Amount Of Surface Hydroxyl Groups Research Articles

Surface Hydroxyl and Oxygen Vacancies Engineering in ZnSnAl LDH: Synergistic Promotion of Photocatalytic Oxidation of Aromatic VOCs.

Photocatalytic oxidation has gained great interest in environmental remediation, but it is still limited by its low efficiency and catalytic deactivation in the degradation of aromatic VOCs. In this study, we concurrently regulated the surface hydroxyl and oxygen vacancies by introducing Al into ZnSn layered double hydroxide (LDH). The presence of distorted Al species induced local charge redistribution, leading to the remarkable formation of oxygen vacancies. These oxygen vacancies subsequently increased the amount of surface hydroxyl and elongated its bond length. The synergistic effects of surface hydroxyl and oxygen vacancies greatly enhanced reactant adsorption-activation and facilitated charge transfer to generate •OH, •O2-, and 1O2, resulting in highly efficient oxidation and ring-opening of various aromatic VOCs. Compared with commercial TiO2, the optimized ZnSnAl-50 catalyst exhibited about 2-fold activity for the toluene and styrene degradation and 10-fold activity for the chlorobenzene degradation. Moreover, ZnSnAl-50 demonstrated exceptional stability in the photocatalytic oxidation of toluene under a wide humidity range of 0-75%. This work marvelously improves the photocatalytic efficiency, stability, and adaptability through a novel strategy of surface hydroxyl and oxygen vacancies engineering.

Adsorption-Controlled Wettability and Self-Cleaning of TiO2.

Molecular adsorption on solids is inevitable and has significant influences on the wettability of materials, while the tuning mechanism of the wettability from molecular adsorption is yet to be understood. Using molecular dynamics (MD) simulations, we comprehensively studied the relation between the wettability of the TiO2 surface and the adsorption of water and carboxylic acid molecules. Our results reveal that the increasing amount of surface hydroxyl groups from the decomposition adsorption of H2O increases the hydrophilicity of TiO2, providing molecular-level evidence for the previously proposed mechanism of photo-induced hydrophilicity. By contrast, the surface wettability becomes tunable with water contact angles changing from 0 to ∼130° through length adjustment of the adsorbed carboxylic acids. The TiO2 surface is hydrophilic with the adsorption of short-alkyl-chain carboxylic acids (e.g., HCOOH) and becomes hydrophobic when longer-alkyl-chain carboxylic acids (H(CH2)nCOOH, n > 2) are present. Furthermore, long-alkyl-chain acids also increase surface oleophilicity, while the adsorption of HCOOH and CH3COOH significantly enhances the oleophobicity of TiO2. Water molecules can also more easily penetrate the space between oily contaminants and adsorbed short acid molecules, thereby further increasing its self-cleaning capacity. The present simulations not only reveal the mechanism of wettability caused by molecular adsorption but also provide a promising method to create materials with controllable wettability and high self-cleaning efficiency.

Significantly enhancing CO2 adsorption on Amine-Grafted SBA-15 by boron doping and acid treatment for direct air capture

Among the most studied adsorbents for CO2 capture is amine-grafted mesoporous silica SBA-15. In this work, boron, a heteroatom, was incorporated into the SBA-15 framework and removed by acid treatment to increase the amount of surface hydroxyl groups. It was discovered that the removal of boron resulted in the formation of silanol nests, with four silanol groups in each nest. Compared with the common method of air calcination for SBA-15, acid-treated boron doped SBA-15, exhibited higher silanol density, as well as higher amine loading after amine grafting. This work is the first to study the use of the silanol nests to graft amines and interact with CO2 directly; the results show more than doubling of the CO2 adsorption capacity for direct air capture.

Metal Oxyhydroxide Catalysts Promoted CO2 Absorption and Desorption in Amine-Based Carbon Capture: A Feasibility Study.

The huge energy penalty of CO2 desorption is the greatest challenge impeding the commercial application of amine-based CO2 capture. To deal with this problem, a series of metal oxide and oxyhydroxide catalysts were synthesized in this study to kinetically facilitate the CO2 desorption from 5.0 M monoethanolamine (MEA). The effects of selected catalysts on CO2 absorption kinetics, CO2 absorption capacity, CO2 reaction enthalpy, and desorption duty reduction of 2.0 M MEA were investigated by a true heat flow reaction calorimeter to access the practical feasibility of the catalytic CO2 desorption. The kinetic study of catalytic CO2 desorption was also carried out. CO2 desorption chemistry, catalyst characterization, and structure-function relationships were investigated to reveal the underlying mechanisms. Results show that addition of the catalyst had slight effects on the CO2 absorption kinetics and CO2 reaction enthalpy of MEA. In contrast, the CO2 desorption efficiency greatly increased from 28% in reference MEA to 52% in ZrO(OH)2-aided MEA. Compared to the benchmark catalyst HZSM-5, ZrO(OH)2 exhibited a 13% improvement in CO2 desorption efficiency. More importantly, compared to the reference MEA, the CO2 desorption duties of ZrO(OH)2 and FeOOH-aided MEA significantly reduced by 45 and 47% respectively, which are better than those of most other reported catalysts. The large surface area, pore volume, pore diameter, and amount of surface hydroxyl groups of ZrO(OH)2 and FeOOH afforded the catalytic performance by promoting the adsorption of alkaline speciation (e.g., MEA and HCO3 -) onto the particle surface.

Mesoporous Spherical Silica Filler Prepared from Coal Gasification Fine Slag for Styrene Butadiene Rubber Reinforcement and Promoting Vulcanization.

Coal gasification fine slag (CFS) is a solid contaminant produced by an entrained flow gasifier, which pollutes fields and the air in the long term. CFS is a potential polymer reinforcement filler and has been used in polypropylene and acrylonitrile butadiene styrene resins. Coal gasification fine slag mesoporous silica (FS-SiO2) was prepared by acid leaching, calcination, and pH adjustment, with a larger specific surface area and less surface hydroxyl compared to the commercial precipitated silica (P-silica). The cure characteristics, crosslink density, mechanical properties, the morphology of the tensile fractures, dynamic mechanics, and rubber processing of the prepared styrene butadiene rubber (SBR) composites filled with P-silica and FS-SiO2 were analyzed, respectively. The results indicated that FS-SiO2 was dispersed more uniformly in the SBR matrix than P-silica owing to its smaller amount of surface hydroxyl and spherical structure, resulting in a better mechanical performance and wet skid resistance. In particular, the SBR composites with a filler pH of 6.3 exhibited the highest crosslink density and tensile strength, being superior to commercial P-silica. Significantly, the curing time decreased with the increase in the pH of FS-SiO2, which caused the rubber processing to be more efficient. This strategy can reduce the cost of rubber composites and the environmental pollution caused by CFS.

Hydrothermal Modification of TS-1 Zeolites with Organic Amines and Salts to Construct Highly Selective Catalysts for Cyclopentene Epoxidation

Developing efficient heterogeneous catalysts for cyclic olefins epoxidation is highly attractive for meeting the growing need for various cyclic epoxides. Herein, hierarchical TS-1 zeolite with relatively abundant mesopores and less amount of surface hydroxyl groups was obtained by hydrothermal modification of an as-synthesized TS-1 zeolite with a mixed solution of ammonia, tetrapropylammonium bromide (TPABr) and KCl. The post-modified TS-1 zeolite exhibited much higher catalytic activity (52% conversion) and epoxide selectivity (98%) for the epoxidation of cyclopentene than the conventional TS-1 zeolites. The excellent catalytic activity of the hierarchical TS-1 could be mainly assigned to the enhancement of the mass transport ability and the accessibility of the active Ti species, while the improvement of epoxidation selectivity may be mainly related to the introduction of a certain amount of K+ that can effectively modulate the coordination environment of Ti species as well as the polarity of the zeolite. This work demonstrated that a highly active and selective catalyst for the H2O2-mediated cyclopentene epoxidation could be obtained by concurrently generating mesopore and extinguishing the unfavorable defective hydroxyl groups through the simple hydrothermal treatment of the conventional TS-1 zeolite with a mixed base/salt solution.

Soft Tissue Interface with Various Kinds of Implant Abutment Materials.

Various materials, such as titanium, zirconia and platinum-gold (Pt-Au) alloy, have been utilized for dental implant trans-mucosal parts. However, biological understanding of soft tissue reaction toward these materials is limited. The aim of this study was to compare the response of cell lines and soft tissue to titanium, zirconia and Pt-Au substrata. The surface hydroxyl groups and protein adsorption capacities of the substrata were measured. Next, gingival epithelial-like cells (Sa3) and fibroblastic cells (NIH3T3) were cultured on the materials, and initial cell attachment was measured. Immuno-fluorescent staining of cell adhesion molecules and cytoskeletal proteins was also performed. In the rat model, experimental implants constructed from various materials were inserted into the maxillary tooth extraction socket and the soft tissue was examined histologically and immunohistochemically. No significant differences among the materials were observed regarding the amount of surface hydroxyl groups and protein adsorption capacity. Significantly fewer cells of Sa3 and NIH3T3 adhered to the Pt-Au alloy compared to the other materials. The expression of cell adhesion molecules and a well-developed cytoskeleton was observed, both Sa3 and NIH3T3 on each material. In an animal model, soft tissue with supracrestal tissue attachment was observed around each material. Laminin-5 immuno-reactivity was seen in epithelia on both titanium and zirconia, but only in the bottom of epithelia on Pt-Au alloy. In conclusion, both titanium and zirconia, but not Pt-Au alloy, displayed excellent cell adhesion properties.

Novel Intense-pulsed-light synthesis of amorphous SnO2 electron-selective layers for efficient planar MAPbI3 perovskite solar cells

Although perovskite solar cells (PSCs) have achieved a high power conversion efficiency (PCE) within a short period of development, the high-temperature sintering of the constituent electron-selective layers (ESLs) impedes the commercialization. In this report, we demonstrate the effectiveness of an intense-pulsed-light (IPL) treatment for the rapid and damage-free sintering of amorphous-SnO2 ESLs for use in PSCs. The IPL treatment of amorphous-SnO2 substantially reduced the amount of surface hydroxyl groups, modified the surface energy, and enabled the growth of a low-stress perovskite layer with large grain sizes, all of which enhanced the photovoltaic properties and led to the proper alignment of band structures for efficient PSCs. Through comprehensive optimization of the IPL conditions, a PCE of 17.68% was achieved from the MAPbI3 planar PSC based on an amorphous-SnO2 IPL treated for a few tens of seconds, which was significantly increased compared with a PCE (7.06%) of nontreated SnO2 based counterpart. In addition, the PCE of the IPL-treated SnO2 based PSC is comparable to the best PCE (18.16%) of PSCs fabricated with SnO2 ESL annealed for three hours at 185 °C. Because of its ultrafast sintering time and tendency to not damage SnO2 ESLs, the new IPL process is expected to open new opportunities for the commercialization of PSCs.

Selective hydrogenation of benzene over Ru supported on surface modified TiO2

A series of catalysts with ruthenium nanoparticles (NPs) loaded on the binary oxide TS (TiO2-SiO2) support were prepared by facile sol-gel method for benzene selective hydrogenation. Different mole ratios of Ti/Si were investigated. The catalytic structure, composition, hydrophilicity, electronic state and acidity were characterized. The results indicate that the acidity of the samples increases gradually with the increase of the SiO2 amount. The dispersion of ruthenium nanoparticles was improved on binary oxide support compared with TiO2 and an obvious Ru size effect appeared with the increase of Ti/Si molar ratio. It was also found that the hydrophilicity of the supports could be efficiently improved by introducing a small amount of SiO2 to TiO2, which may be due to the large amount of surface hydroxyl groups on the binary oxide samples after SiO2 introduction. This result was consistent with the increasing trend of cyclohexene yield, indicating that the surface hydroxyl groups play a significant role in the motivation of cyclohexene desorption. Ru/TS (7: 1) showed the best catalytic performance of 38.2% yield to cyclohexene with the highest initial selectivity to cyclohexene (S0) of 87.3%. The catalytic stability experiments showed that the yield of cyclohexene could maintain at 30% after five cycles.

Effect of phosphate on the adsorption of antibiotics onto iron oxide minerals: Comparison between tetracycline and ciprofloxacin

With the broadly application of antibiotics to treat infectious diseases in humans and animals, antibiotic contaminants such as tetracycline (TC) and ciprofloxacin (CIP) have been detected in soil environments, where iron oxide minerals and phosphate are ubiquitous. To date, the influence of phosphate on the adsorption behaviors of TC/CIP onto iron oxides is still poorly understood. In this study, the effects of phosphate on the adsorptions of TC and CIP onto iron oxide minerals were investigated. Adsorption isotherms showed that the adsorption affinities of TC and CIP onto the three iron oxide minerals were in the order of goethite > hematite > magnetite with or without phosphate, the trend was dominated by different surface area and amount of surface hydroxyl groups of iron oxide minerals. Meanwhile, TC contains more functional groups than CIP for bonding, which resulted in greater adsorption affinity of three iron oxides to TC than that to CIP. Interestingly, phosphate weakened TC adsorption, while enhanced CIP adsorption, on the three iron oxides. This observation was ascribed to that phosphate anion enhanced the surface negative charge of iron oxides, which reinforced the electrostatic repulsion between iron oxides and negatively charged TC, also reinforced the electrostatic attraction between iron oxides and positively charged CIP. Furthermore, the inhibitory effect of phosphate on TC adsorption was dramatically enhanced at high pH, while the promoting effect of phosphate on CIP adsorption was slightly changed with various pH. Our results highlight the importance of phosphate in exploring the environmental fate of antibiotics in natural environment.

Excellent visible light responsive photocatalytic behavior of N-doped TiO2 toward decontamination of organic pollutants

In this work, N-doped TiO2 (N-TiO2) with ample and tunable OVs was successfully synthesized, deriving from facile hydrothermal method and baked in the NH3 atmosphere. N-doping boosts the amount of surface hydroxyl and superoxide (O2−) of TiO2, demonstrated by XPS and nitroblue tetrazolium (NBT)-O2− quantitative reaction. Rich and tunable OVs were confirmed by low temperature electron spin resonance (ESR) results, demonstrating that doping of N into TiO2 can definitely construct higher OVs than the reference TiO2. Surface photovoltage spectrum (SPS) test, fluorescence experiments and electrochemical measurements all display that N-TiO2 photocatalysts with OVs have a higher severance efficiency of photogenerated e-/h+ pairs than the pristine TiO2. Photocatalytic evaluation results exhibit that N-TiO2 photocatalysts demonstrate better performance than the reference TiO2 toward decontamination of rhodamine B and tetracycline. TiO2 treated in ammonia atmosphere for 1 h shows the highest photocatalytic property. The visible light responsive catalytic behavior of TiO2 treated in ammonia atmosphere for 1 h is much higher than that of commercial TiO2 (P25) and the pristine TiO2, separately. The ameliorated visible light behavior of N-TiO2 photocatalysts is attributable to rich oxygen vacancies produced through introducing N into TiO2 and the boosted severance of photoactivated e-/h+.

Ru/TiO2 catalyst for selective hydrogenation of benzene: Effect of surface hydroxyl groups and spillover hydrogen

Three Ru/TiO2 catalysts were prepared via an impregnation-chemical reduction method by supporting Ru on three different TiO2 supports, namely TiO2-A (anatase), TiO2-R (rutile) and TiO2-A-750 (annealing TiO2-A at 750 °C). The amount of surface hydroxyl groups in the TiO2 supports and Ru/TiO2 catalysts is evaluated by the FTIR technique, which is found to be affected by crystal and textural property of TiO2. It is found that, for the Ru/TiO2 catalyst, the presence of more spillover hydrogen, and more hydroxyl groups that lead to stronger surface hydrophilicity and lower benzene diffusion rate, thereby improve its catalytic activity and selectivity towards selective hydrogenation of benzene. For the Ru/TiO2-A catalyst, it has much more spillover hydrogen and hydroxyl groups than the other two, hence showing the best catalytic activity (TOF of 0.8 s−1) and cyclohexene selectivity (66%) at a benzene conversion of 50%.

Highly Efficient MnO2/AlOOH Composite Catalyst for Indoor Low-Concentration Formaldehyde Removal at Room Temperature

Indoor formaldehyde from substandard furniture and decorative materials seriously endangers human health. How to remove effectively indoor formaldehyde with low concentration at room temperature is a challenging problem. Using a MnO2/AlOOH composite by the MnO2 modification as a catalyst provides an effective approach to solve this challenge. Here, a new type of MnO2/AlOOH composite catalyst with high ability to remove indoor low-concentration formaldehyde was prepared by redox reaction at room temperature. A MnO2/AlOOH composite with a homogeneous dispersion of MnO2 has high specific surface area and a large amount of surface hydroxyl (-OH) which plays a major role in the adsorption of formaldehyde. A partially crystalline structure was observed in the composite, which contains multivalent Mn ions and a large number of vacancy defects. The surface -OH of composite shows strong oxidation activity through the charge exchange of multivalent Mn ions and vacancy defects. The composite has a higher ability to remove indoor low-concentration formaldehyde compared to the birnessite MnO2 at room temperature. This study proposes a new idea for the improvement of catalytic performance in the structure and composition of the catalyst.

Surface Functional Group Engineering of CeO2 Particles for Enhanced Phosphate Adsorption.

Surface functional groups play a dominating role in determining the adsorption performance of metal oxide particles. The ability to manipulate the surface functional groups is vital in designing an effective adsorbent for water decontamination. In this study, a facile method is proposed for tuning the amount of the surface hydroxyl groups of CeO2 particles. The volume of water added during the ethylene glycol-mediated solvothermal synthesis of CeO2 particles can be used to adjust the amount of surface hydroxyl groups. By simple reduction in the volume of water, the number of surface hydroxyl groups of CeO2 particles can be increased and the phosphate adsorption capacity can be greatly improved. Our results show that the obtained CeO2 particles have high phosphate adsorption capacity at low phosphate concentrations, fast adsorption kinetics, and the ability to achieve an ultralow phosphate concentration in the real sewage effluent. This study provides an effective strategy for designing highly effective metal oxide adsorbents through surface functional group engineering.

Fe3O4-assisted laser desorption ionization mass spectrometry for typical metabolite analysis and localization: Influencing factors, mechanisms, and environmental applications

Fe3O4 has been suggested as an efficient matrix for small-molecule analysis by laser desorption ionization mass spectrometry (LDI-MS), but thus far there has been no systematic study exploring the influencing factors of nano-Fe3O4 on the detection of typical metabolites, or the mechanism by which nano-Fe3O4 assists the desorption and ionization of analytes after receiving laser energy. In this study, Fe3O4 nanoparticles with different physicochemical properties were synthesized and characterized. The results revealed that smaller particle size and greater surface hydroxyl amount of nano-spherical Fe3O4 could improve the intensity and relative standard deviation of typical metabolites by LDI-MS. The thermally driven desorption process played a vital role in LDI performance, but the chemical interactions between nano-Fe3O4 and analytes did not. Good intra- or inter-spot repeatability and linearity of analytes were obtained by the optimum Fe3O4-assisted LDI-MS. Finally, the developed method was successfully used for the rapid analysis and localization of endogenous metabolites in biofluids and whole zebrafish tissue section samples. Our results not only elucidate the influencing factors and mechanisms of nano-Fe3O4 for the detection of typical metabolites in LDI-MS but also reveal an innovative tool for the imaging of chemicals in the regions of interest in terms of eco-toxicological research.

Nanocomposites SnO2/SiO2:SiO2 Impact on the Active Centers and Conductivity Mechanism.

This paper is focused on the effect of the stabilizing component SiO2 on the type and concentration of active sites in SnO2/SiO2 nanocomposites compared with nanocrystalline SnO2. Previously, we found that SnO2/SiO2 nanocomposites show better sensor characteristics in CO detection (lower detection limit, higher sensor response, and shorter response time) compared to pure SnO2 in humid air conditions. Nanocomposites SnO2/SiO2 synthesized using the hydrothermal method were characterized by low temperature nitrogen adsorption, XRD, energy dispersive X-ray spectroscopy (EDX), thermo-programmed reduction with hydrogen (TPR-H2), IR-, and electron-paramagnetic resonance (EPR)-spectroscopy methods. The electrophysical properties of SnO2 and SnO2/SiO2 nanocomposites were studied depending on the oxygen partial pressure in the temperature range of 200–400 °C. The introduction of SiO2 results in an increase in the concentration of paramagnetic centers Sn3+ and the amount of surface hydroxyl groups and chemisorbed oxygen and leads to a decrease in the negative charge on chemisorbed oxygen species. The temperature dependences of the conductivity of SnO2 and SnO2/SiO2 nanocomposites are linearized in Mott coordinates, which may indicate the contribution of the hopping mechanism with a variable hopping distance over local states.

Catalytic ozonation of humic acid in water with modified activated carbon: Enhancement and restoration of the activity of an activated carbon catalyst

Catalytic ozonation of organic compounds in water is an important research area for addressing the current pollution crisis. The objective of the present study was to find a modification method for enhancing and restoring the activity of the activated carbon (AC) catalyst applied in the catalytic ozonation of the humic acid (HA) aquatic contaminant. A three-step treatment consisting of an initial thermal treatment, oxidation treatment, and further thermal treatment increased the amount of surface hydroxyl groups (COH) of AC while reducing the amounts of other surface groups, such as basic, carboxyl, lactone, and carbonyl groups. The obtained ACN2O2N2 shows better catalytic performance for HA ozonation than virgin AC, and the COD removal improved from 71% to 96% after reacting for 10 min. This modification method could also restore the catalytic activity of used ACN2O2N2, as the COD removal improved from 74% to 97% after reacting 10 min. The apparent first-order rate constant (kapp) was obtained by fitting the evolution of TOC. The regression analyses of the relationships between the kapp and the surface chemical properties, textural properties, and degree of AC graphitization showed that the increase in the amount of COH was the main factor driving the enhancement and restoration of the AC catalyst activity.

Crucial Role of Surface Hydroxyls on the Activity and Stability in Electrochemical CO2 Reduction.

The role of surface hydroxyls is significant for understanding catalytic performance of metallic oxides for CO2 electroreduction reaction (CO2ER). This Communication describes, employing SnO x as a model system, how to moderate coverage of hydroxyl to derive a stable Sn branches catalyst for CO2ER with a 93.1% Faradaic efficiency (FE) of carbonaceous products. With use of in situ attenuated total reflection surface enhanced infrared adsorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations, we found thata proper amount ofsurface hydroxyls offered effective sites to boost CO2 adsorption via hydrogen bond. However, a higher surface coverage of hydroxyls leads to self-reduction of Sn-OH. We also explained the competition between self-reduction and CO2 reduction over Sn-based catalysts. The findings revealed the quantitative correlation between surface coverage of hydroxyl and CO2ER activity and suggested a logical extension to other metal oxide catalysts for CO2ER.

Adjustment of Hydrophilic-Lipophilic Balance of Hexamethyldisilazane-Modified Nanosilica for Enhanced Oil Recovery

Different dosages of hexamethyldisilazane (denoted as HMDS), a silane coupling agent, were adopted to modify nanosilica (denoted as NS) to afford a series of HMDS-NS nanoparticles with different hydrophilic-lipophilic balance governed by the amount of surface hydroxyl. The amounts of the hydrophilic hydroxyl of the as-prepared HMDS-NS nanoparticles and their water contact angles were measured, and their dispersing behavior in water and oil was examined in relation to their transfer behavior therein. Moreover, the effects of the as-prepared HMDS-NS nanofluids on the oil–water interfacial tension as well as the oil recovery were investigated based on interfacial tension measurements and simulated rock core flooding tests. Findings indicate that the hydrophilic-lipophilic balance of HMDS-NS nanoparticles highly depends on the amount of the surface hydroxyl, and the surface hydroxyl amount can be well adjusted by properly selecting the dosage of HMDS modifier. Besides, the transfer behavior of HMDS-NS nanoparticles in oil and water is closely related to their hydrophilic-lipophilic balance, and they can greatly reduce the oil–water interfacial tension and increase the oil recovery by 7.7–11.1% as compared with conventional water flooding. This is because the surface grafting of the hydrophobic segments of HMDS leads to a significant increase in the hydrophobicity of nanosilica, thereby changing the wettability of oil on the sand surface and favoring the stripping of oil droplets. Particularly, the HMDS-NS nanofluid obtained with 2[Formula: see text]wt.% of HMDS modifier has a water contact angle of 83.6∘ and can dramatically reduce the oil–water interfacial tension from 20.22[Formula: see text]mN/m to 0.28[Formula: see text]mN/m, showing desired hydrophilic-lipophilic balance and potential for enhanced oil recovery associated with chemical flooding.

Ammonia Synthesis Activity of Alumina-Supported Ruthenium Catalyst Enhanced by Alumina Phase Transformation

The increase of alumina calcination temperature from 800 °C to 1300 °C results in the transformation of γ-Al2O3 to α-Al2O3 phase accompanying a decrease of specific surface area and the amount of tetrahedral Al3+ sites. Over Ru–Ba/alumina catalysts, an increase in alumina calcination temperature would broaden the size distribution of Ru particles, enlarge the metal-to-oxide ratio of Ru, decrease the amount of surface hydroxyl groups, as well as lower the temperature for N2 desorption. As a result, the increase of alumina calcination temperature lessens the effect of hydrogen poisoning and decreases the activation energy for ammonia synthesis. The Ru–Ba/Al2O3 catalyst with alumina calcined at 980 °C having both θ-Al2O3 and α-Al2O3 shows ammonia synthesis rate three times higher than that with alumina calcined at 800 °C having a γ-Al2O3 phase.