Superior Iodine Uptake Capacity Enabled by an Open Metal-Sulfide Framework Composed of Three Types of Active Sites

Open AccessCCS ChemistryRESEARCH ARTICLES22 Jul 2022Superior Iodine Uptake Capacity Enabled by an Metal-Sulfide Framework Composed of Three Types Active Sites Yugang Zhang†, Linwei He†, Tingting Pan†, Jian Xie, Fuqi Wu, Xinglong Dong, Xia Wang, Lixi Chen, Shicheng Gong, Wei Liu, Litao Kang, Junchang Lanhua Long Yu Han and Shuao Wang Zhang† State Key Laboratory Radiation Medicine Protection, School for Radiological Interdisciplinary Sciences (RAD-X), Collaborative Innovation Center Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123 †Y. Zhang, L. He, T. Pan contributed equally to this work.Google Scholar More articles author , He† Pan† Advanced Membranes Porous Materials (AMPM) Center, Physical Engineering Division, King Abdullah University Science Technology (KAUST), Thuwal 23955-6900 Xie Life Sciences, Civil Engineering, Shaoxing 312000 Google Wu Dong Chen Gong Liu Environmental Yantai 264005 Kang *Corresponding authors: [email protected], E-mail Address: protected] https://doi.org/10.31635/ccschem.022.202201966 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Efficient adsorption gaseous radioiodine is pivotal the sustainable development nuclear energy long-term radiation safety ecological system. However, state-of-the-art adsorbents (e.g. metal–organic frameworks covalent–organic frameworks) currently under exploration suffer severely from limited capacity, especially a real-world scenario with extremely low concentration elevated temperature. This mostly originates relatively weak sorption driving forces mainly determined iodine-adsorbent interaction consisting noncovalent interactions small fraction strong chemical bonding. Here, we document discovery open metal-sulfide framework ((NH4)2(Sn3S7), donated as SCU-SnS) constructed three different types active sites superior iodine adsorbent. Benefiting ability pre-enrichment into charge-balancing NH4+ through N–H···I interaction, efficient reduction I2 affording I? S2?, high binding affinity between Sn4+ I?, SCU-SnS exhibit record-breaking capacity (2.12 g/g) dynamic breakthrough conditions highest static (6.12 among all reported inorganic adsorbents, both at 348 K. Its facile synthesis cost endow powerful application potential industry. Download figure PowerPoint Introduction removal during reactor operation, used fuel (UNF) reprocessing, accidents significant industry physical health general public.1 how efficiently capture molar diatomic harsh temperature humidity2,3 in off-gas streams (I2, 90%?100%; organic iodine, 0%?10%) remains unresolved issue. Apart traditional wet scrubbing method, solid-phase another practicable approach eliminate reprocessing plants merit generating negligible liquid waste. To date, increasing number solid-state have been investigated their performance. Activated carbon (AC) has extensively traps benign even though it not suitable handling UNF light its poor ignition point.4 Although (MOFs)5–9 (COFs),10,11 cutting-edge classes porous materials, excellent capacities moderate stability (e.g., acids) limit practical applications.12–15 importantly, capability relies on and/or interactions, which leads undesirable properties low-concentration temperatures. Silver-immersed or silver-exchanged zeolites are commercially utilized industry, benefiting well-known reaction silver iodine.16,17 availability gives rise modest performance that critically need improvement. Furthermore, extensive use costs accompanied inevitable environmental pollution. Therefore, crucial seek more economic removing conditions. Chalcogen-based aerogels (chalcogels) promising getters due combined sulfur iodine.18–22 randomly broadly distributed nanoscale pores arbitrarily arranged atoms, these chalcogels slow kinetics, efficiency, scant capacity. In addition, complex time-consuming process restricts widespread application. As crystalline analogues chalcogels, metal sulfides,23–29 versatile composition perforated frameworks, considered scavenger candidates. The precisely configured exposed coordination atoms sulfides provide approachable adsorption. inherent pore structure offers accessible diffusion path potentially leading enhanced kinetics. Herein, rationally designed prepared microporous two-dimensional thiostannate containing surface polarizability removal. First, given components, abundant hydrogen originating can pre-enrich via hydrogen-bond (N–H?I).30,31 Second, soft Lewis base S2? acid coupled propensity towards I?.32 Third, demonstrated be getter much higher preference iodization than Ag+ terms Gibb’s free energy.33 expected, integration single material uptake amount displays K materials. idea materials entirely composed well-arranged inspires new design strategy constructing adsorbents. Experimental Methods Characterization Synthesis mixture tin powder (357 mg, 3 mmol), (224 7 diethylenetriamine (2.5 mL) was added 20 mL stainless steel polytetrafluoroethylene vial. vial heated 180 °C 4 days, then cooled room rate 6 °C/h. Yellow block crystals black substances were obtained. After density variation bromoform, purified product finally acquired yellow SCU-SnS. Results Discussion Structure characterizations solvothermal powders presence affords pure yield 68.4%. Singl-crystal X-ray diffraction analysis reveals crystallizes centrosymmetric space group P63/mmc ( Supporting Information Table S1). asymmetric unit contains two crystallographically distinct ions, six ammonium cations. All Sn coordinate five diverse S forming SnS5 trigonal bipyramids Figure S1a), further connect generate Sn3S10 polyhedrons S1b). core integrates edge sharing, form 2D [Sn3S7]n2n? anionic layer parallel [001] plane. layers stacked AA sequence along c axis (Figure 1b). interlayer distance measured 5.876 Å. Originating thermal decomposition diethylenetriamine, cations counterions identified N–H?S bonds 1a). features network 12 × Å2 channels 1c), similar Fujian Institute Research Matter (FJSM)-SnS,24 Cs-SnS-1,34 TMA-SnS-1 (TMA = tetramethylammonium).35 solvent molecules highly disordered channels, whose amounts taking consideration results crystallographic data, element S2), thermogravimetric (TGA, S3). 1 | strategies corresponding deficiencies (i) chalcogen-based (ii) zeolites. (iii) SCU-SnS: (a) secondary SCU-SnS; (b) view ac plane; (c) large windows ab orange; indigo blue. nitrogen omitted clarity. consistency experimental simulated (PXRD) patterns indicates phase purity S2). shown scanning electron microscopy (SEM) image S4, micromorphology lamellar accordance crystal structural topology. energy-dispersive spectroscopy (EDS) spectrum, show ratio Sn?S 3.09?6.86, consistent results. Moreover, characteristic peak located nearly 0.4 keV demonstrates N S4).36 study SCU-SnS, TGA performed ranging 30 900 atmosphere. An approximately 1.97% weight loss before 100 resulted water molecules. second 31.56% indicated volatilization (b.p. 206 °C) when increased ca. 400 °C. Then sample gradually transformed SnS temperature.24 hydrolytic also tested soaking aqueous solutions pH values. S5 shows maintain crystallinity over wide 11. Intriguingly, maintains original after treatment 200 kGy ? ? irradiations S6). thermal, hydrolytic, irradiation suggests absorption radioactive temperature, moisture, intensive field). Static efficiency vapor Considering robust densely (S2? Sn4+), toward first closed system (the saturated pressure 1.6 kPa, corresponds volumetric 104 ppm bar according National Standards empirical formula).37,38 property ambient evaluate recording function time. Remarkably, rapidly adsorbed 401 wt % within 18 h reached maximum 612 120 2a). Even below some COFs (iCOF-OH-AB, JUC-561)39,40 polymers (POPs) ([email TBIM [T 2,4,6-trichloro-1,3,5-triazine, BIM biimidazole])41–45 respect density, area, nitrogen-rich structure, significantly those S4), vast majority MOF materials46–48 (MOF-808, CuBTC, ZIF-8), functionalized carbon49 (KOH-AC) same evidently Brunauer–Emmett–Teller areas. synergistic effect abundantly layers, well pores, dramatically improves molecule. confirmed well-fitted pseudo-second-order model S7 retention experiments conducted exposing I2-loaded (denoted I2@SCU-SnS) samples air verify major type I2@SCU-SnS mass least days S8), indicating derived molecule instead interaction. intriguingly, doses 60Co ?-irradiation ?-irradiation (provided accelerator), unchanged 2b). 2 resistance evaluated capacities. curves 298 (blue dots) (red dots). (d) Bar graphs dynamically captured dry humid (e) comparison various (note: uptakes MIL-101-Cr-TED MIL-101-Cr-HMTA condition 150 I2). Breakthrough studies probe applications, experiment carried out fixed-bed column setup, N2 (flow rate: 10 mL/min bar; concentration: ppm) pass sorbent bed packed 70 mg adsorbent set inductively plasma-mass spectrometry. For K, initially detected effluent h, plateaued until complete achieved 2c). Discrepant behavior observed Very significantly, time takes longer, approaching times recently COF materials.37,39 According increment, total 166 212 It should noted such HISL (53 %, hydrophobicity-intensified silicalite-1)4 Ag0@MOR38 (8 %), only lower iCOF-AB-50 (279 %) COF-OH-50 (170 %)39 S5). Note attributed porosity channel capturing weakened increases, owing activation I2. phenomenon greatly decreased K.37,39 On contrary, remarkably contrasting sharply case Ag0@MOR exothermal only.50 fact, best our knowledge, record value distinctly 2e, above exceptional rationalized following. one hand, endothermal process,51 promotes transformation other accelerates formation SnI4.33 Sn4+, theoretical very close actual quantity %. Since dissolved certain extent vapor, (RH 50%) respectively. 155.8 164.2% completely breaks through, representing slight decrease compared 2d). Despite contact angle measurement S9), still These illustrate probably most candidate packing date affirms stable feasible way remove humidity. estimated Ag0@MOR. S7, round adsorption, almost 300 Ag0@MOR, savings equal Of note, although silver-containing zeolite partially reused, reduced oxidation migration inner networks.16,17 regeneration presents tough issue because released contaminate related equipment. Instead, irreversible nature simple scalable possibility direct disposal I2-incorporated waste radioiodine. Investigation mechanism outstanding encouraged us investigate mechanisms. S10, iodine-saturated changes pristine morphology, color turns black, Elemental mapping images using SEM-EDS homogenous distribution I S11). species comprehensive PXRD, Raman (RM), Fourier transform infrared (FT-IR) PXRD pattern exhibits intense peaks assigned SnI4 3b). generation visually newly formed orange solid adhering columns Figures S12 S13). spectrum 3a, band 109 cm?1 ascribed I3?, quite vibrational overtones molecular 183 cm?1.52,53 result charge transfer occurred iodine. Significantly, additional 218 symmetric S–S vibrations.54 FT-IR spectra S14), there no clearly observable SO42? bands 1097 cm?1.32 Taking consideration, elemental (S8) likely SO42?. Thus, possible schemes described follows: (NH4)2Sn3S7 + ? NH4[I?•I2] S8. polyiodide anions I3? I?. I2@SCU-SnS. I2@SCU-SnS, SnI4. 3d XPS 1s schematic diagram blue; bluish violet. photoelectron (XPS) measurements explore host-guest S15). 3c, verified energies 630 610 eV. Actually, 628.95 617.45 eV typically 3d3/2 3d5/2, sample.55 chemisorption accounts 400.4 observed, confirming host–guest 3d).39 Based mechanisms overall inferred follows. pervade diffusion. “soft-soft” Further, oxidize resulting S8 Meanwhile, physically adsorbs produced electrostatic attraction bond. continuously progresses, promoted so 3e). provides fundamental principle route creation content Conclusion contribution, present philosophy high-performance facilely synthesized one-pot method yields. Coupled possesses (400 far surpasses Importantly, advantage MOFs, COFs, comprehens