Solid-state 13C CPMAS Research Articles

Linking plant phytochemistry to soil processes and functions: the usefulness of 13C NMR spectroscopy

The organic matter cycle is one of the most fundamental processes in ecosystems affecting the soil and controlling its functions. The soil complex microbiome is made up of thousands of bacterial and hundreds of fungal strains that coexist on the many different available organic carbon sources. In natural plant communities, freshly fallen leaf-litter and dead roots are subject to decomposition by a complex food-web composed of both microbial saprotrophs and invertebrate detritivores. The litter chemical composition varies dramatically among species in relation to plant life forms (conifer, broadleaf, nitrogen-fixing, graminoid) and, within species, with plant organs (leaf, root, woody tissues). This paper reviews the usefulness of advanced chemical technologies to study the composition of both plant litter and organic amendments, supporting the description of their mechanism of action and attention to their potential applications. First, a critical review is presented on the limitations of C/N and lignin/N ratios, still widely used as basic indicators of litter chemistry. Second, the potential of the solid state 13C-CPMAS NMR is reported as a powerful tool to assess the chemical composition of both litter and organic amendments. Finally, six different study cases are reported to provide evidence of the usefulness of such metabolomic approach for the description of organic matter chemistry aimed to an effective prediction of its impact on soil ecosystem functions.

Synthesis, Characterization, and Solid State Dynamic Studies of a Hydrogen Bond-Hindered Steroidal Molecular Rotor with a Flexible Axis.

A novel steroid molecular rotor was obtained in four steps from the naturally occurring spirostane sapogenin diosgenin. The structural and dynamic characterization was carried out by solution NMR, VT X-ray diffraction, solid state 13C CPMAS, and solid state 2H NMR experiments. They allowed the identification of a fast dynamic process with a frequency of 14 MHz at room temperature, featuring a barrier to rotation Ea = 7.87 kcal mol-1. The gathered experimental evidence indicated the presence of a hydrogen bond that becomes stronger as the temperature lowers. This interaction was characterized using theoretical calculations, based on topological analyses of the electronic density and energies. In addition, combining theoretical calculations with experimental measurements, it was possible to propose a partition to Ea (∼8 kcal/mol) into three contributions, that are the cost of the intrinsic rotation (∼2 kcal/mol), the hydrogen bond interaction (∼2 kcal/mol), and the packing effects (∼2-3 kcal/mol). The findings from the present work highlight the relevance of the individual components in the function of molecular machines in the solid state.

Synthesis of ferrocenylazobenzene-functionalized MCM-41 via direct co-condensation method

Ferrocenylazobenzene-functionalized mesoporous MCM-41 material (Fc-Az-M14), was synthesized directly through co-condensation of 4-triethoxysilyl-3′-ferrocenylazobenzene (TEFA) and tetraethyl orthosilicate (TEOS), under basic conditions, using cetyltrimethylammmonium bromide (CTAB) as structure-directing agent. The template was removed through solvent extraction, to yield the ferrocenylazobenzene-containing ordered mesoporous organosilicas Fc-Az-M41. The prepared material was characterized by nitrogen adsorption, X-ray diffraction (XRD), solid state 29Si MAS NMR and 13C CP-MAS NMR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Thermogravimetric analysis (TGA) and diffuse reflectance UV-Vis spectroscopy (DR UV). The results showed that Fc-Az-M41 had an ordered two-dimensional hexagonal mesostructure, high BET surface area and pore volume. The pore diameter, BET surface area, and pore volume of the extracted material were 3.8 nm, 1070 m2/g and 0.80 cm3/g, respectively. The mean pore diameters of MCM-41 clearly decreased by ca. 0.65 nm upon incorporation of Fc-Az groups. UV-Vis spectrum of Fc-Az-M41 was determined by a diffuse reflectance method after UV irradiation. The presence of the azobenzene chromophores in this material can be clearly observed in the DR UV-Vis spectra of surfactant-free Fc-Az-M41. This spectra shows that the framework of this material is formed predominantly by trans isomer, and the π-π* and the n-π* absorption bands were affected by metal-to-ligand charge transfer (MLCT).

A novel hybrid of β-cyclodextrin grafted onto activated carbon for rapid adsorption of naphthalene from aqueous solution

A novel hybrid material was prepared by grafting β-cyclodextrin (β-CD) onto the surface of oxidized AC for the rapid adsorption of naphthalene. AC and CDACs were characterized using the N2 adsorption–desorption method, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and solid state CP MAS 13C NMR. All the results demonstrate that β-CD grafted successfully onto AC. Batch experimental adsorption datas had a higher correlation to Freundlich isotherm model and the pseudo-second-order model. The adsorption equilibrium capacity of 178.73mg·g−1 was reached in just 10s at an AC/β-CD grafting ratio value of 1:1. It had a faster adsorption rate than many reported adsorbents. Additionally, the positive free energy change (∆G°), and the positive enthalpy change (∆H°) suggest that it is a viable, spontaneous and endothermic process, which will provided a new path to a highly-efficient and fast-adsorption-rate adsorbent for naphthalene or its analogues discharged into the environment.

Preparation of chitosan sulfate and vesicle formation with a conventional cationic surfactant

Chitosan of high molecular weight and 85% deacetylation was used to prepare chitosan sulfate (CHS) by employing an industrial recognized green and highly reactive sulfating agent gas SO3. FT-IR and solid-state CP-MAS 13C NMR spectra confirmed that sulfate groups were successfully introduced into chitosan chains with a sulfur content of 16.50% and the substitution degree of 1.75 according to the results of elemental analysis. The aggregation behavior of the mixture of chitosan sulfate polyelectrolyte and oppositely charged surfactant cetyltrimethylammonium bromide (CTAB) was characterized by surface tension, steady-state fluorescent, turbidity, ζ potential and transmission electron microscopy. The results indicate that the CHS/CTAB mixture has pretty high surface activity and low critical aggregation concentration. The CHS/CTAB mixture successively forms spherical aggregates, precipitation, vesicles and micelle aggregates coated by CHS chains by increasing surfactant concentration due to the cooperative hydrophobic and electrostatic interactions.

Charcoal in Organic Horizon and Surface Mineral Soil in a Boreal Forest Fire Chronosequence of Western Quebec: Stocks, Depth Distribution, Chemical Properties and a Synthesis of Related Studies

Wildfires are a major driver of carbon stocks and ecosystem development in Canadian boreal forests, but there is little information on amounts and properties of the charcoal produced. Using data and samples available from a previous study, we determined amounts, depth distribution and chemical properties of visually-determined charcoal (> 2 mm) in a boreal chronosequence in the Abitibi region of Quebec, Canada. Sites ranged from 24 to 2355 years since fire (ysf) and originated from low- and high-severity soil burns (> 5 cm or < 5 cm organic horizon unburned, respectively). Two or three pits were sampled at 1-cm depth intervals from 20 jack pine (Pinus banksiana) sites (one low severity and 19 high severity) and 31 black spruce (Picea mariana) sites (12 low severity and 19 high severity). Site-level charcoal stocks ranged from 50 to 5527 kg ha-1 with high within-site variability and lower stocks for the oldest sites. Depth distributions typically peaked around the organic-mineral interface, but some low-severity sites also had charcoal layers within the organic horizon. Means from 30 samples were 569 mg g-1 total C, 4.1 mg g-1 total N and 140 C/N (molar), with total C and C/N showing a trend of decline with time since fire, and total N showing an increase. Solid-state 13C CPMAS NMR spectra of nine samples showed high variability among the younger samples, but a trend to higher aromaticity for the older ones. A literature survey focusing on boreal forests similarly showed highly variable stocks and chemical properties of charcoal in organic horizon and upper mineral soil, with reduction of variance and lower stocks after several hundred years. This initial variation was also consistent with reports of highly variable temperatures and duration of charring in wildfires. Adding reports available for char production, and considering that most studies of char stocks and production are limited to the organic horizon (forest floor), suggests that initial production of charred material from boreal wildfires might be around 5-10 tonnes ha-1.

Mechanism of Initiation in the Phillips Ethylene Polymerization Catalyst: Ethylene Activation by Cr(II) and the Structure of the Resulting Active Site

The structure and mechanism of the formation of sites which initiate ethylene polymerization in the atomically dispersed Phillips catalyst (Cr/SiO2) are two of the great unsolved mysteries of heterogeneous catalysis. After CO or C2H4 reduction of silica-supported CrVI ions to CrII ions in the precatalyst, exposure to ethylene results in the formation of organoCrIII sites that are capable of initiating polymerization without recourse to an external alkylating cocatalyst. In this work, a Phillips catalyst prepared, via sol–gel chemistry, as a mesoporous, optically transparent monolith was reduced with CO to the spectroscopically determined CrII end point. Ethylene causes rapid reoxidation of these CrII sites to CrIII, even at low temperatures. Solid-state 13C CP-MAS NMR, IR, and Raman spectroscopies reveal that the resulting sites contain a vinyl ligand, described as (≡SiO)2CrIII–CH═CH2 although likely with a higher coordination number, which are capable of initiating polymerization. The formation of these ...

Heteroatom-rich porous organic polymers constructed by benzoxazine linkage with high carbon dioxide adsorption affinity

We report the synthesis and characterization of a new type of porous organic polymers linked by benzoxazine. The polymers were readily synthesized by condensation reaction of diamines, triphenol and paraformaldehyde. The formation of the linkage and porous structures were studied by infrared spectroscopy, solid-state 13C-CP MAS NMR and nitrogen sorption measurements. The porosity study revealed the resultant polymers are porous materials with surface area as high as 231m2g−1. Benzoxazine backbone endows the polymers with abundant heteroatoms (N and O), which makes these polymers promising candidates for carbon dioxide adsorption and storage. We found that the best polymer showing the highest carbon dioxide adsorption up to 6.81wt% at 273K and 1bar, which is due to the most microporous structure and largest adsorption affinity. These results demonstrate a convenient approach to synthesize heteroatom-rich porous organic polymers for gas adsorption and storage.

A multi-technique approach to assess the fate of biochar in soil and to quantify its effect on soil organic matter composition

Differentiation of biochar and native soil organic matter (SOM) is required to assess the effect of biochar amendment on in-situ changes of SOM. Therefore, we used C4 biochar produced at high temperature (1200°C) by gasification (BCGS) and measured the 13C abundance of density and particle size fractions. We quantified the BCGS effects on distinct native C3-SOM pools of a grassland topsoil one year after BCGS amendment. The chemical composition was analyzed with solid-state 13C CPMAS NMR, whereas information on the nanostructure of BCGS were obtained by Raman microspectroscopy measurements. Our aim was to assess BCGS induced chemical changes of SOM and physical fractions and to validate the accuracy of BCGS detection by 13C NMR spectroscopy. Quantification by isotopic measurements and 13C NMR spectroscopy for aromatic C yielded similar estimates of BC in soils. Of the total BCGS, 52% were recovered as free particulate organic matter (POM) and 33% were located in aggregated soil structures isolated as occluded POM particles. Around 4% of the total BCGS was detected in the clay fraction. After one year of field exposure, the surface of the BCGS particles decreased in unordered graphitic-like structures. The higher ordered BC residue is supposed to be more recalcitrant. The native SOC stock increase (p=0.06, n=4) in the clay fraction indicated increased sequestration of organic matter as mineral-bound SOM due to BCGS amendment. With respect to soil functionality, the BCGS amendment induced a tremendous shift from a soil system dominated by organo-mineral associations to POM−dominated OC storage, resulting in increased soil air capacity.

Effect of feedstock and pyrolysis temperature on properties of biochar governing end use efficacy

The aim of this study was to systemically evaluate how feedstock characteristics and temperature influence biochar evolution during pyrolysis and to establish their relationships with biochar potential for soil amendments. We produced four biochar thermosequences from oak, pine, sugarcane and peanut shell at twelve temperatures (350–900 °C), and characterised them by yield, proximate analysis, elemental analysis, pH, electrical conductivity (EC) and carbon (C) functional groups using FTIR and solid-state 13C CPMAS NMR spectroscopy, along with principal component and cluster analyses. The results showed that not all biochar properties changed consistently with increasing pyrolysis temperature during slow pyrolysis. The significant increase in biochar pH with increasing pyrolysis temperature, was only observed between 350 and 500 °C (p < 0.05). Three principal components (PC) explained 88.9% of the variances in biochars. PC1 (ash, Mn, K, Fe, N, P and EC) and PC3 (Ca, Na and Mg) scores were essentially determined by feedstock type with notable influence of low pyrolysis temperatures. PC2 (O, H, C, volatile matter, fixed matter and pH) score was greatly influenced by pyrolysis temperature. Sugarcane derived biochars had high PC1 score but low PC3 score, while peanut shell derived biochars were contributed by both PC1 and PC3. The wood derived biochars had low scores of both PC1 and PC3, but the low temperature end of wood derived biochar thermosequences had significant higher PC2 scores than the high temperature end (p < 0.05). Understanding how biochar feedstock characteristics and pyrolysis temperature regulate biochar evolution will benefit tailored biochar manufacture.

Selective CO2 Sequestration with Monolithic Bimodal Micro/Macroporous Carbon Aerogels Derived from Stepwise Pyrolytic Decomposition of Polyamide-Polyimide-Polyurea Random Copolymers.

Polymeric aerogels (PA-xx) were synthesized via room-temperature reaction of an aromatic triisocyanate (tris(4-isocyanatophenyl) methane) with pyromellitic acid. Using solid-state CPMAS 13C and 15N NMR, it was found that the skeletal framework of PA-xx was a statistical copolymer of polyamide, polyurea, polyimide, and of the primary condensation product of the two reactants, a carbamic-anhydride adduct. Stepwise pyrolytic decomposition of those components yielded carbon aerogels with both open and closed microporosity. The open micropore surface area increased from <15 m2 g-1 in PA-xx to 340 m2 g-1 in the carbons. Next, reactive etching at 1,000 °C with CO2 opened access to the closed pores and the micropore area increased by almost 4× to 1150 m2 g-1 (out of 1750 m2 g-1 of a total BET surface area). At 0 °C, etched carbon aerogels demonstrated a good balance of adsorption capacity for CO2 (up to 4.9 mmol g-1), and selectivity toward other gases (via Henry's law). The selectivity for CO2 versus H2 (up to 928:1) is suitable for precombustion fuel purification. Relevant to postcombustion CO2 capture and sequestration (CCS), the selectivity for CO2 versus N2 was in the 17:1 to 31:1 range. In addition to typical factors involved in gas sorption (kinetic diameters, quadrupole moments and polarizabilities of the adsorbates), it is also suggested that CO2 is preferentially engaged by surface pyridinic and pyridonic N on carbon (identified with XPS) in an energy-neutral surface reaction. Relatively high uptake of CH4 (2.16 mmol g-1 at 0 °C/1 bar) was attributed to its low polarizability, and that finding paves the way for further studies on adsorption of higher (i.e., more polarizable) hydrocarbons. Overall, high CO2 selectivities, in combination with attractive CO2 adsorption capacities, low monomer cost, and the innate physicochemical stability of carbon render the materials of this study reasonable candidates for further practical consideration.

Crystal structure, quantum mechanical study and spectroscopic studies of nitrate and perchlorate salts of 3-chloroaniline, [C6H7ClN]NO3 (I) and [C6H7ClN]ClO4 (II)

Two new organic-inorganic hybrid compounds, 3-chloroanilinium nitrate (I) and 3-chloanilinium perchlorate (II), have been synthesized by an acid/base reaction at room temperature in the presence of 3-chloroaniline as an organic-structure directing agent and their structures were determined by single crystal X-ray diffraction. Compound I, [C6H7ClN]NO3, crystallizes in the orthorhombic space group Pbca with a = 10.4137(16), b = 9.6232(11), c = 16.059(2) Å, V = 1609.3(4) and z = 8. Full-matrix least-squares refinement converged at R = 0.041 and Rw = 0.121. Compound II, [C6H7ClN]ClO4, belongs to the monoclinic system, space group P21/n with the following parameters: a = 10.684(2), b = 7.2667(12), c = 12.229(2) Å, β = 104.27(2)°, V = 920.1(3) and z = 4. The structure was refined to R = 0.054 and Rw = 0.102.Both salts form anionic parallel layers alternating with thick slabs of [C6H7NCl]+ organic molecules. Charge balance is achieved by the protonated amine which interacts with the inorganic framework through hydrogen bonding. Solid-state 13C CP-MAS NMR spectroscopy is in agreement with the X-ray structures. Ab initio calculations allow the partial attribution of carbon signals to the various atoms of the organic groups. Electronic properties such as HOMO and LUMO energies were studied by Quantum mechanical evaluation by using the B3LYP/6-31+G* method.

Synthesis and characterization of two organic cation hydrogensulfates: 1-(2,5-dimethylphenyl)piperazine-1,4-diium bis(hydrogensulfate) monohydrate (SI) and 1-(2,3-dimethylphenyl)piperazine-1,4-diium bis(hydrogensulfate) (SII)

Treatment of 1-(2,5-dimethylphenyl)piperazine and 1-(2,3-dimethylphenyl)piperazine with H2SO4 in 2:1 molar ratio at RT affords the corresponding sulfate salts [C12H20N2][HSO4]2·H2O (SI) and [C12H20N2][HSO4]2 (SII). These compounds have been characterized by X-ray diffraction, thermal analysis and spectroscopic investigations (IR and NMR). In the atomic arrangement of (SI) the HSO4− anions are associated by pairs linked to the water molecules forming corrugated ribbons, while in the (SII) structure, the pairs of the HSO4− anions form corrugated chains. Solid-state 13C and 15N CP-MAS NMR spectroscopies are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. NMR peaks were attributed with the aid of DFT calculations. The electronic properties such as HOMO and LUMO energies were determined.

1,4-Phenylenediamine based covalent triazine framework as an electro catalyst

Herein, we report the synthesis of 1,4-phenylenediamine based covalent triazine framework (CTF) by reacting cyanuric chloride with 1,4-phenylenediamine under basic conditions. The as synthesized polymeric framework was characterized by solid state 13C-CPMAS and 15N NMR, FT-IR, Raman, SEM, TEM, UV-Vis and N2 sorption isotherm. Commercially available glassy carbon electrode is modified with the as synthesized polymer and its electro catalytic activity towards the reduction of nitrobenzene and oxygen evolution reaction (OER) is studied. Performance of the bare CTF material resembles the performance of commercial GC (glassy carbon) electrode.

Structural, vibrational and DFT studies of di-(pipecolinium acid) squarate

A racemic mixture of (R)- and (S)-pipecolic acid (piperidine-2-carboxylic acid, P2C) forms a stable crystalline complex with squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione, H2SQ), at the 2:1 ratio (1). The crystals are built of two pipecolic acid cations (P2C+H) and squarate dianion (SQ2−). Complex 1 has been characterized by single-crystal X-ray analysis, Raman, FTIR and 13C CP MAS spectroscopy. The title complex crystallizes in monoclinic C2/c space group with Z=4 and Z’=0.5. In the crystal structure two types of C2-symmetric complexes with different chirality are identified as [(R)-P2C+H]2SQ2− and [(S)-P2C+H]2SQ2−. The molecules are linked through the COOH⋯O–C of 2.587(1) Å and two N+H⋯O–C hydrogen bonds of 2.756(1) and 2.759(1) Å. In the optimized structure, at the B3LYP/6–311++G(d,p) level of theory, pipecolic acid zwitterion and cation interact with the hydrogen squarate anion. Charge delocalization has been analysed using the Natural Bond Orbital (NBO) method. Solid-state Raman, FTIR and 13C CP MAS spectra have been measured. The potential energy distributions (PED) have been used to assign the vibrational spectra. The crystal and optimized structures have been compared.

MALDI-TOF, 13C NMR and FTIR analysis of the cross-linking reaction of condensed tannins by triethyl phosphate

Reaction of condensation and cross-linking of catechin monomer as a model of condensed (flavonoid) tannin extracts and of mimosa tannin itself, as well as of resorcinol with triethyl phosphate (TEP) have been investigated. FTIR, solid state CP-MAS 13C NMR, 31P NMR and MALDI-ToF spectroscopy studies revealed that reaction occurs mainly on the C3 of the flavonoid heterocycle ring and on the aromatic C4′ and C5′ carbons of the flavonoids B-ring, while TEP does not appear to react on the A-ring. A difference in the relative proportions of these two reaction sites for tannin and catechin has been noticed. The reactions appear to be dependent on the temperature. According to the thermogravimetric analysis, materials obtained from the reaction of tannin with TEP showed high thermal stability.

Fabrication of New Synthetic Routes for Functionalized Si-MCM-41 Materials as Effective Adsorbents for Water Remediation

The removal of toxic dyes (Methyl Violet, MV; Congo Red, CR; and Malachite Green, MG, respectively) from water using Si-MCM-41 functionalized with aspartic acid (APA), polyethylenimine (PEI), and β-cyclodextrin (β-CD) developed through new facile synthetic routes is reported here. The successful functionalizations of Si-MCM-41 were examined by means of TGA, solid-state 13C CP MAS NMR spectra, FTIR, XRD, nitrogen sorption, FESEM, and TEM. Beside this, the sorption behavior of those sorbents using sorbates is determined by considering some factors like the pH of the medium, contact time, temperature of the medium, concentration of the dye medium, sorbent dose, and agitation speed. The kinetics data fitted a pseudo-second-order model. It is noticed that the Langmuir equation yields an accurate description of these sorption data, implying that monolayer adsorption took place in all sorption processes. The proficient sorption capacities of these adsorbents (qm = 374.89 mg g–1 for MV on Si-MCM-41–APA, qm = 458....

Following the structure and reactivity of Tuncbilek lignite during pyrolysis and hydrogenation

Combustion, pyrolysis and hydropyrolysis reactivity of Tuncbilek lignite was monitored by temperature programmed pyrolysis (TPP) under pure nitrogen flow, temperature programmed oxidation (TPO) under air flow and temperature programmed hydrogenation (TPH) under hydrogen flow at atmospheric pressure in a packed bed reactor.The structures of the organic and inorganic components were analyzed by NMR spectroscopy and XRD. Only methane and hydrogen were the main products of TPP while small amounts of CO and CO2 were also observed. Solid-state 1H and 13C CPMAS and 1H liquid Nuclear Magnetic Resonance (NMR) Spectroscopy of the pristine lignite, as well as tar and char products of pyrolysis and hydrogenation (hydropyrolysis), revealed similar tar compositions. TGA of pyrolysis chars indicated that there were more residual volatiles in hydropyrolysis char in comparison to pyrolysis char. Elemental analysis of pyrolysis and hydropyrolysis chars revealed that 25% of sulfur was lost during pyrolysis, whereas >90% of sulfur was lost during hydropyrolysis indicating efficiency of atmospheric pressure hydropyrolysis for both desulfurization and tar production. Volatile matter and fixed carbon, mostly aromatic, gave rise to distinct oxidation peaks during TPO. The oxidation peak due to volatiles was missing from TPO of pyrolysis char as well as from organic contents determined by NMR spectroscopy.

Structural, Hirshfeld surface and spectroscopic studies of the noncentrosymmetric 1-ethylpiperazinediium pentachloroantimonate (III) monohydrate

1-Ethylpiperazinediium pentachloroantimonate (III) monohydrate, C6H16N2SbCl5·H2O, has been synthesized by the reaction of antimony trioxide (Sb2O3) and 1-ethylpiperazine in an aqueous solution of hydrochloric acid. The structure crystallizes in orthorhombic system, in the non-centrosymmetric space group Pca21 and consists of isolated [C6H16N2]2+ cations, square pyramidal [SbCl5]2− anions and lattice water molecules. OH⋯Cl hydrogen bonds link the [SbCl5]2− anions and water molecules to form double chains stretching along the [101] direction. The chains in turn are linked to the organic cations via NH⋯Cl, CH⋯Cl, CH⋯O and NH⋯O hydrogen bonds to form a three-dimensional network. This structure presents an example of a general square pyramidal complex ion containing a stereo-chemically active lone pair of electrons. Solid state 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure, and vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks and IR absorption bands. The interactions variability of the two independent cations and ten chloride atoms is analyzed via Hirshfeld surface analysis.

Zinc(II) complex immobilized on amine functionalized silica gel: a novel, highly efficient and recyclable catalyst for multicomponent click synthesis of 1,4-disubstituted 1,2,3-triazoles

We report a highly efficient and recyclable heterogeneous zinc catalytic system via covalent immobilization of 2-hydroxyacetophenone (2-HAP) onto an amine functionalized silica gel followed by metallation with zinc chloride and its catalytic application in three component click synthesis of 1,4-disubstituted 1,2,3-triazoles. The structure of the synthesized organic–inorganic hybrid material (SiO2@APTES@2HAP-Zn) has been confirmed by various physicochemical characterization techniques, such as solid-state 13C CPMAS NMR spectroscopy, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction analysis (XRD), Brunauer–Emmett–Teller (BET) surface area analysis, scanning electron microscopy (SEM), atomic absorption spectroscopy (AAS), energy-dispersive X-ray fluorescence spectroscopy (ED-XRF), and elemental analysis. The newly designed catalyst works under mild reaction conditions and also exhibits excellent performance in terms of good product yield and high turnover number (TON). One of the most important attributes of the present methodology is that the catalyst can be recycled several times without appreciable loss in its activity as proved by FTIR spectroscopy and SEM analysis. Besides, the heterogeneity test also confirms that no leaching of active catalytic species occurs from the silica supported zinc catalyst which confirms its remarkable structural stability under the reaction conditions.