HAP Catalyst Research Articles

Promotional Effects of Mg-Substituted Ni/MgxHAP Catalysts on Carbon Resistance during Dry Reforming of Methane

Promotional Effects of Mg-Substituted Ni/Mg_<i>x</i>HAP Catalysts on Carbon Resistance during Dry Reforming of Methane

Viability of Au/La2O3/HAP catalysts for the CO preferential oxidation reaction under reformate gas conditions

The viability of gold supported on lanthanum-modified HAP catalysts is investigated for CO preferential oxidation (PROX) in H2-rich stream. All samples comprise small nanoparticles (NPs) of Au (< 4 nm). Addition of La enhances the chemisorption of CO, whereas it lowers that of H2 and H2O. Moreover, lanthanum improves the reducibility of the catalysts and the mobility of oxygen. FTIR studies show that under CO oxidation conditions Au exists in two distinct forms on La-promoted samples, namely Auσ+ and Au+ species. The catalytic tests under different PROX conditions show an improvement of the performance with lanthanum addition. The observed improvement is linked to suitable chemical properties, whereas efficiency dependence on Au NP sizes is rather secondary. At 80 °C, La-rich catalysts completely eliminate CO and prove to be selective (66%) under realistic PROX conditions (in the presence of H2O and CO2). Moreover, they are exceptionally stable during an extended period (240 h).

Reaction analysis and global kinetics of partial oxidation of methane using Ni–hydroxyapatite composite catalysts

Reaction analysis and global kinetics of the partial oxidation of methane (POM) were investigated for Ni–hydroxyapatite composite catalysts (Ni–HAp) containing 5- and 20-wt% Ni. The composite particles were prepared using slurry precursor materials. The amount of each gas component at the exit of the reactor was determined on the basis of the change in the gas volume obtained from the total mass balance. As the Ni–HAp catalyst is believed to undergo a direct mechanism of the POM reaction, in the proposed multiple reaction analysis, we assumed the following three independent reactions; direct POM, complete combustion of methane, and a water–gas shift reaction. The extent of these reactions clearly revealed the dominating reaction profile at each temperature. The results indicate that both direct and indirect mechanisms of the POM reaction were followed in parallel even at high temperatures. The activation energy of POM using Ni–HAp catalyst containing 5-wt% Ni was found to be 71.3 kJ/mol. The catalyst were characterized using XRD, BET method, CO pulse method, and TGA. The results of these tests showed the positive effect of changing the Ni loading on the catalyst structure.

Promotional effects of defects on Ni/HAP catalyst for carbon resistance and durability during dry reforming of methane

Excellent carbon resistance and stable operations are essential for the industrialization of catalytic dry reforming of methane (DRM). In this study, a series of Ni/HAP and Ni/HAP-D catalysts are used to investigate their DRM reaction performance, including activity, durability, and resistance to carbon deposition. Combined with H2-TPR and XPS results, Ni in the Ni/HAP prefers to replace the external Ca atoms in hydroxyapatite. The inherently “Ca-deficient” HAP-D support facilitates a more robust anchor positioning for the Ni metal, and a significant fraction of the Ni atoms will be embedded in the inner structure of hydroxyapatite in the form of Ni2+[I] and Ni2+[II]. The catalytic activity of the Ni/HAP-D series of catalysts for CH4 and CO2 is significantly higher than that of the Ni/HAP series of catalysts, demonstrating that the Ni morphology, the combined form between Ni and support plays a crucial role in the DRM reaction. The deactivation rate of the Ni0.5/HAP-D catalyst is only 0.008% h−1 and 0.007% h−1 for CH4 and CO2, respectively, in a 200-h durability test. In the spent Ni0.5/HAP catalyst after 118-h reaction, the presence of NiO crystalline phase is detected, indicating that partial Ni is oxidized by CO2 during the reaction, and amorphous carbon and graphitic carbon are also detected. In contrast, no NiO crystalline phase is detected in the spent Ni/HAP-D catalyst after 200-h reaction, and only trace amounts of graphitic carbon are observed, indicating that the Ni presence pattern of Ni0.5/HAP-D contributes to its stability and resistance to carbon deposition. This work provides insights into the design of supported nickel-based catalysts with both excellent stability and surprisingly resistant to carbon deposits for DRM applications.

Development of a New Ternary Al2O3-HAP-Pd Catalyst for Diethyl Ether and Ethylene Production Using the Preferential Dehydration of Ethanol.

This study aims to convert ethanol to higher value-added products, particularly diethyl ether and ethylene using the catalytic dehydration of ethanol. Hence, the gas-phase dehydration of ethanol over Al2O3-HAP catalysts as such and modified by addition of palladium (Pd) in a microreactor was evaluated. The commercial Al2O3–HAP catalyst was first prepared by the physical mixing method, and then, the optimal ratio of the Al2O3–HAP catalyst (2:8 by wt %) was impregnated with Pd to develop a new functional catalyst to alter surface acidity. Based on the results, the combination of Al2O3 and HAP catalysts generated significant quantities of weak acid sites which demonstrates an enhancement in catalytic activity. In addition, Pd modification in the optimal composition ratio of the Al2O3–HAP catalyst extremely increased the amount of weak acid sites as well as weak acid density due to the synergistic effect between the Pd and Al2O3–HAP catalyst that are supposed to suggest the active sites in the reaction. Among all catalysts, the Al20-HAP80-Pd catalyst displayed brilliant catalytic performance in the course of diethyl ether yield (ca. 51.0%) at a reaction temperature of 350 °C and ethylene yield (ca. 75.0%) at a reaction temperature of 400 °C having an outstanding stability under time-on-stream for 10 h. This is recognized to the combination of the effects of weak acid sites (Lewis acidity), small amount of strong acid sites, and structural characteristics of the catalytic materials used.

Substitution of Fe in hydroxyapatite as an efficient single-atom catalyst for oxygen reduction reaction in biofuel cells: A first-principles study

Single-atom biological catalysts have attracted enormous attentions for low cost, high stability and catalytic activity in therapeutics and biomedical devices. The properties of Fe atom substituted CaII in HAP surface (Fe@HAP) and Fe adsorbed over HAP surface (Fe/HAP), and the detailed kinetic and thermodynamic behaviors of the oxygen reduction reaction (ORR) processes have been investigated by using the first-principles study. It is found that Fe dopant by substituted CaII ion into HAP surface could be more stably anchored at HAP surface than Fe adsorbate, and the introduced Fe dopant can enormously increase the endogenous ORR catalytic activity of magnetic HAP catalysts. Furthermore, the ORR process on Fe@HAP prefers to the 4e- pathway with the small reaction barrier (0.73 eV) for the rate-limiting step, and the two OH species formed from the hydrogenation of the adsorbed O2 prefer to further hydrogenate into two H2O molecules and their self-dehydrogenation is not preferable according to the transition states simulation, which is also confirmed by the Gibbs free energy calculation. Consequently, our results revealed that the Fe@HAP could be an efficient catalyst as cathode material in the applications of the implantable biofuel cells and shed light on the design of biomaterials for various applications.

Study of the Use of Hydrotalcite–Hydroxyapatite as Heterogeneous Catalysts for Application in Biodiesel Using By-Product as Raw Material

The materials hydrotalcite—HT, hydroxyapatite—HAp and hydrotalcite–hydroxyapatite—HT–HAp were synthesized using the co-precipitation method at constant pH (pH 10), in which first the materials of HT and HAp were synthesized and later a reaction mixture for the formation of HT–HAp material. The materials were characterized by X-ray diffraction (XRD), N2 adsorption and desorption, infrared spectral analysis (FT-IR), thermogravimetric analysis (TG) and morphology. The results indicated that the analysis by XRD confirmed that all materials (HT, HAp, and HT–HAp) presented the typical basal peaks of HT and HAp and that in the HT–HAp material it presented a better crystalline ordering. The analysis of specific surface area (BET) showed that the mixture of materials (HT–HAp) caused a loss of the specific area, indicating a possible interaction between the particles of both materials. The pore diameters showed mesoporosity. In addition, the materials HT, HAp and HT–HAp had their catalytic activity determined through transesterification reactions using different lipid raw materials (commercial soy oil and vegetable oil deodorization distillate-VODD) obtaining ethyl esters (biodiesel) as a product. The results for the raw material commercial soybean oil showed that the catalysts HT and HAp obtained incomplete reactions, that is, they presented low conversions in ethyl esters (about 39–65% in 6 h of reaction). On the other hand, the study of the influence of temperature on the calcination of the HT–HAp catalyst obtained high conversions in ethyl esters, about 98% for the catalyst calcined at 700 °C, under conditions of 45:1 ethanol/oil molar ratio, temperature of 70 °C, catalyst concentration of 5% and 6 h of reaction. With the transesterification of soybean oil as a comparative form, the catalyst in its best conditions was used to transesterify the VODD by-product. Which results of conversion into considerable ethyl esters were found (about 88%, in just 6 h of reaction), thus confirming that the chemical catalyst was able to form the main esters of fatty acids even using different lipid sources.

Platinum supported on lanthana-modified hydroxyapatite samples for realistic WGS conditions: On the nature of the active species, kinetic aspects and the resistance to shut-down/start-up cycles

The performance of a series of Pt/La(x)/HAP catalysts was investigated in the WGS reaction. It was found that the addition of La into the Pt/HAP catalyst enhances its OSC, hinders the incorporation of Pt species into the HAP framework, promotes its reducibility, decreases the Pt particle size and markedly improves its WGS activity. Moreover, the shut-down/start-up experiments demonstrate the high resistance of the investigated samples and the possibility of their use in mobile device applications.Kinetic data show that the reaction orders measured on Pt/La(4)/HAP agree with those corresponding to 1%Pt/Al2O3 catalyst. By contrast, the general tendency found on the rest of our samples, including the unpromoted one, resembles that shown by a Pt/CeO2 catalyst. Due to the presence of OH− vacant sites on our Ca-deficient HAP, it seems that it plays a role similar to that exhibited by the CeO2 reducible support.

Copper supported on Co substituted hydroxyapatite for complete oxidation of diesel engine exhaust and VOC

The Co substituted HAp catalysts were prepared by co-precipitation method followed by the deposition of Cu and used for complete oxidation of CO, propene, as the model component of diesel engine exhaust and toluene as VOC. The activity of Co substituted Cu/HAp was compared with Cu/HAp. The Cu/Co0.4HAp showed 100% CO conversion at 157 °C whereas Cu/HAp at 376 °C. Furthermore, Cu/CoxHAp showed propene and toluene conversion at 310 and 315 °C respectively, whereas Cu/HAp showed 100% conversion at 400 and 340 °C respectively. The PXRD, ATR-FTIR, H2-TPR, XPS, EDS, HRTEM techniques were used for characterization of catalysts. The Cu/Co0.4HAp showed improved sulfur tolerance compared to the Cu/Hap. The characterization demonstrates that the Co substituted HAp improved the surface redox properties of CuOx species and preserver hydrotalcite structure. The spherical shape of smaller Cu species was observed at CoxHAp surface. However, Cu/HAp showed formation of quasi spherical Cu on HAp surface. Co and HAp interaction could improve the activation of hydrocarbon at a lower temperature compared to the Cu/HAp. The weakly bound oxygen on the Cu/CoxHAp surface could be responsible for the facile activation of CO and hydrocarbon at lower temperature which further oxidized into CO2. The Co doped Cu/HAp catalyst showed higher and stable activity at lower and higher temperature window respectively. The kinetic and mechanistic aspects of Cu/Hap and Cu/CoxHap for oxidation has been explained in detail.

Catalytic performance of Cu/hydroxyapatite catalysts in CO preferential oxidation in H2-rich stream

Abstract A series of Cu/HAP catalysts was prepared by impregnation and characterised by TEM, BET, DRS, XPS, H2-TPR, XRD, TEM and FTIR techniques. H2-TPR and DRS data revealed that at low concentration ( The activity of the reduced samples in COTOX and COPROX processes revealed remarkable differences when the Cu content was increased from 0.8 to 14.8%. For instance, analysing the TOF values calculated for the two processes and the characterisation data, it was concluded that the catalysts with low Cu loadings (0.8% and 3.6%) were the most active ones and their sites involved in the CO oxidation reaction were almost similar. The addition of CO2 and water seemed to affect the performances of the two catalysts via different pathways. Indeed, in contrast to the Cu(4)/HAP, the Cu(1)/HAP catalyst became more selective in the presence of CO2 and water. Moreover, under these realistic COPROX conditions, the latter was 6.6 times more active than the former. A correlation with the characterisation data showed that the most efficient species consisted of those presenting strong interaction with the HAP support. By contrast, the sites exhibiting high concentration of Cu lattice imperfections showed a relatively low activity.

Water-gas shift reaction over a novel Cu-ZnO/HAP formulation: Enhanced catalytic performance in mobile fuel cell applications

CuO-ZnO/HAP catalysts were prepared by co-impregnation and tested in the water-gas shift reaction. The prepared samples were thoroughly characterised by a wide number of analytical techniques including N2 physisorption, XRD, DRS, XPS, H2-TPR, N2O chemisorption, CO-TPD, H2-TPD, CO2-TPD, OSCC and OSC techniques. The properties of the synthesised materials were compared with those of a CuO-ZnO/Al2O3 sample. In contrast to the alumina support, the hydroxyapatite seems to favour the deposition of the CuO and ZnO phases exhibiting an intimate contact. Owing to this suitable distribution and the rich surface chemistry of the support, the CO-TPD, H2-TPD and CO2-TPD data point out that, with independence of the adsorbed molecule, the Cu-ZnO/HAP surface results as the most reactive and provide the largest density of the adsorption sites compared to the Cu-ZnO/Al2O3. The OSCC and OSC data, moreover, show that the former provides relatively high reducibility and larger amounts of reactive oxygen atoms. In realistic WGS reaction conditions the Cu-ZnO/HAP system proves to be highly active and exhibits an excellent stability at 250 °C. The reported data also suggest that the sample with the intermediate copper loading (12 wt.%) represents an optimum chemical composition (Cu/Zn = 3) providing the best catalytic performance. Furthermore, while previous research findings consider the Cu-ZnO as less practical for mobile applications, the current study sheds light on its great potential when supported on hydroxyapatite materials. Indeed, besides its higher activity the CuZn(3)/HAP catalyst successfully withstand the shut-down/start-up conditions exhibiting only 14% activity loss after six cycles. This excellent performance is linked to suitable textural, structural and chemical properties, provided by the HAP support, which make the active sites highly sintering-resistant.

Glycerol valorization to lactic acid catalyzed by hydroxyapatite‐supported palladium particles

AbstractBACKGROUNDCatalytic formation of lactic acid from biomass glycerol is a sustainable alternative to the conventional fermentation process starting from carbohydrate and the chemical route using HCN and acetaldehyde. Highly concentrated glycerol can be effectively converted to lactic acid using hydroxyapatite‐supported palladium particles in the presence of NaOH.RESULTSThe 3% hydroxyapatite‐supported palladium catalyst (Pd3/HAP) demonstrates excellent activity (TOF = 1274 h−1 for a batch time of 90 min) with a high selectivity (95%) towards lactic acid at 99% glycerol conversion (230 °C, NaOH:glycerol molar ratio = 1.1, and glycerol/total Pd intake = 1926). Under the same reaction conditions, the selectivities of lactic acid were 82% and 90% on Pd0.75/HAP and Pd1.5/HAP catalysts, respectively. The Pd3/HAP catalyst was recycled five times in a batch set‐up without a significant drop in activity and lactic acid selectivity, which is indicative of good catalyst stability.CONCLUSIONSPd‐based catalysts on available hydroxyapatite supports are efficient catalysts for glycerol selective oxidation. The catalysts possess active PdO and Pd0 species well dispersed on the functionalized hydroxyapatite support. Pd0 nanoparticles and NaOH synergistically catalyze the reaction process. © 2018 Society of Chemical Industry

Effect of Ni Addition on the Low Temperature Carbon Monoxide Oxidation over Au/HAP Nanocatalyst

Supported gold catalysts with their uniquely catalytic properties have found extensive applications. A challenge for gold catalyst research is now to prevent the sintering of gold particles at high temperature maintaining their high activities simultaneously. Herein, Au/Ni–HAP catalyst with high activity and sintering-resistance was prepared by a deposition–precipitation method. Samples were characterized by XRD, TEM, SEM, UV–Vis, ICP, XPS, FT-Raman and O2-TPD, and their catalytic performance for CO oxidation was tested. TEM results indicated that Au/Ni–HAP catalyst had the smaller gold nanoparticles than Au/HAP catalyst. In UV–Vis spectra, the addition of Ni to Au/HAP catalyst gave rise to larger absorption into visible light, changing the electronic structure of Au/HAP catalyst. Based on XPS studies, nickel existed mainly as NiO in Au/Ni–HAP catalyst, and a small amount of Ni(OH)2 also was formed in Au/Ni–HAP catalyst. Profiles of O2-TPD revealed that Au/Ni–HAP catalyst performed bigger adsorption of oxygen and possessed more new oxygen adsorption sites compared with Au/HAP catalyst. Results showed that Au/Ni–HAP catalyst had better catalytic activity and sintering-resistance than Au/HAP catalyst. The enhanced activity could be attributed to the synergistic effect of gold, nickel and HAP in Au/Ni–HAP catalyst, which created plenty of oxygen vacancies and changed the electronic structure of Au/HAP catalyst.

Catalytic Conversion of Glycerol to Lactic Acid Over Hydroxyapatite-Supported Metallic Ni0 Nanoparticles.

Catalytic conversion of low-priced biomass glycerol to value-added lactic acid is an alternative route to the conventional fermentation process using sugar as the starting material. Nanosized hydroxyapatite-supported metallic Ni0 nanoparticles (Nix/HAP) prepared by the wetness chemical reduction method effectively catalyzed the conversion of high-concentrated glycerol (1.5-3 mol L-1) to lactic acid in a NaOH aqueous solution. The Nix/HAP catalysts exhibited higher catalytic activity for glycerol conversion to lactic acid than the sole metallic Ni0 nanoparticles. When the reaction was carried out over the Ni0.2/HAP catalyst with the initial glycerol and NaOH concentrations of 2.0 and 2.2 mol L-1 at 200 °C for 2 h, the selectivity of lactic acid reached 94.7% at the glycerol conversion of 92.1%.

Behaviour of Rh supported on hydroxyapatite catalysts in partial oxidation and steam reforming of methane: On the role of the speciation of the Rh particles

Rh/hydroxyapatite samples were prepared by impregnation and investigated for the partial oxidation (POM) and steam reforming (SRM) of methane. The catalysts were analysed by BET, XRD, DRS, XPS, H2-TPR, TEM, H2 chemisorption, CO2-TPD and NH3-TPD techniques. The characterisation results showed that, after calcination, Rh existed in three different forms in the samples: (i) large crystallites of Rh2O3 deposited on the surface of the catalysts, (ii) RhOx in small particles exhibiting strong interaction with the support and (iii) a phase of Rh2+ species which incorporated the hydroxyapatite framework.Operating in the POM and SRM processes the reduced Rh(x)/HAP catalysts resulted highly active and exhibited excellent stability at 973 K (for 30 h). This behaviour was explained by their high coke-resistance. The activity of the catalyst with the optimum loading (1%), in SRM, was compared with that of a commercial Rh/Al2O3 catalyst. The conversion and H2 and CO yields values achieved on the former were all close to those exhibited by the latter. This comparable behaviour was explained by suitable properties provided by the HAP support such as reducibility, lower surface acidity and larger pore sizes (ensuring a better diffusion of the reactants and the products during the SRM reaction). These properties seemed to compensate the low dispersion of the Rh active phase induced by its low specific surface area.

Catalytic properties of cobalt-promoted Pd/HAP catalyst for CO-cleanup of H2-rich stream

The promoting effect of Co addition on the behaviour of the Pd/HAP system in WGS reaction has been investigated. Hydroxyapatite-supported bimetallic PdCo samples have been prepared by two consecutive impregnation steps with solutions of Co and Pd precursors, respectively. The resulting catalysts have been thoroughly characterised by BET, XRD, H2-TPR, XPS, OSCC and OSC techniques.The progressive addition of cobalt drives to an abundance of the Pd species exhibiting an intimate contact with Co and an eminent enhancement of the redox properties of the Pd/Co(x)/HAP catalysts. This results in an improvement of their performance in WGS reaction. The Pd species presenting an intimate contact with cobalt seems to be the responsible of the improvement of the CO conversion. However, this PdCo interaction leads to an increase in the methanation activity at the expense of WGS activity. When small amounts of O2 is added to the WGS mixture, the activity is exclusively enhanced in the presence of Co species exhibiting easier reducibility.

Partially Fluoride-Substituted Hydroxyapatite as a Suitable Support for the Gold-Catalyzed Homocoupling of Phenylboronic Acid: An Example of Interface Modification

Interface modification of hydroxyapatite-supported nanogold by fluoride ion improved the activity of the catalyst toward aerobic homocoupling of phenylboronic acid. In the aerobic homocoupling reaction of PhBF3K catalyzed by hydroxyapatite-supported gold nanoclusters (Au:HAP), a study on the reactivity and reusability of the Au:HAP catalyst showed an unusual yield profile for the reaction. Intensive characterization of the catalyst by X-ray diffraction, transmission electron microscopy, and energy-dispersive X-ray spectroscopic analysis exhibited that the structure of the metal oxide support undergoes transformation from HAP to fluorapatite (FAP) and finally to calcium fluoride (CaF2) during the course of these cycles of homocoupling of PhBF3K. Investigations of the interactions of Au:HAP with PhBF3K and of the fluoride ion-induced structural changes in both the support and the AuNCs, indicating that partially fluoride-substituted HAP (F-HAP) is the optimal support for the homocoupling of PhB(OH)2. This i...

CO elimination processes over promoter-free hydroxyapatite supported palladium catalysts

The catalytic performance of synthesised calcium-deficient hydroxyapatite supported Pd catalysts are examined for various CO elimination processes, namely CO total oxidation, CO preferential oxidation and water gas shift reactions. The prepared samples loaded with different amounts of palladium (0.5–2%) are thoroughly characterised by a wide number of analytical techniques including N2 physisorption, XRD, H2-TPR, TEM, CO-TPD, H2 chemisorption, OSCC and OSC techniques. The characterisation results show that, besides an incorporation of 0.3wt% Pd into hydroxyapatite structure, on the Pd(0.5)/HAP sample, small Pd particle sizes (7.6nm) are deposited on the HAP support surface presenting relatively high dispersion (19%). The OSCC and OSC studies show that the highly dispersed Pd species lying on the HAP surface present high reducibility and high oxygen mobility.In the three investigated CO elimination processes the Pd(0.5)/HAP catalyst proves to be highly active and exhibits higher stability compared to that of the Pd(1)/HAP and Pd(2)/HAP catalysts. The catalytic performance of the series of the catalysts demonstrates their structure-sensitivity in the investigated processes. The latter are remarkably enhanced in the presence of small Pd particle sizes which provide high reducibility and high oxygen storage capacity. Moreover, the performances of the Pd/HAP catalysts evidence the potential of HAP support as promising alternative to those reported in the available literature.

Reductive amination of furfural toward furfurylamine with aqueous ammonia under hydrogen over Ru-supported catalyst

Poly(N-vinyl-2-pyrrolidone)-capped ruthenium-supported hydroxyapatite (Ru-PVP/HAP) shows significant activity for the synthesis of furfurylamine (FAM) via the reductive amination of furfural. As-prepared 5 wt% Ru-PVP/HAP affords 50 % yield of FAM in 25 % NH3 aqueous solution under pressurized H2 gas (2.5 atm), and the highest yield approaches 60 % at 4.0 H2 atm. Comparison between the activities over four Ru-supported HAP catalysts prepared with different methods and the results of X-ray absorption spectroscopy suggested that the metallic Ru cluster is the active center for the reductive amination of furfural. Transmission electron microscope and inductively-coupled plasma analysis indicated that the as-prepared 5 wt% Ru-PVP/HAP catalyst possessed 4.0 wt% PVP-capped Ru clusters with average diameter of 1.7 ± 0.3 nm on HAP support. It was also demonstrated that the reductive amination approach with Ru-PVP/HAP catalyst, NH3 aq. and pressurized H2 gas has capability for transformation of aromatic aldehydes to the corresponding aromatic amines. According to these results, it is concluded that Ru(0) cluster supported on HAP will represent a suitable catalyst for widely-usable reductive amination to convert an aldehyde functionality towards an amine.

Selective Hydrogenation of Phenol to Cyclohexanone over Pd–HAP Catalyst in Aqueous Media

AbstractThe production of pure cyclohexanone under mild conditions over catalysts with high reactivity, selectivity, compatibility, stability, and low cost is still a great challenge. Here we report a hydroxyapatite‐bound palladium catalyst (Pd–HAP) to demonstrate its excellent performance on phenol hydrogenation to cyclohexanone. Based on catalyst characterization, the Pd nanoclusters (≈0.9 nm) are highly dispersed and bound to phosphate in HAP. Only basic active sites on HAP surface are detected. At 25 °C and ambient H2 pressure in water, phenol can be 100 % converted into cyclohexanone with 100 % selectivity. This system shows a universal applicability to temperature, pH, solvent, low H2 purity, and pressure. The catalyst reveals high stability to be recycled without deactivation or morphology change; and Pd nano‐clusters barely aggregate even at 400 °C. During the reaction, HAP adsorbs phenol, and Pd nanoclusters activate and spillover H2. The mechanism is also investigated, proposed, and verified.