1 Supplementary Data Development of adsorbents based on phosphate-containing hyper-cross- linked polymers for selective removal of tetracycline from water: unveiling the role of phosphate groups in adsorption Joanna Wolskaa,b,*, Anetta Zioła-Frankowskaa, Jacek Jenczykc, Adrian Zaletaa, Kamila Sobańskab, Piotr Pietrzykb, Lukasz Wolskia a Faculty of Chemistry, Adam Mickiewicz University, Poznań, ul. Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland b Faculty of Chemistry, Jagiellonian University, ul. Gronostajowa 2, 30-387 Kraków, Poland c NanoBioMedical Centre, Adam Mickiewicz University, Poznań, ul. Wszechnicy Piastowskiej 3, 61-614 Poznań, Poland 2 Table of content 1. Extended experimental section ...................................................................................... 4 1.1. Synthesis of hyper-cross-linked polymers ....................................................................... 4 1.2. Estimating the cost of adsorbent preparation ................................................................. 5 Table S1. Detailed breakdown of the estimated cost of preparing 1 gram of P1-HCP1. .......... 5 1.3. Characterization of HCP-based adsorbents .................................................................... 6 1.4. Adsorption experiments ................................................................................................... 8 1.5. Reuse tests and regeneration procedure ....................................................................... 12 Table S2. Main physicochemical properties of real water matrices used for the adsorption experiments. ............................................................................................................................. 13 Fig. S1. Relationship between concentration of the TC and its absorbance at λmax = 275 nm. 14 Fig. S2. Comparison of the solid-state 13C MAS NMR spectra of all HCPs with the liquid-state 13C NMR spectra of 4,4'-bis(chloromethyl)-1,1'-biphenyl (BCMB) and diphenyl phosphate (DPP) monomers in CDCl3 solution in the 165–115 ppm region, highlighting the most downfield signal (ca. 150 ppm) observed only in MAS NMR spectra of the P-HCPs, attributed to the aromatic carbons directly bonded to the phosphate groups in DPP unit.. ...................... 15 Table S3. Atomic surface concentration of elements estimated from XPS data using Casa XPS software. ................................................................................................................................... 16 Table S4. Chemical composition of the polymer-based adsorbents. ....................................... 16 Fig. S3. SEM images of the HCP, P1-HCP, P2-HCP, and P3-HCP at various magnifications. . ........................................................................................................................................ 17 Fig. S4. SEM-EDS elemental mapping for C, P, and O for the HCP, P2-HCP, and P3-HCP. 18 Fig. S5. Low-temperature nitrogen adsorption–desorption isotherms of all investigated HCPs, highlighting the more pronounced changes in the shape of the desorption branch and the hysteresis loop. ......................................................................................................................... 19 Scheme S1. TGA profile for all HCPs accompanied by a summary of Td10 values. ............... 20 Fig. S6. Speciation of TC at different pH values. .................................................................... 21 Fig. S7. Surface Zeta potential of P1-HCP and HCP materials at different pH values. .......... 22 3 Table S5. TC adsorption kinetic parameters for P1-HCP adsorbent derived from the pseudo- first order (PFO) and pseudo-second order (PSO) linear and non-linear models. ................... 23 Fig. S8. The effect of temperature on TC removal in the presence of P1-HCP adsorbent.. .... 24 Fig. S9. Graphs used for assessing the pseudo-second order (PSO) kinetic model for the TC adsorption on the P1-HCP adsorbent at different temperature.. .............................................. 25 Fig. S10. Comparison of XPS spectra of TC powder, fresh P1-HCP, and P1-HCP after TC adsorption (P1-HCP+TC) in the P 2p, N 1s and O 1s binding energy ranges. ........................ 26 Fig. S11. ATR-FTIR spectra of powdered TC, fresh P1-HCP and spent P1-HCP1 after TC adsorption in the range of 1300-740 cm-1.. .............................................................................. 27 Table S6. Main characteristics of five different structure drugs selected to evaluate versatility of P1-HCP adsorbent. ............................................................................................................... 28 Table S7. Adsorption capacity of other adsorbents reported in previous literature data, to the adsorptive removal of tetracycline and other selected pharmaceuticals studied in this work. . 29 Fig. S12. Comparison of XPS spectra of fresh P1-HCP and P1-HCP after 5th adsorption- desorption (ads.-des.) cycle in the P 2p and O 1s binding energy ranges. ............................... 35 4 1. Extended experimental section 1.1. Synthesis of hyper-cross-linked polymers The yield of hyper-cross-linked polymer synthesis was calculated using the following equation (Eq. S1): 𝑌𝑖𝑒𝑙𝑑 = 𝑚𝑝𝑜𝑙𝑦𝑚𝑒𝑟 𝑚𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 × 100% (Eq. S1) Where 𝑚𝑝𝑜𝑙𝑦𝑚𝑒𝑟 and 𝑚𝑚𝑜𝑛𝑜𝑚𝑒𝑟𝑠 stand for the weight of the dry polymer and the weight of the BCMB and DPP monomers, respectively. Additionally, 𝑚𝑝𝑜𝑙𝑦𝑚𝑒𝑟 includes the 𝑚𝑚𝑜𝑛𝑜𝑚𝑒𝑟 and the mass of the ethylene cross-linking bridges formed as a by-product of Friedel-Crafts alkylation with the solvent (DCE) [Macromolecules 57 (2024) 5507, doi: 10.1021/acs.macromol.4c00503] with a small residue of chlorine, as confirmed by XPS analysis (see Table S3). The chlorine species may originate from terminated chloroalkyl groups (–CH2Cl and/or –CH2CH2Cl), derived from both BCMB and DCE. Consequently, the yield of HCPs may exceed 100% [Adv. Mater. (2024) 2307579, doi: 10.1002/adma.202307579; ACS Appl. Mater. Inter. 14 (2022) 7369, doi: 10.1021/acsami.1c24393]. 5 1.2. Estimating the cost of adsorbent preparation Estimated costs per gram of P1-HCP material have been calculated using the reagents required for its synthesis (see Experimental Methods, pages 5-6). Unit prices found on Merck's website (www.sigmaaldrich.com/PL/pl) as of March 9, 2025 were used for all calculations. A minimum reagent purity of ≥95% was required. Work-up steps, such as washing, were excluded from the calculations as quantities of work-up reagents are often not disclosed, hence, estimating cost is not possible. The operating time, synthesis time, and power were also not factored into the calculation. A detailed breakdown of the estimated costs is provided in Table S1 shown below. The total cost of this P1-HCP material only takes into account lab-scale production. Table S1. Detailed breakdown of the estimated cost of preparing 1 gram of P1-HCP1. Reagent Unit Price (€) (Quantity/Volume) Reagent Quantity/Volume for 1 g of Polymer Price of Reagent per 1 g of Polymer (€) 4,4'-bis(chloromethyl)- 1,1'-biphenyl 98 (250 g) 0.9 g 0.3 diphenyl phosphate 207 (25 g) 0.4 g 3.5 1,2-dichloroethane 249 (1000 mL) 41.0 mL 10.1 ferric chloride 92 (1000 g) 3.3 g 0.3 Total cost of preparing of P1-HCP adsorbent (€/g) 14.3 6 1.3. Characterization of HCP-based adsorbents Solid-state 13C NMR spectra were acquired at ambient conditions on a 400 MHz Agilent spectrometer equipped with Wide Bore Triple Resonance T3 MAS XY probe. Samples were placed into a 4 mm diameter zirconia rotor. Spectra were recorded using Cross-Polarization (CP) sequence with CP contact time set to 1550 μs. 13C detection with dipolar decoupling of protons was used. Experiments were performed under magic angle spinning (MAS) conditions with a spinning frequency of 10 kHz. 4000 transients were accumulated for each spectrum. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of the polymers were acquired in the range of 4000 cm-1 to 400 cm-1 (resolution 4 cm˗1, number of scans = 64) using an IRSpirit-X spectrophotometer (Shimadzu) equipped with attenuated total reflectance (QATR-S) module (Shimadzu). X-ray photoelectron spectroscopy (XPS) was performed using an ultra-high vacuum photoelectron spectrometer based on a Phoibos150 NAP analyzer (Specs, Germany). The analysis chamber was operated under vacuum with a pressure close to 5 × 10‒9 mbar and the sample was irradiated with a monochromatic AlKα (1486.6 eV) radiation. Any charging that might occur during the measurements (due to incomplete neutralization of ejected surface electrons) was accounted for by rigidly shifting the entire spectrum by a distance needed to set the binding energy of the C 1s assigned to adventitious carbon to the assumed value of 284.8 eV. Elemental analysis (EA) of the HCPs was carried out with an Elementar Analyser Vario EL III. The samples were weighed in tin capsules (4 mg) and introduced into the reactor with a precisely defined portion of oxygen. After combustion at 900-1000 °C, the exhaust gases were transported in helium flow to the second reactor, and then through the water trap to the chromatographic column, which separated the generated gases. Finally, the separated 7 gases were detected by a thermal conduction detector (TCD). The measurements were repeated three times for each investigated sample. The quantitative detection of phosphorus and iron involved digesting the polymer samples using a piranha solution, prepared by mixing concentrated sulfuric acid and hydrogen peroxide in a 3:1 volume ratio (v:v). The resulting solution was then diluted with deionized (DI) water, and the phosphorus and iron content was analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Scanning electron microscopy (SEM) images combined with energy dispersive X-ray spectroscopy (EDS) were recorded using a Quanta 250 FEG, FEI instrument. Samples were mounted on carbon tape on aluminium stubs, without any coating treatment. N2 adsorption-desorption isotherms were obtained at ‒196 °C using an Autosorb iQ Analyzer (Quantachrome). Before measurements, the samples were degassed at 80 °C for 22 h. The specific surface area of the materials obtained was calculated by the Brunauer-Emmett- Teller (BET) method, and the average pore size was estimated by the Barrett-Joyner-Halenda (BJH) method from the desorption branch of the isotherm. Thermogravimetric analysis (TGA) experiments of polymers were performed with a STA 6000 apparatus from Perkin Elmer, under a nitrogen atmosphere, at the heating rate of 10 °C/min from room temperature up to a maximum of 900 °C. The zeta potential measurements as a function of the pH of aqueous dispersions of the HCP and P1-HCP polymers (Cpolymer = 1 g/L) were carried out using a Zetasizer Nano ZS (Malvern). The zeta potential was estimated from electrophoretic mobility using the Henry equation: 𝑈E = 2εζ𝐹(ka)/3η, where 𝑈E represents the electrophoretic mobility, ζ is the zeta potential, ε denotes the dielectric constant, 𝐹(ka) is Henry’s function (set to 1.5 as in the Smoluchowski approximation), and η is the viscosity. The pH was adjusted using 0.5 mol/L solutions of HCl or NH3 in H2O. 8 1.4. Adsorption experiments The efficiency of tetracycline removal from tap water carried out using very low (trace) concentration of the antibiotic (50 or 100 µg/L) was performed using LC–MS/MS included a Shimadzu Liquid Chromatography system coupled to a Shimadzu 8050 triple quadrupole mass spectrometer (Shimadzu, Japan). Optimized MRM transitions for tetracycline were as follows: 445.4-410.0, 445.4-154.0. The UHPLC system consisted of a solvent delivery system (two pumps Nexera X2 LC-30AD), an autosampler (Nexera X2 SIL-30AC), degasser (DGU-20A5R), a column oven (CTO-20AC) and a system controller (CBM-20A). Compounds were chromatographically separated on a Kinetex C18 (2.1 × 100 mm, 2.6 μm) column with isocratic elution using (A) water (0.1% formic acid) and (B) acetonitrile (0.1% formic acid) as mobile phases A and B (60%:40%), respectively. The flow rate was 0.4 mL/min, and the total run time was 5.0 min. Operating conditions of the mass spectrometer were as follows: Ionization: ESI positive; DL temp.: 250 °C; Interface temp.: 300 °C; Block heater temp.: 500 °C; Nebulizer gas flow: 3 L/min; Drying gas flow: 10 L/min; Heating gas flow: 10 L/min; Dwell time: 20 ms; Pause time: 1 ms. Standards solutions were prepared from tetracycline with the concentration of 1000 mg/L in methanol (Merck, Poland) for LC-MS/MS. Adsorption kinetic parameters were determined by using linearized form of the pseudo- first order (PFO) (Eq. S2) and pseudo-second order (PSO) (Eq. S3) models described by Ho and McKay [Process Biochem. 34 (1999) 451, doi: 10.1016/S0032-9592(98)00112-5], where 𝑞(𝑡) and 𝑞𝑒 are the amount of adsorbate adsorbed at any given time, 𝑡 and at equilibrium, respectively, 𝑘1 and 𝑘2 corresponds to adsorption rate constant for pseudo-first order and pseudo-second order model, respectively. ln(𝑞𝑒 − 𝑞(𝑡)) = −𝑘1𝑡 + 𝑙𝑛𝑞𝑒 (Eq. S2) 𝑡 𝑡(𝑞) = ( 1 𝑞𝑒 ) 𝑡 + 1 𝑘2𝑞𝑒 2 (Eq. S3) 9 𝑘1 and 𝑘2 values were determined by plotting ln(𝑞𝑒 − 𝑞(𝑡)) vs 𝑡 and 𝑡 𝑡(𝑞) vs 𝑡 for PFO and PSO, respectively. The kinetics parameters were then estimated from the slope and intercept of the best fit line such that, if 𝑚 = slope and 𝑏 = intercept, 𝑘1 = −𝑚 and 𝑞𝑒 = 𝑒𝑥𝑝 (𝑏) for PFO, while 𝑘2 = 𝑚2 𝑏 and 𝑞𝑒 = 𝑚−1 for PSO [Clean. Eng. Technol. 1 (2020) 100032, doi: 10.1016/j.clet.2020.100032]. Additionally, experimental data were also fitted to the non-linear forms of PFO and PSO models [Surf. Interfaces 22 (2021) 100806, doi: 10.1016/j.surfin.2020.100806]. Experimental 𝑞𝑒 values were estimated on the basis of adsorption tests using the following formula (Eq. S4): 𝑞𝑒 = 𝑉(𝐶0−𝐶𝑡) 𝑚 (Eq. S4) where, 𝐶0 is an initial concentration of drug (mg/L), 𝐶𝑡 is concentration of drug (mg/L) after a given adsorption time, 𝑡 (min), 𝑉 is the volume of the reaction mixture (L), and 𝑚 is the mass of the adsorbent (g). Adsorption kinetics was also analyzed using Weber–Morris intraparticle diffusion (IPD) model (Eq. S5) [J. Sanit. Eng. Div. Am. Soc. Civ. Eng. 89 (1963) 31, doi: 10.1061/JSEDAI.0000430]. 𝑞𝑡 = 𝐾𝑖𝑑𝑡 1 2 + 𝐶 (Eq. S5) where 𝑞𝑡 is the adsorption capacity at any time (mg/g), 𝐾𝑖𝑑 is the intraparticle diffusion rate constant (mg g‒1 min‒1/2), 𝑡 is the time taken for the adsorption process (min) and 𝐶 is a constant for the any experiment (mg/g) that gives an idea about the thickness of the boundary layer. When a graph of 𝑞𝑡 is plotted against 𝑡 1 2, a linear graph is obtained with regression linear coefficient, 𝑅2, close to unity. The slope of the graph reveals the intraparticle diffusion rate constant, 𝐾𝑖𝑑, while intercept of the graph stands for 𝐶. 10 Isotherms of the tetracycline adsorption were recorded in the bath mode using an Easy Max 102 Advanced Thermostat system (Mettler Toledo). Experimental data were fitted to Langmuir and Freundlich adsorption models. Adsorption isotherm parameters were determined by using linearized form of the Langmuir (Eq. S6) and Freundlich (Eq. S7) [SN Appl. Sci. 2 (2020) 187, doi: 10.1007/s42452-020-1978-y]. 𝐶𝑒 𝑞𝑒 = 1 𝑞𝑚 (𝐶𝑒) + 1 𝑞𝑚𝐾𝐿 (Eq. S6) log10 𝑞𝑒 = 1 𝑛 log10 𝐶𝑒 + log10 𝐾𝐹 (Eq. S7) In the case of linear form of Langmuir model (Eq. S6), 𝑞𝑒 is the amount of adsorbate per unit mass of adsorbent at equilibrium (mg/g), 𝐾𝐿 is the adsorption capacity constant (L/g), 𝐶𝑒 is the concentration of adsorbate at equilibrium (mg/L) and 𝑞𝑚 is the maximum adsorption capacity (mg/g). When graph of 𝐶𝑒 𝑞𝑒 is plotted against 𝐶𝑒, a linear graph is a acquired with regression linear coefficient, R2, close to unity. The 𝑞𝑚 and 𝐾𝐿 are obtained from the slope and intercept of the graph. Both the slope and intercept of the graph represent the values for 1 𝑞𝑚 and 1 𝑞𝑚𝐾𝐿 , respectively. In the case of linear form of Freundlich model (Eq. S7), where 𝑞𝑒 is the amount of adsorbate per unit mass of adsorbent at equilibrium (mg/g), 𝐾𝐹 is the adsorption capacity constant (L/g), 𝐶𝑒 is the concentration of the adsorbate at equilibrium (mg/L), 𝑛 is the heterogeneity factor and 1 𝑛 is the adsorption intensity. When a graph of log10 𝑞𝑒is plotted against log10 𝐶𝑒, a linear graph is acquired with regression linear coefficient, R2, close to unity. The 𝑛 and 𝐾𝐹 are obtained from the slope and intercept of the graph. Both the slope and intercept of the graph represent the values for 1 𝑛 and log10 𝐾𝐹, respectively. 11 Additionally, experimental data were also fitted to the non-linear forms of Langmuir and Freundlich isotherm adsorption models [Surf. Interfaces 22 (2021) 100806, doi: 10.1016/j.surfin.2020.100806]. Gibbs free energy (∆𝐺0), was determined according to Eq. (S8). ∆𝐺 = −𝑅𝑇 ln(𝐾𝐿) Eq. (S8) where, 𝑇 is the solution temperature (K, 20°C), 𝑅 is the ideal gas constant (8.314 J mol-1 K-1) and 𝐾𝐿 is the adsorption capacity constant (L/g) derived from Langmuir isotherm model. Since 𝐾𝐿 should be unitless to get the correct units, the Langmuir isotherm coefficient 𝐾𝐿 was converted into a dimensionless constant by multiplying it by 1000 [J. Serb. Chem. Soc. 72 (2007) 1363, doi: 10.2298/JSC0712363M]. Activation energy (𝐸𝑎) was calculated using the linear form of Arrhenius equation (Eq. S9): ln 𝑘 = − 𝐸𝑎 𝑅𝑇 + ln 𝐴 (Eq. S9) where, 𝐸𝑎 (J mol‒1) is the apparent activation energy of the reaction; 𝑅 is the ideal gas constant (8.314 J mol‒1 K‒1), 𝑇 is reaction temperature (K), 𝑘 is a coefficient. Since the adsorption process is in accordance with pseudo-second order kinetic model, the apparent activation energy was calculated by the coefficient of 𝑘 derived from pseudo-second order kinetic model. When a graph of ln 𝑘 is plotted against 1/𝑇, a linear graph is acquired with regression linear coefficient, R2, close to unity. The 𝐸𝑎 is obtained from the slope of the graph. The slope of the graph represents the values for −𝐸𝑎/𝑅. 12 1.5. Reuse tests and regeneration procedure In a standard reuse experiment, 20 mg of P1-HCP (adsorbent loading = 0.10 g/L) was added to 200 mL of TC solution (C0 = 30 mg/L) and stirred vigorously (600 rpm). After 24 h of agitation at room temperature (adsorption step), the P1-HCP material was separated from the solution through PTFE filter paper (Biosens, 0.22 µm) on a glass vacuum filtration apparatus (Whatman). Concentration of the TC in the filtrate was analyzed on the basis of UV-vis measurements, and the efficiency of antibiotic removal after a given adsorption cycle was determined using equation (Eq. 1, see in main text). To regenerate the spent adsorbent, the polymer collected and separated after the adsorption step was dispersed in 100 mL of a regenerator solution composed of EtOH and 2.0 M HCl in a 1:1 (v:v) ratio and stirred for 3 h at room temperature (stirring rate = 300 rpm). The regenerated polymer was then thoroughly rinsed with deionized water until neutral pH was achieved and subsequently used for the next adsorption cycle. The regeneration performance of P1-HCP was evaluated over five consecutive adsorption-desorption cycles. 13 Table S2. Main physicochemical properties of real water matrices used for the adsorption experiments. Parameter (unit) deionized water tap water Warta River pH 6.8 7.4-7.5 8.0-8.4 Total carbon (mg/L) 0.67 54.14 48.13 Total organic carbon (mg/L) 0.40 > 0.50 at.% b Surface concentration of Fe [at.%] determined based on SEM-EDS. Table S4. Chemical composition of the polymer-based adsorbents. Polymer Elemental composition Elemental analysisa ICP-OESb SEM-EDSc C [wt.%] H [wt.%] P [wt.%] Fe [wt.%] Fe [wt.%] Fe [at.%] HCP 85.83 ± 0.26 4.99 ± 0.03 - - - - P1-HCP 71.38 ± 0.09 4.59 ± 0.01 3.15 ± 0.01 1.42 ± 0.01 0.99 ± 0.08 0.23 ± 0.02 P2-HCP 66.95 ± 0.02 4.28 ± 0.06 3.49 ± 0.01 0.78 ± 0.01 1.19 ± 0.09 0.29 ± 0.02 P3-HCP 63.30 ± 0.01 3.95 ± 0.01 5.46 ± 0.01 1.48 ± 0.01 1.01 ± 0.07 0.24 ± 0.02 a Average values derived from three measurements based on EA. b Average values derived from three measurements based on ICP-OES. c Content of iron on the surface of polymers determined based on SEM-EDS. 17 Fig. S3. SEM images of the HCP (grey panel), P1-HCP (red panel), P2-HCP (blue panel), and P3-HCP (green panel) at various magnifications. 18 Fig. S4. SEM-EDS elemental mapping for C, P, and O for the HCP (left-hand vertical panel), P2-HCP (middle vertical panel), and P3-HCP (right-hand vertical panel). C P O HCP P2-HCP P3-HCP 50 µm 50 µm 50 µm 50 µm 50 µm 50 µm 50 µm 50 µm 50 µm 50 µm 50 µm 50 µm 19 0 0.2 0.4 0.6 0.8 1 adsorption desorption V o lu m e a d s o rb e d , c m 3 g -1 ( S T P ) Relative pressure, p/p0 200 HCP 0 0.2 0.4 0.6 0.8 1 adsorption desorption V o lu m e a d s o rb e d , c m 3 g -1 ( S T P ) Relative pressure, p/p0 50 P1-HCP 0 0.2 0.4 0.6 0.8 1 adsorption desorption V o lu m e a d s o rb e d , c m 3 g -1 ( S T P ) Relative pressure, p/p0 80 P2-HCP 0 0.2 0.4 0.6 0.8 1 adsorption desorption V o lu m e a d s o rb e d , c m 3 g -1 ( S T P ) Relative pressure, p/p0 100 P3-HCP Fig. S5. Low-temperature nitrogen adsorption–desorption isotherms of all investigated HCPs, highlighting the more pronounced changes in the shape of the desorption branch and the hysteresis loop. 20 150 300 450 600 750 900 0 20 40 60 80 100 Temperature, °C W e ig h t % , % HCP P1-HCP P2-HCP P3-HCP D e ri v a ti v e w e ig h t % ( % m in -1 ) 0.5 Scheme S1. TGA profile for all HCPs accompanied by a summary of Td10 values, which correspond to the temperature at which 10% of the polymer's initial weight is lost. Adsorbent Td10 [°C] HCP 500 P1-HCP 464 P2-HCP 431 P3-HCP 426 21 Fig. S6. Speciation of TC at different pH values [Environ. Sci. Technol. 48 (2014) 4893, doi: 10.1021/es5003428; J. Colloid Interf. Sci. 351 (2010) 254, doi: 10.1016/j.jcis.2010.07.034; Appl. Clay Sci. 40 (2008) 179, doi: 10.1016/j.clay.2007.08.003]. 22 2 4 6 8 10 -30 -20 -10 0 10 20 30 HCP P1-HCP Z e ta p o te n ti a l, m V pH Fig. S7. Surface Zeta potential of P1-HCP and HCP materials at different pH values. 23 Table S5. TC adsorption kinetic parameters for P1-HCP adsorbent derived from the pseudo- first order (PFO) and pseudo-second order (PSO) linear [Clean. Eng. Technol. 1 (2020) 100032, doi: 10.1016/j.clet.2020.100032] and non-linear [Surf. Interfaces 22 (2021) 100806; doi: 10.1016/j.surfin.2020.100806] models. Representative graphs used for estimating of the adsorption kinetics are shown in Fig. 8.a Equation type qe (exp)b [mg/g] PFO PSO k [1/min] qe(cal)c [mg/g] R2 k [g/mg/min] qe (cal)c [mg/g] R2 Linear 330.0 0.00379 196.0 0.9795 0.00006 339.0 0.9988 Non-linear 0.02175 283.0 0.8536 0.00010 310.0 0.9417 a Adsorption conditions: 200 mL of TC solution (C0 = 20 mg/L), 10 mg of the polymer (adsorbent dosage = 0.05 g/L), initial pH ~ 4.5 (before addition of the adsorbent), room temperature, stirring rate: 600 rpm. b Maximum adsorption capacity of the sample derived from the experiments. c Maximum adsorption capacity of the sample calculated based on a given kinetic model. 24 0 250 500 750 1000 1250 1500 0 15 30 45 60 75 90 25°C 40°C 60°C T C r e m o v a l e ff ic ie n c y , % Time, min Fig. S8. The effect of temperature on TC removal in the presence of P1-HCP adsorbent. Adsorption conditions: 200 mL of TC solution (C0 = 20 mg/L), 10 mg of the polymer (adsorbent dosage = 0.05 g/L), initial pH ~ 4.5 (before addition of the adsorbent), stirring rate: 600 rpm. 25 0 250 500 750 1000 1250 1500 0 1 2 3 4 5 experimental data linear PSO model t/ q (t ) Time, min 25 °C y = 0.00296x + 0.13932 R2 = 0.998 0 250 500 750 1000 1250 1500 0 1 2 3 4 experimental data linear PSO model t/ q (t ) Time, min y = 0.00288x + 0.11985 R2 = 0.99854 40 °C 0 250 500 750 1000 1250 1500 0 1 2 3 4 experimental data linear PSO model t/ q (t ) Time, min 60 °C y = 0.00285x + 0.08507 R2 = 0.99942 Fig. S9. Graphs used for assessing the pseudo-second order (PSO) kinetic model for the TC adsorption on the P1-HCP adsorbent at different temperature. Adsorption conditions: 200 mL of the antibiotic solution (C0 = 20 mg/L), 10 mg of P1-HCP (adsorbent dosage = 0.05 g/L), initial pH ~ 4.5 (before addition of the adsorbent), stirring rate: 600 rpm. 26 141 138 135 132 129 126 TC powder 40 -PO3(OH) C o u n ts p e r s e c o n d P1-HCP 25 134.6 Binding energy, eV P1-HCP+TC 25 P 2p 134.2 increase in electron density on phosphorus species after TC adsorption 408 404 400 396 392 TC powder N 1s -N-(CH3)2-C(O)-NH2 70 398.8 C o u n ts p e r s e c o n d P1-HCP 103 400.5 Binding energy, eV P1-HCP+TC 30 401.7 399.6 decrease in electron density on nitrogen species after TC adsorption 540 536 532 528 524 520 TC powder P1-HCP+TC 300 O 1s 531.6 increase in electron density on oxygen species after TC adsorption C o u n ts p e r s e c o n d P1-HCP 300 532.7 Binding energy, eV 300 532.4 -PO3(OH) Fig. S10. Comparison of XPS spectra of TC powder, fresh P1-HCP, and P1-HCP after TC adsorption (P1-HCP+TC) in the P 2p, N 1s and O 1s binding energy ranges. 27 1300 1200 1100 1000 900 800 T ra n s m it a n c e , % Wavenumber, cm-1 TC powder P1-HCP P1-HCP+TC 5 a b c 1200 1170 1210 1173 1083 1075 940 919 Fig. S11. ATR-FTIR spectra of powdered TC, fresh P1-HCP and spent P1-HCP1 after TC adsorption in the range of 1300-740 cm-1. The highlighted ranges corresponds to the bands attributed to (a) stretching vibrations of the P=O bond (b) stretching vibrations of the P–OH bond, and (c) stretching vibrations of the P–O bond. 28 Table S6. Main characteristics of five different structure drugs selected to evaluate versatility of P1-HCP adsorbent. Pharmaceutical Name Chemical structure Abbreviation Chemical formula Molecular weight [g/mol] pKa in RT References Antibiotics Tetracycline TC C22H24N2O8 444.44 3.3 (pKa,1) 7.7 (pKa,2) 9.7 (pKa,3) Environ. Sci. Technol. 48 (2014) 4893, doi: 10.1021/es5003428 Ciprofloxacin CIP C17H18FN3O3 331.35 5.9 (pKa,1) 8.9 (pKa,2) J. Ind. Eng. Chem. 93 (2021) 57, doi: 10.1016/j.jiec.2020.09.023 Non-steroidal inflammatory drugs Diclofenac DCF C14H11Cl2NO2 296.15 4.0 (pKa,1) Environ. Earth Sci. 79 (2020) 277, doi: 10.1007/s12665-020-09017-z Ibuprofen IBU C13H18O2 206.28 4.4 (pKa,1) Chem. Eng. J. 277 (2015) 360, doi: 10.1016/j.cej.2015.04.097 Naproxen NPX C14H14O3 230.26 4.2 (pKa,1) J. Pharm. Biomed. Anal. 42 (2006) 126, doi: 10.1016/j.jpba.2005.11.029 29 Table S7. Adsorption capacity of other adsorbents reported in previous literature data, to the adsorptive removal of tetracycline and other selected pharmaceuticals studied in this work. Adsorbent Type of adsorbent Adsorbent loading [g/L] Cₒ [mg/L] pH Temp. [°C] Time [min] Adsorption capacity (qe) [mg/g] References Tetracycline CPS Agriculture waste coated with zinc oxide 200.0- 10000.0 30-70 3.0-9.0 25-35 0-120 99 Arab. J. Chem. 13 (2020) 4629, doi:10.1016/j.arabjc.2019.10.010 Zn-BTC@SBC Metal-organic framework porous biochar composite 0.4 20 3.0- 11.0 25 1440 126 J. Mol. Liq. 384 (2023) 122283, doi:10.1016/j.molliq.2023.122283 HCP-N/S-2 Hyper-cross-linked polymer 5.0 50 6.0 25 180 138 Mater. Sci. Eng. B 303 (2024) 117335, doi: 10.1016/j.mseb.2024.117335 PMGO Magnetic graphene oxide nanocomposite 0.2 22-71 2.0- 10.0 25 - 194 React. Funct. Polym. 191 (2023) 105701, doi:10.1016/j.reactfunct- polym.2023.105701 NaY zeolite Zeolite 500.0 80 7.0 30 1440 202 J. Clean. Prod. 172 (2018) 602, doi:10.1016/j.jclepro.2017.10.180 SKTPS Hyper-cross-linked polymer 1.0 0.044 7.0 RT 5 209 ACS Appl. Mater. Interfaces. 14 (2022) 7369, doi:10.1021/acsami.1c24393 HCP-BPA-Na Hyper-cross-linked polymer 0.075 0.125 3.0 25-45 - 268 J. Water Process Eng. 40 (2021) 101902, doi:10.1016/j.jwpe.2020.101902 HCP-MAH Hyper-cross-linked polymer 0.125 30 7.0 25 1440 273 J. Environ. Chem. Eng. 9 (2021) 106047, doi:10.1016/j.jece.2021.106047 La-impregnated MCM-41 Zeolite 0.06 100 7.0 RT 1440 303 Environ. Technol. 31 (2010) 233, doi:10.1080/09593330903453210 https://doi.org/10.1016/j.molliq.2023.122283 30 ZIF-8 Metal-organic framework 0.5 50 4.0 30 240 313 J. Hazard. Mater. 366 (2019) 563, doi:10.1016/j.jhazmat.2018.12.047 CRAC@Fe2O3 Magnetic activated carbon 0.05-0.5 50 2.0- 10.0 30 300 313 Chemosphere 310 (2023) 136892, 10.1016/j.chemosphere.2022.136892 P1-HCP Hyper-cross-linked polymer 0.05 20 4.5 RT 1440 330 This work sHCP1 Hyper-cross-linked polymer 0.025 15 6.5 RT 180 413 J. Environ. Chem. Eng. 11 (2023) 110429, doi:10.1016/j.jece.2023.110429 HCP-COOH Hyper-cross-linked polymer 0.125 30 7.0 25 1440 418 J. Environ. Chem. Eng. 9 (2021) 106047, doi:10.1016/j.jece.2021.106047 Cu-MOF@ Co-MOF Bimetallic organic framework 0.5 10-450 2.0- 11.0 25-45 0.5-25 435 Sci. Rep. 14 (2024) 17607, doi:10.1038/s41598-024-67986-8 MBCP Modified bentonite 0.2 100 6.0 25 0-90 476 Sep. Purif. Technol. 274 (2021) 119059, doi:10.1016/j.seppur.2021.119059 Ciprofloxacin MgO/Chit/GO Chitosan-based nanocomposite 0.5 30-1500 7.0 25 360 23 Microchim. Acta. 186 (2019) 459, doi:10.1007/s00604-019-3563-x Chit/CNT Chitosan-carbon nanotubes hydrogel beads 1.5 40 7.0 RT 720 24 J. Hazard. Mater. Adv. 13 (2024) 100404, doi: 10.1016/j.hazadv.2024.100404 PIM-1 Polymer of intrinsic microporosity 0.4 73 7.0 RT 1440 31 Sci. Rep. 10 (2020) 1, doi:10.1038/s41598-020-57616-4 poly(styrenesulf onate)/Al2O3 Polyelectrolyte 5.0 10 6.0 RT 90 35 J. Mol. Liq. 309 (2020) 113150, doi:10.1016/j.molliq.2020.113150 CBHB Chitosan-based hydrogel 0.25 50 3.0 30 - 37 Sci. Total Environ. 639 (2018) 560, doi:10.1016/j.scitotenv.2018.05.129 https://doi.org/10.1016/j.chemosphere.2022.136892 31 CS/MMT/ZnO Nanocomposite 0.03 30 7.0 RT 120 57 J. Water Process Eng. 63 (2024) 105449, doi: 10.1016/j.jwpe.2024.105449 JLUE-HCOPs Covalent organic framework 1.0 20 6.0 RT 2880 84 Eur. Polym. 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Technol. 274 (2021) 119059, doi:10.1016/j.seppur.2021.119059 spherical MgO Metal-based nanomaterial 0.1 25 9.0 RT 50 ~460 J. Environ. Chem. Eng.8 (2020) 104256, doi: 10.1016/j.jece.2020.104256 sHCP(1:4) Hyper-cross-linked polymer 0.025 30 6.8 RT 180 758 Sep. Purif. Technol. 343 (2024) 127147, doi: 10.1016/j.seppur.2024.127147 nickel sulphide/ L-glutathione Nanomaterial 0.333 50 4.5 RT 1440 972 Colloids Surf. A Physicochem. Eng. Asp. 586 (2020) 124264, doi: 10.1016/j.colsurfa.2019.124264 Diclofenac ZN Natural zeolite 2.000 20 2.0 20 120 ~8 CSCEE 9 (2024) 100575, doi: 10.1016/j.cscee.2023.100575 32 fibrous silica KCC-1 Silica-based composite 1.000 160 4.0 RT 40 65 J. Environ. Chem. Eng. 11 (2023) 111295, doi: 10.1016/j.jece.2023.111295 MWCNT- OH/COOH- Fe@coffee Functionalized carbon nanotubes 1.500 119 ~7.0 RT 20 77 Environ. Res. 251 (2024) 118733, doi: 10.1016/j.envres.2024.118733 HCP-N/S-2 Hyper-cross-linked polymer 5.000 50 6.0 25 180 141 Mater. Sci. Eng. 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Pharm. 29 (2022) 100757, doi: 10.1016/j.scp.2022.100757 UiO-66 Metal-organic frameworks 0.05 9 4.4 25 600 89 Chem. Eng. J. 360 (2019) 645, doi: 10.1016/j.cej.2018.12.021 https://doi.org/10.1016/j.scp.2022.100757 34 HCP1-N Hyper-cross-linked polymer 0.025 15 6.0 RT 360 102 Environ. Res. 268 (2025) 120791, doi: 10.1016/j.envres.2025.120791 P1-HCP Hyper-cross-linked polymer 0.05 20 4.5 RT 1440 117 This work GTFPAC Activated carbon 0.5 100 4.0 25 180 129 J. Environ. Chem. Eng. 9 (2021) 106820, doi: 10.1016/j.jece.2021.106820 Cu-doped Mil- 101(Fe) Metal-organic framework 0.1 20 - RT 180 178 Sci. Total Environ. 797 (2021) 149179, doi: 10.1016/j.scitotenv.2021.149179 35 140 136 132 128 P1-HCP after 5th ads.-des. cycle 20 P 2p -PO3(OH) C o u n ts p e r s e c o n d Binding energy, eV P1-HCP 20 540 536 532 528 524 C o u n ts p e r s e c o n d P1-HCP O 1s 150 150 Binding energy, eV P1-HCP after 5th ads.-des. cycle -PO3(OH) Fig. S12. Comparison of XPS spectra of fresh P1-HCP and P1-HCP after 5th adsorption- desorption (ads.-des.) cycle in the P 2p and O 1s binding energy ranges.