Preparation of Mg–Al layered double hydroxides intercalated with alkyl sulfates and investigation of their capacity to take up N,N-dimethylaniline from aqueous solutions

This study examined the effect of the interlayer spacing of a Mg–Al layered double hydroxide (Mg–Al LDH) on the ability of the Mg–Al LDH to take up a nonionic organic material. Mg–Al LDHs, intercalated with 1-propanesulfonate (PS^?), 1-hexanesulfonate (HS^?), and 1-dodecanesulfonate (DS^?), were prepared by coprecipitation, yielding PS·Mg–Al LDH, HS·Mg–Al LDH, and DS·Mg–Al LDH, respectively. The increase in the alkyl chain lengths of the Mg–Al LDHs (PS^? < HS^? < DS^?) resulted in the perpendicular orientation of the organic acid anions in the interlayer of Mg–Al LDH, which in turn resulted in more organic acid anions being accommodated in the interlayer space. An organic acid anion with a large molecular length was more easily intercalated in the interlayer of Mg–Al LDH than one with a small molecular length. This was attributed to the hydrophobic interaction between the alkyl chains, affecting the intercalation of the organic acid anions. The uptake of N,N-dimethylaniline (DMA) by Mg–Al LDHs increased in the order PS·Mg–Al LDH < HS·Mg–Al LDH < DS·Mg–Al LDH. The uptake was attributed to the hydrophobic interactions between DMA and the intercalated PS^?, HS^?, and DS^?. Thus, Mg–Al LDH, which has a lot of large interlayer spacings when intercalated with organic acid anions, can take up a large number of DMA molecules from an aqueous solution.     

High-temperature transformations of Cu-rich hydrotalcites

CuM(II)Al ternary hydrotalcites (M(II) = Ni, Co and Mg) with a (Cu+M(II))/Al atomic ratio of 3.0 and Cu/M(II) atomic ratio of 5.0 were synthesized by coprecipitation under low supersaturation. Powder X-ray diffraction of the as-synthesized samples showed a pattern characteristic of hydrotalcite-like (HT-like) structure (JCPDS: 41-1428). Thermal analyses of these samples showed four stages of weight loss/heat change when recorded in nitrogen. Analysis of the evolved gases characterized the nature of these transformations. The thermoanalytical effects differed significantly especially for the high-temperature transformations, when the treatment was performed in oxygen. In situ powder X-ray diffraction of the samples was carried out to elucidate the phase evolution of these compounds. Surprisingly formation of CuO was noted at temperatures around 200°C well below the destruction of the layered network. The nature of the resulting phases varied with both the nature of the co-bivalent metal ion and the heating atmosphere. FT-IR spectroscopy confirmed the retention of carbonate ions at higher temperatures (above 700°C), although the concentration of carbonate anion (most likely unidentate) varied with the calcination temperature. The crystallinity of CuO increased significantly above 600°C, probably through dissociation of copper oxycarbonate. Significant differences in the thermal transformation temperatures (for the third and the fourth transformations) of these samples containing different co-bivalent metal ions were not observed. This suggests that an association of the co-bivalent metal ions and/or trivalent metal ion in this phase is unlikely. A plausible thermal evolution scheme of these hydrotalcites is proposed.     

Iron-57 Mössbauer effect study of the distribution of divalent and trivalent ions in potassium transition metal fluorides having the tetragonal bronze structure

Mössbauer studies are reported for compounds of the type KM^IIM^IIIF₆ (M = first-row transition metal ion, Zn, or Mg) which have the tetragonal bronze structure. The results of this investigation provide evidence that the trivalent ions are located on the 8(j) sites of the bronze structure and that the divalent ions are distributed over both the 8(j) and 2(c) sites.     

Thermodynamic equilibrium analyses of the uptake of aromatic compounds from an aqueous solution by magnesium–aluminum (Mg–Al) layered double hydroxide intercalated with 1-naphthol-3,8-disulfonate

Magnesium–aluminum layered double hydroxide (Mg–Al LDH) intercalated with 1-naphthol-3,8-disulfonate (1-N-3,8-DS²⁻) was prepared by coprecipitation. Thermodynamically, the prepared Mg–Al LDH showed greater preferential uptake of 1,3-dinitrobenzene (DNB) than of 1,2-dimethoxybenzene (DMB). This preferential uptake of aromatic compounds, which is adequately expressed by the Dubinin–Radushkevich adsorption isotherm, was attributed to the π–π stacking interactions between the benzene ring of the aromatic compounds and the naphthalene core of 1-N-3,8-DS²⁻ intercalated in the interlayer spaces of Mg–Al LDH. Negative values of ΔG for DNB and DMB indicate that the adsorption process is spontaneous at all temperatures. The value of ΔS for DNB was much lower than that for DMB. This implies that DNB was far more strongly adsorbed to 1-N-3,8-DS²⁻ than was DMB, resulting in a lower degree of freedom for and higher uptake of DNB than those in the case DMB. The absolute values of |ΔH| for DNB and DMB were less than 20 kJ mol⁻¹, indicating that the uptake of DNB or DMB by 1-N-3,8-DS·Mg–Al LDH can be considered a physical adsorption process caused by π–π stacking interactions.     

Synthesis and adsorption properties of p-sulfonated calix[4 and 6]arene-intercalated layered double hydroxides

The intercalation of water-soluble p-sulfonated calix[4 and 6]arene (CS4 and CS6) in the interlayer of the Mg-Al and Zn-Al layered double hydroxide (LDH) by the coprecipitation method has been investigated, as well as the adsorption properties of the resulting CS/LDHs for benzyl alcohol (BA) and p-nitrophenol (NP) to prepare new microporous organic-inorganic hybrid adsorbents. The amount and arrangement of CS intercalated was different by the kind of the host metal ions. CS4 cavity axis was perpendicular for the Mg-Al LDH basal layer and parallel for the Zn-Al LDH basal layer, while CS6 cavity axis was perpendicular for both the LDH basal layers. In the BET surface area measurement, the surface area of the Zn-Al/CS4/LDH was four times than that of the Mg-Al/CS4/LDH, expecting that the former has higher adsorption capacity than the latter. In fact, the adsorption ability of the CS/LDHs for BA and NP in aqueous solution was found to be larger in the Zn-Al/CS4/LDH than in the Mg-Al/CS4/LDH. In addition, the adsorption ability of both the LDHs was larger in the CS6/LDHs than in the CS4/LDHs. These results were explained by the difference in the amount and arrangement of CS intercalated in the LDH interlayer space.     

Structural arrangements of the ternary metal boride carbide compounds MB2C4 (M=Mg, Ca, La and Ce) from first-principles theory

The structural arrangements of the ternary metal borocarbides MB₂C₄ (M=Mg, Ca; La and Ce) are investigated using density-functional theory (DFT) calculations within the generalized gradient approximation (GGA). Results indicate that these compounds adopt a layered structure consisting of graphite-like B₂C₄ layers alternating with metal sheets. Within the hexagonal layers, the coloring with the -C-C-C-B-C-B- sequence is energetically more stable than that with the -C-C-C-C-B-B- one. The electronic structures of these compounds, mainly determined by the B₂C₄ sheets, can be rationalized with the simple valence electron distribution M²⁺[B₂C₄]²⁻xe⁻, with the metals essentially acting as two-electron donors with respect to the boron-carbon network, the other x electrons remaining in the relatively narrow d and/or f bands of the metals. Accordingly, MB₂C₄ are narrow band-gap semiconductors (ΔE≈0.2-0.4 eV) with M=Mg and Ca. On the other hand, with M=La and Ce, the compounds are conducting with a relatively high density of states at the Fermi level predominantly metal in character with substantial B/Cπ* antibonding state admixture.     

Aldol condensation of furfural and acetone on layered double hydroxides

The Aldol condensation of furfural (Fur) with acetone (Ac) to 4-(2-Furyl)-3-buten-2-one (FAc) is one of the most important processes in the aqueous-reforming of oxygen-containing biomass derivatives and has been carried out in the presence of solid-base catalysts, calcined-rehydrated Layered Double Hydroxides (LDH). The Mg-Al Layered Double Hydroxides has been prepared by the coprecipitation, calcination and regeneration from mixed oxides by rehydration. The catalyst prepared with different Mg/Al molar ratios showed different catalytic performance and the best catalyst was with the Mg/Al molar ratio of 2.5. Phenol adsorption showed that the best catalyst had the largest numbers of accessible basic sites. The appropriate rehydration temperature and time for mixed oxides obtained by calcination were also investigated. The Mg-Al LDH catalysts can be regenerated by calcination at 773 K and rehydration in decarbonate water, but the regeneration is complex and incomplete. In addition, the catalyst calcined at high temperature also had activity, which was attributed to the formation of the Mg-Al spinels.     

Structure and photoluminescence of Mg-Al-Eu ternary hydrotalcite-like layered double hydroxides

A series of Mg-Al-Eu ternary hydrotalcite-like layered double hydroxides (LDHs), with Eu/Al atomic ratios of ∼0.06 and Mg/(Al+Eu) atomic ratios ranging from 1.3 to 4.0, were synthesized by a coprecipitation method. The Mg-Al-Eu ternary LDHs were investigated by various techniques. X-ray diffraction (XRD) results indicated that the crystallinity of the ternary LDHs was gradually improved with the increase of Mg²⁺/(Al³⁺+Eu³⁺) molar ratio from 1.3/1 to 4/1, and all the samples were a single phase corresponding to LDH. The photoluminescent (PL) spectra of the ternary Mg-Al-Eu LDHs were described by the well-known ⁵D₀-⁷F_J transition (J=1, 2, 3, 4) of Eu³⁺ ions with the strongest emission for J=2, suggesting that the host LDH was favorable to the emissions of Eu³⁺ ions. The asymmetry parameter (R) relevant to ⁵D₀-⁷F_J transition (J=1, 2) dependant of the atomic ratios of Mg²⁺/(Al³⁺+Eu³⁺) was discussed, and was consistent with the result of XRD.     

Sulfonylcalix[4]arenetetrasulfonate as pre-column chelating reagent for selective determination of aluminum(III), iron(III), and titanium(IV) by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection

Sulfonylcalix[4]arenetetrasulfonate (SO₂CAS) has been examined as a pre-column chelating reagent for ultratrace determination of metal ions by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection. Metal ions were converted into the SO₂CAS chelates in an acetic buffer solution (pH 4.7). The chelates were injected onto a n-octadecylsilanized silica-type Chromolith™ Performance RP-18e column and were eluted using a methanol (50 wt.%)-water eluent (pH 5.6) containing tetra-n-butylammonium bromide (7.0 mmol kg⁻¹), acetate buffer (5.0 mmol kg⁻¹), and disodium ethylendiamine-N,N,N′,N′-tetraacetate (0.10 mmol kg⁻¹). Under the conditions used, Al(III), Fe(III), and Ti(IV) were selectively detected among 21 kinds of metal ions [Al(III), Ba(II), Be(II), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ga(III), Hf(IV), In(III), Mg(II), Mn(II), Mo(VI), Ni(II), Pb(II), Ti(IV), V(V), Zn(II), and Zr(IV)]. The detection limits on a 3σ blank basis were 8.8 nmol dm⁻³ (0.24 ng cm⁻³) for Al(III), 7.6 nmol dm⁻³ (0.42 ng cm⁻³) for Fe(III), and 17 nmol dm⁻³ (0.80 ng cm⁻³) for Ti(IV). The practical applicability of the proposed method was checked using river and tap water samples.     

Synthesis and characterization of Mg–M (M: Al,Fe, Cr) layered double hydroxides and their application in the hydrogenation of benzaldehyde

Layered double hydroxides or hydrotalcite-like compounds with different kinds of metal ions (Mg–Al, Mg–Fe and Mg–Cr) in the brucite-like sheets were prepared by a co-precipitation method with Mg/M³⁺ molar ratio of ~2. The hydrotalcites were characterized by chemical analysis, X-ray diffraction, Fourier transform infrared spectroscopy, temperature programmed reduction, SEM microscopy, and specific surface area measurements. The activity is evaluated for benzaldehyde reaction. The selectivity to benzyl alcohol is always 90 % even though benzaldehyde conversion depends on the nature of the metal active phase and reaction conditions.     

Crystal structure, optical properties and colouring performance of karrooite MgTi2O5 ceramic pigments

Karrooite, MgTi₂O₅, is a promising ceramic pigment due to its high refractoriness and refractive indices, as well as its ability to host transition metal ions in two crystallographically distinct octahedral sites. The colouring performance was investigated combining X-ray powder diffraction with UV-vis-NIR spectroscopy on karrooite doped with V, Cr, Mn, Fe, Co or Ni (M) according to the formula Mg_1−xTi_2−xM_2xO₅, with x=0.02 and 0.05. Transition metals solubility in the karrooite lattice is not complete and a second phase is always present (geikielite or rutile). Structural data proved that incorporation of different chromophore ions into the karrooite structure affects unit cell parameters, bond length distances and angles, site occupancies and therefore cation order-disorder. Optical spectra exhibit broad absorbance bands of Co(II), Cr(IV), Fe(III), Mn(II), Mn(III), Ni(II), V(IV) with distinct contributions by cations in the M₁ and M₂ sites. Karrooite pigments have colours ranging from orange to brown-tan (Cr, Fe, Mn, V) to green (Co) and yellow (Ni) that are stable in low-temperature (<1050 °C) ceramic glazes and glassy coatings.     

Comparative Study of Mg/M(III) (M=Al, Ga, In) Layered Double Hydroxides Obtained by Coprecipitation and the Sol-Gel Method

Various layered double hydroxides (LDHs) consisting of magnesium and a trivalent metal (Al, Ga or In) in an Mg/M(III) ratio of 3 were prepared by precipitation from the corresponding nitrates and also from magnesium ethoxide and the acetylacetonates of the trivalent metals using the sol-gel method. The six LDHs thus obtained were calcined at 500°C. All solids were characterized by XRD and IR spectroscopy prior to and after calcination. Their textural properties were determined from nitrogen adsorption measurements and their surface chemical properties by CO₂ chemisorption.     

Thiacalix[4]arenetetrasulfonate as specific pre-column chelating reagent for nickel(II) ion in kinetic differentiation mode high-performance liquid chromatography

Thiacalix[4]arenetetrasulfonate (TCAS) has been examined as a pre-column chelating reagent for the determination of trace metal ions by kinetic differentiation mode (KD) ion-pair reversed-phase high-performance liquid chromatography (HPLC) with spectrophotometric detection. Among 14 kinds of common metal ions tested here, viz. Al(III), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Hg(II), Mg(II), Mn(II), Ni(II), Pb(II), V(V), and Zn(II) ion, only Ni(II) ion was detected as the TCAS chelate in the HPLC separation stage in spite of TCAS forming the chelates with various metal ions except for Al(III), Ca(II), and Mg(II) at the pre-column chelation stage. The undetected metal-TCAS chelates seemed to be dissociated on an HPLC column where no added TCAS was present in the mobile phase because of their kinetic unstability. The calibration graph for Ni(II) ion gave a wide linear dynamic range (40-20,000 nM) with the very low detection limit (DL) (3σ base-line fluctuation) to be 5.4 nM (0.32 ng ml⁻¹). The practical applicability of the KD-HPLC method with TCAS was demonstrated with the determination of trace Ni in coal fly ash.     

NMR Crystallography Reveals Carbonate Induced Al-Ordering in ZnAl Layered Double Hydroxide

Layered double hydroxides (LDHs) serve a score of applications in catalysis, drug delivery, and environmental remediation. Smarter crystallography, combining X-ray diffraction and NMR spectroscopy revealed how interplay between carbonate and pH determines the LDH structure and Al ordering in ZnAl LDH. Carbonate intercalated ZnAl LDHs were synthesized at different pH (pH 8.5, pH 10.0, pH 12.5) with a Zn/Al ratio of 2, without subsequent hydrothermal treatment to avoid extensive recrystallisation. In ideal configuration, all Al cations should be part of the LDH and be coordinated with 6 Zn atoms, but NMR revealed two different Al local environments were present in all samples in a ratio dependent on synthesis pH. NMR-crystallography, integrating NMR spectroscopy and X-ray diffraction, succeeded to identify them as Al residing in the highly ordered crystalline phase, next to Al in disordered material. With increasing synthesis pH, crystallinity increased, and the side phase fraction decreased. Using ¹H−¹³C, ¹³C−²⁷Al HETCOR NMR in combination with ²⁷Al MQMAS, ²⁷Al-DQ-SQ measurements and Rietveld refinement on high-resolution PXRD data, the extreme anion exchange selectivity of these LDHs for CO₃²⁻ over HCO₃⁻ was linked to strict Al and CO₃²⁻ordering in the crystalline LDH. Even upon equilibration of the LDH in pure NaHCO₃ solutions, only CO₃²⁻ was adsorbed by the LDH. This reveals the structure directing role of bivalent cations such as CO₃²⁻ during crystallization of [M²⁺₄M³⁺₂(OH)₂]²⁺[A²⁻]₁⋅yH₂O LDH phases.     

New basic catalysts obtained from layered double hydroxides nanocomposites

A new route for the preparation of basic mixed oxides using nanocomposite precursors obtained from layered double hydroxides (LDH) was investigated. These nanocomposites have been prepared by intercalation of negatively charged guest entities containing Ca²⁺, Sr²⁺, Ba²⁺ or La³⁺ cations in the interlayer space of host Mg/Al LDH by anionic exchange. The guest entities have been previously prepared by complexation of the required cations in the presence of edta or citrate chelating anions. Intercalation of [Mⁿ⁺(edta)]^(4?n)? or [La(cit)OH]^? complexes is proved by elemental analysis, XRD analysis and FT-IR spectroscopy. However, in order to satisfy the charge equilibrium in the materials, (edta)^4? and (citrate)^3? species are also co-intercalated in the nanocomposites. The basic properties of the mixed oxides obtained after thermal decomposition of the nanocomposites precursors were evaluated in the disproportionation of 2-methyl-3-butyn-2-ol (MBOH) and the transesterification of 1-phenylethanol with diethylcarbonate (DEC). The Sr- and Ba-containing mixed oxides exhibit basicity close to the one of MgO and Mg(La)O mixed oxides. A comparative study of the reactivity of La-containing mixed oxides obtained following different preparation routes, i.e. coprecipitation or anionic exchange, allows to conclude that the nanocomposite route led to the most active samples.     

Substitutional Effects of 3d Transition Metals on the Magnetic and Structural Properties of Quasi-Two-Dimensional La5Mo4O16

Substituted phases with the composition La₅Mo_4−xT_xO_16−δ (T=Co, Fe, Mn, and Mg and x∼0.7) were prepared by fused-salt electrolysis and/or conventional solid-state methods. The crystal structure of the parent compound, La₅Mo₄O₁₆, contains perovskite-like corner-sharing MoO₆ octahedral units in the ab plane separated by Mo₂O₁₀ bioctahedral units along the c direction. Detailed single-crystal X-ray diffraction studies on the Co-substituted phase, La₅Mo_3.31Co_0.69O_16−δ, indicated that the unit cell is triclinic (space group C-1) with Co exclusively replacing Mo atoms in the perovskite layers. X-ray absorption measurements revealed that the transition metal ions are divalent, consistent with the crystal structure analysis. The anomalous magnetic transition observed at 180 K in the parent compound shifts to lower temperatures upon substitution with transition metal ions. No long-range magnetic order was evident in the Mg²⁺-substituted compositions. The electrical resistivity of all the substituted phases was at least 3 orders of magnitude higher than that of the parent compound. Variations in the magnetic and electrical properties have been ascribed to the disruption of exchange correlations caused by substitutional disorder at the Mo sites.     

Mg-Al类水滑石负载金催化醇选择氧化中Mg/Al比例的影响

为研究Mg/Al比例对Mg-Al类水滑石(LDH)负载Au催化醇选择氧化的影响,采用共沉淀—水热晶化法合成了不同Mg/Al比的y Mg-Al LDH,采用液相还原法负载纳米Au颗粒.对样品进行XRD、N_2物理吸附、ICP-AES、AAS、TEM、CO_2-TPD、CO_2-In-situ DRIFTS和XPS等表征.在无附加碱条件下,Au/yMg-Al LDH催化剂催化1-苯乙醇选择氧化的催化活性随Mg/Al比增大呈现递增趋势,Au/4Mg-Al LDH活性最佳.载体表面弱碱性强度随Mg/Al比增大变化不大,弱碱位略有增多,对醇羟基脱氢有促进作用.载体层板Mg_3OH基团随Mg/Al比增大而增多有利于Au在层板边缘沉积,二者可形成有效协同,促进醇氧化过程进行.     

Periodic trends in metal–metal bonding in edge-shared [M2Cl10] systems

Periodic trends in metal–metal interactions in edge-shared [M₂Cl₁₀]⁴⁻ systems, involving the transition metals from groups 4 through 8 and electronic configurations ranging from d¹d¹ through d⁵d⁵, have been investigated by calculating metal–metal bonding and spin-polarization (exchange) effects using density functional theory. The trends found in this study are compared with those for the analogous face-shared [M₂Cl₉]³⁻ systems reported in earlier work. Strong linear correlations between the metal–metal bonding and spin-polarization terms have been obtained for all groups considered. In general, spin polarization and electron localization are predominant in 3d–3d species whereas electron delocalization and metal–metal bonding are favoured in 5d–5d species, with more variable results observed for 4d–4d systems. As previously found for face-shared [M₂Cl₉]³⁻ systems, the strong correlations between the metal–metal bonding and spin polarization energy terms can be related to the fact that both properties appear to be similarly affected by the changes in the metal orbital properties and electron density occurring within the dⁿdⁿ groups. A significant difference between the face-shared and edge-shared systems is that while the 4d metals in the former show a strong tendency for delocalized metal–metal bonded structures, the edge-shared counterparts display much greater variation with both metal–metal bonded and weakly coupled complexes observed. The tendency for weaker metal–metal interactions can be traced to the inability of the edge-shared bridging structure to accommodate the smaller metal–metal distances required for strong metal–metal bonding.     

喜树碱插层的镁铝型层状双金属氢氧化物的合成及表征

采用共沉淀法把抗癌药物喜树碱（Camptothecin, CPT）插入层状双金属氢氧化物(layered double hydroxide, LDH)层间, 合成了CPT-LDH纳米杂化物。结果表明,在CPT-LDH纳米杂化物中,CPT在层间的排布方式有两种,即平行于层板的单层排列和垂直于层板的双层排列;缓释研究表明,CPT-LDH在pH 7.5的磷酸缓冲液中具有明显的缓释效果,其释放速率较相同pH值时CPT和LDH物理混合物的释放速率明显降低;考察了CPT-LDH的药物释放机理,在 pH 7.5的缓冲溶液中,释放过程受粒内扩散过程控制;CPT-LDH纳米杂化物的释放动力学符合准一级动力学过程。     

＂Intelligent＂ reforming catalysts： Trace noble metal-doped Ni/Mg（A1）O derived from hydrotalcites

Trace amounts of noble metal-doped Ni/Mg(Al)O catalysts were prepared starting from Mg-Al hydrotalcites (HTs) and tested in daily start-up and shut-down (DSS) operation of steam reforming (SR) of methane or partial oxidation (PO) of propane. Although Ni/Mg(Al)O catalysts prepared from Mg(Ni)-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg(Al)O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR ofmethane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a “memory effect” of HTs. Moreover, the noble metal-doped Ni/Mg(Al)O catalysts exhibited “intelligent” catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2+ in Mg(Ni,Al)O periclase to Ni0 assisted by hydrogen spillover from Pt (or Pt-Ni alloy). The self-regenerative activity was accomplished by self-redispersion of active Ni0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg(Al)O periclase crystal; surface Ni0 was oxidized to Ni2+ by steam and incorporated into Mg(Ni2+,Al)O periclase, whereas the Ni2+ in the periclase was reduced to Ni0 by the hydrogen spillover and appeared as the fine Ni0 particles on the catalyst surface. Further a “green” preparation of the Pt/Ni/[Mg3.5Al]O catalysts was accomplished starting from commercial Mg3.5-Al HT by calcination, followed by sequential impregnation of Ni and Pt.