of hybrid CuO–ZnO–Al2O3/HZSM-5 for the synthesis of DME from CO2 hydrogenation

A series of CuO–ZnO–Al₂O₃/HZSM-5 hybrid catalysts with different Cu/Zn ratios and disparate Al₂O₃ doping were prepared and characterized by XRD, BET, H₂-TPR, NH₃-TPD and XPS techniques. The optimal Cu/Zn ratio is 7 : 3, and the introduction of a suitable amount of Al₂O₃ to form hybrid catalysts increased the BET specific area and micropore volume, facilitated the CuO dispersion, decreased the CuO crystallite size, increased the interaction between CuO and ZnO, enhanced the number of weak acid sites, altered the copper chemical state and improved the catalytic performance consequently. The highest CO₂ conversion, DME selectivity and DME yield of 27.3%, 67.1% and 18.3%, respectively, were observed over the CZA₇H catalyst. The suitable temperature of 260 °C and the appropriate space velocity of 1500 h⁻¹ for one-step synthesis of dimethyl ether (DME) from carbon dioxide (CO₂) hydrogenation were also investigated. The 50 h stability of the CZA₇H catalyst was also tested.

The introduction of Al₂O₃ increased the number of weak acid sites, altered the copper chemical state and improved the catalytic performance and stability consequently.     

Reduction of imines with a reusable bimetallic PdCo–Fe3O4 catalyst at room temperature under atmospheric pressure of H2

Bimetallic nanocatalysts have been used for the development of organic reactions, owing to the synergistic effect between the transition metals. A new procedure for synthesizing amines by the reduction of imines with H₂ at atmospheric pressure and room temperature in the presence of PdCo–Fe₃O₄ nanoparticles is reported. The straightforward procedure, mild reaction conditions, high turnover number, and recyclability extend the scope of this reaction to practical applications.

A catalytic procedure that has mild reaction conditions, high turnover number, and the recyclability of the catalyst is presented, whereby the synthesis of amines through the reduction of imines employing PdCo–Fe₃O₄ under atmospheric pressure of H₂ is achieved.     

Direct synthesis of amides and imines by dehydrogenative homo or cross-coupling of amines and alcohols catalyzed by Cu-MOF

Oxidative dehydrogenative homo-coupling of amines to imines and cross-coupling of amines with alcohols to amides was achieved with high to moderate yields at room temperature in THF using Cu-MOF as an efficient and recyclable heterogeneous catalyst under mild conditions. Different primary benzyl amines and alcohols could be utilized for the synthesis of a wide variety of amides and imines. The Cu-MOF catalyst could be recycled and reused four times without loss of catalytic activity.

Oxidative dehydrogenative homo or cross-coupling of amines with alcohols to imines and amides was achieved with high to moderate yields at room temperature using Cu-MOF as an efficient and recyclable heterogeneous catalyst.     

Novel blended catalysts consisting of a TiO2 photocatalyst and an Al2O3 supported Pd–Au bimetallic catalyst for direct dehydrogenative cross-coupling between arenes and tetrahydrofuran

Dehydrogenative cross-coupling (DCC) is a clean methodology to make C–C bonds by using abundant C–H bonds. The blended catalyst, developed in this study, consists of a TiO₂ photocatalyst and an Al₂O₃ supported Pd–Au bimetallic catalyst and shows superior activity to the conventional TiO₂ photocatalyst loaded with the corresponding metal co-catalyst for the direct DCC between various arenes and tetrahydrofuran, with concomitant evolution of hydrogen gas. The reactions were done under mild conditions without consuming any oxidising agent or other additional chemicals. This new approach of separating the photocatalyst and the metal catalyst parts allows their independent modification to improve the overall catalytic performance.

A TiO₂ photocatalyst physically mixed with a supported Pd–Au bimetallic catalyst is more efficient than Pd loaded TiO₂ sample for the photocatalytic DCC between arene and THF.     

Metal–support interaction induced ZnO overlayer in Cu@ZnO/Al2O3 catalysts toward low-temperature water–gas shift reaction

The water–gas shift reaction (WGSR) plays a pivotal role in many important industrial processes as well as in the elimination of residual CO in feed gas for fuel cells. The development of a high-efficiency low-temperature WGSR (LT-WGSR) catalyst has attracted considerable attention. Herein, we report a ZnO-modified Cu-based nanocatalyst (denoted as Cu@ZnO/Al₂O₃) obtained via an in situ topological transformation from a Cu₂Zn₁Al-layered double hydroxide (Cu₂Zn₁Al-LDH) precursor at different reduction temperatures. The optimal Cu@ZnO/Al₂O₃-300R catalyst with appropriately abundant Cu@ZnO interface structure shows superior catalytic performance toward the LT-WGSR with a reaction rate of up to 19.47 μmol_CO g_cat⁻¹ s⁻¹ at 175 °C, which is ∼5 times larger than the commercial Cu/ZnO/Al₂O₃ catalyst. High-resolution transmission electron microscopy (HRTEM) proves that the reduction treatment results in the coverage of Cu nanoparticles by ZnO overlayers induced by a strong metal–support interaction (SMSI). Furthermore, the generation of the coating layers of ZnO structure is conducive to stabilize Cu nanoparticles, accounting for long-term stability under the reaction conditions and excellent start/stop cycle of the Cu@ZnO/Al₂O₃-300R catalyst. This study provides a high-efficiency and low-cost Cu-based catalyst for the LT-WGSR and gives a concrete example to help understand the role of Cu@ZnO interface structure in dominating the catalytic activity and stability toward WGSR.

The water–gas shift reaction (WGSR) plays a pivotal role in many important industrial processes as well as in the elimination of residual CO in feed gas for fuel cells.     

Ni nanocatalysts supported on mesoporous Al2O3–CeO2 for CO2 methanation at low temperature

The selectivity and activity of a nickel catalyst for the hydrogenation of carbon dioxide to form methane at low temperatures could be enhanced by mesoporous Al₂O₃–CeO₂ synthesized through a one-pot sol–gel method. The performances of the as-prepared Ni/Al₂O₃–CeO₂ catalysts exceeded those of their single Al₂O₃ counterpart giving a conversion of 78% carbon dioxide with 100% selectivity for methane during 100 h testing, without any deactivation, at the low temperature of 320 °C. The influence of CeO₂ doping on the structure of the catalysts, the interactions between the mesoporous support and nickel species, and the reduction behaviors of Ni²⁺ ions were investigated in detail. In this work, the addition of CeO₂ to the composites increased the oxygen vacancies and active metallic nickel sites, and also decreased the size of the nickel particles, thus improving the low temperature catalytic activity and selectivity significantly.

The addition of CeO₂ to form Ni composite catalysts increased the oxygen vacancies and active metallic nickel sites thus improving the low temperature CO₂ methanation performance.     

Copper alumina @ poly (aniline-co-indole) nanocomposites: synthesis,characterization, electrical properties and gas sensing applications

Poly(aniline-co-indole)/copper alumina (PANI-co-PIN/Cu–Al₂O₃) with excellent AC conductivity, dielectric properties, and ammonia gas detecting capabilities were synthesised via in situ chemical oxidative polymerization. The presence of Cu–O bonding vibrations and shift of some characteristic peaks in the Fourier transform infrared spectroscopy (FT-IR) revealed the successful encapsulation of Cu–Al₂O₃ nanoparticles in the copolymer. The XRD studies showed the crystalline peaks of Cu–Al₂O₃ in the PANI-co-PIN nanocomposites. The high-resolution transmission electron microscopy (HR-TEM) images confirmed the reinforcement of the inorganic moiety in the copolymer. The results from thermogravimetric analysis (TGA) showed that the inclusion of Cu–Al₂O₃ in the copolymer matrix greatly increases the thermal stability of PANI-co-PIN. The alternate current (AC) conductivity and dielectric properties of nanocomposites were higher than pure PANI-co-PIN. The improved electrical properties of nanocomposites were due to strong contact between the copolymer and metal oxide surfaces. The gas sensing properties of synthesized copolymer nanocomposites showed excellent sensitivity and response towards ammonia gas at room temperature. The PANI-co-PIN/5 wt% Cu–Al₂O₃ nanocomposite has the best gas sensing characteristics. The higher AC conductivity, dielectric properties and gas sensing characteristics of PANI-co-PIN/Cu–Al₂O₃ might be used to develop electrochemical sensing devices.

PANI-co-PIN/Cu–Al₂O₃ nanocomposites synthesised via in situ polymerization showed excellent electrical and NH₃ gas sensing properties.     

A study on the viscosity reduction mechanism of high-filled silicone potting adhesive by the formation of Al2O3 clusters

Heat dissipation has become a key problem for highly integrated and miniaturized electronic components. High thermal conductivity, good flowability and low coefficient of linear thermal expansion (CLTE) are indispensable performance parameters in the field of electronic potting composite materials. In this study, spherical alumina (Al₂O₃) was surface modified by γ-(2,3-epoxypropoxy) propyltrimethoxy silane (KH560) and γ-aminopropyltriethoxy silane (KH550) and labelled as Al₂O₃-epoxy and Al₂O₃–NH₂, respectively. Al₂O₃-epoxy and Al₂O₃–NH₂ powders were equally filled in vinyl silicone oil to prepare a high Al₂O₃ loading (89 wt%) precursor of silicone potting adhesive. The viscosity of the precursor rapidly decreased with increasing reaction time of Al₂O₃-epoxy and Al₂O₃–NH₂ at 140 °C. The viscosity reduction mechanism may be due to the formation of some Al₂O₃ clusters by the reaction of Al₂O₃-epoxy with Al₂O₃–NH₂, which results in some vinyl silicone oil segments being held in the channel of particles through capillary phenomenon, leading to the friction among Al₂O₃ clusters decreasing considerably. Laser particle size analysis and scanning electron microscopy (SEM) results confirmed the existence of Al₂O₃ clusters. Energy dispersive spectroscopy (EDS) and dynamic viscoelasticity experiments revealed that some segments of vinyl silicone oils were held by Al₂O₃ clusters. When Al₂O₃-epoxy and Al₂O₃–NH₂ reacted for 4 h, the thermal conductivity, CLTE and volume electrical resistivity of the silicone potting adhesive reached 2.73 W m⁻¹ k⁻¹, 75.8 ppm/°C and 4.6 × 10¹³ Ω cm, respectively. A new strategy for preparing electronic potting materials with high thermal conductivity, good flowability and low CLTE is presented.

Surface-modified Al₂O₃-epoxy reacts with Al₂O₃–NH₂ to form clusters that reduce the viscosity of electronic potting composites.     

Photocatalytic activity of Ag/Al2O3–Gd2O3 photocatalysts prepared by the sol–gel method in the degradation of 4-chlorophenol

The photocatalytic activity in the degradation of 4-chlorophenol (4-ClPh) in aqueous medium (80 ppm) using 2.0 wt% Ag/Al₂O₃–Gd₂O₃ (Ag/Al–Gd-x; where x = 2.0, 5.0, 15.0, 25.0 and 50.0 wt% of Gd₂O₃) photocatalysts prepared by the sol–gel method was studied under UV light irradiation. The photocatalysts were characterized by N₂ physisorption, X-ray diffraction, SEM, HRTEM, UV-Vis, XPS, FTIR and fluorescence spectroscopy. About 67.0% of 4-ClPh was photoconverted after 4 h of UV light irradiation using Ag/γ-–Al₂O₃. When Ag/Al–Gd-x photocatalysts were tested, the 4-ClPh photoconversion was improved and more than 90.0% of 4-ClPh was photoconverted after 3 h of UV light irradiation in the materials containing 15.0 and 25.0 wt% of Gd₂O₃. Ag/Al–Gd-25 was the material with the highest efficacy to mineralize dissolved organic carbon, mineralizing more than 85.0% after 4 h of UV light irradiation. Silver nanoparticles and micro-particles of irregular pentagonal shape intersected by plane nanobelts of Al₂O₃–Gd₂O₃ composite oxide were detected in the Ag/Al–Gd-25 photocatalyst. This material is characterized by a lowest recombination rate of electron–hole pairs. The low recombination rate of photo-induced electron–hole pairs in the Ag/Al–Gd-x photocatalysts with high Gd₂O₃ contents (≥15.0 wt%) confirmes that the presence of silver nanoparticles and microparticles interacting with Al₂O₃–Gd₂O₃ composite oxide entities favors the separation of photo-induced charges (e⁻ and h⁺). These materials could be appropriate to be used as highly efficient photocatalysts to eliminate high concentrations of 4-ClPh in aqueous medium.

Ag/Al₂O₃–Gd₂O₃ showed high efficacy to photodegradate 4-chlorophenol, the strong interaction between silver nano-particles and micro-particles and Al₂O₃–Gd₂O₃ entities favors the decrease in the recombination rate.     

Study of resistance performance of Al2O3–ZnO–Y2O3 thermal control coating exposed to vacuum-ultraviolet irradiation

As deep space exploration moves farther and farther away, thermal control coating of the in-orbit spacecraft will suffer a serious vacuum-ultraviolet radiation environment, which seriously threatens the reliability of the spacecraft in orbit. Therefore, it is important to improve the vacuum-ultraviolet resistance performance of the thermal control coating. In this work, the inorganic Al₂O₃–ZnO–Y₂O₃ thermal control coating was in situ fabricated on a 6061 aluminum alloy surface by PEO technology, and its vacuum-ultraviolet resistance performance was investigated. The results show that the Al₂O₃–ZnO–Y₂O₃ thermal control coating has a good resistance performance to vacuum-ultraviolet radiation, which is mainly because the large extinction coefficients of the ZnO and Y₂O₃ materials in the ultraviolet band are conducive to improving the ultraviolet resistance performance. Furthermore, the life prediction model of the Al₂O₃–ZnO–Y₂O₃ thermal control coating shows that its Δα_s value first slightly increases and then tends to be stable with the increase of ultraviolet irradiation time from 0 ESH to 25 000 ESH, and the maximum variation of Δα_s is about 0.0536. This work provides a material basis and technical support for the thermal control system of spacecraft with long life and high reliability.

The Al₂O₃–ZnO–Y₂O₃ thermal control coating in situ fabricated by PEO technology, shows a good resistance performance to vacuum-ultraviolet radiation. Further, its life prediction model at vacuum-ultraviolet irradiation is preliminarily established.     

Efficient access to amides of the carborane carboxylic acid [1-(COOH)–CB11H11]−

The preparation of the carborane acid chloride [1-(COCl)–CB₁₁H₁₁]⁻ from the carboxylic acid [1-(COOH)–CB₁₁H₁₁]⁻ is reported. This acid chloride exhibits remarkable inertness towards moisture and can be stored under ambient conditions for several months. Reaction with amines affords secondary and tertiary carborane amides [1-(CONR¹R²)–CB₁₁H₁₁]⁻ in moderate to high yields under mild conditions. Two of the amide products were characterized by X-ray crystallography in addition to spectroscopic analysis. Preliminary studies show that the amides can be reduced to the corresponding amines and that the acid chloride has the potential to serve as a starting material for carborane ester formation.

The preparation of the carborane acid chloride [1-(COCl)–CB₁₁H₁₁]⁻ from the carboxylic acid [1-(COOH)–CB₁₁H₁₁]⁻ and subsequent amide formation are reported.