Pub Date : 2026-01-10DOI: 10.1016/j.seppur.2026.136864
Jasmina Puc, Nina Mencin, Andreja Krušič, Evelin Nett, Mario Perković, Ugur Sahin, Aleš Štrancar, Rok Sekirnik
Removal of double-stranded RNA (dsRNA) is a critical part of production processes for mRNA vaccines and therapeutics, due to the high immunogenicity of this impurity. dsRNA contaminants are produced during in vitro transcription reaction, and typically removed using ion-pair reverse-phase or cellulose based chromatography. However, removal is challenging because of dsRNA's intrinsically similar physicochemical properties with single stranded RNA (ssRNA). We report a novel approach to remove dsRNA which targets hydrogen bonding as the physico-chemical stabiliser of dsRNA: breaking these hydrogen bonds increases chromatographic differentiation, and can be achieved with pH modulation in a cheap, non-hazardous and scalable technique. We demonstrate that incubation of mRNA at pH ≤3.5 denatures dsRNA within seconds for mRNA/saRNA constructs spanning 1–10 kb, without compromising mRNA integrity. Coupling in-line pH 3 treatment with Oligo dT capture reduced dsRNA from various mRNAs from 0.14 to 0.77% to 0.02–0.09% while achieving ≥90% recovery irrespective of column loading, and improving integrity by concomitantly removing short RNA fragments. This purification approach increased mRNA cellular potency 5-fold in A549 cells and markedly reduced type I interferon signalling, while maintaining cellular viability. This simple, aqueous, and scalable method establishes a new purification paradigm for producing high-quality mRNA drug substance with high recovery, compatible with clinically validated Oligo dT technology.
{"title":"pH denaturation of dsRNA: A novel approach to mRNA purification","authors":"Jasmina Puc, Nina Mencin, Andreja Krušič, Evelin Nett, Mario Perković, Ugur Sahin, Aleš Štrancar, Rok Sekirnik","doi":"10.1016/j.seppur.2026.136864","DOIUrl":"https://doi.org/10.1016/j.seppur.2026.136864","url":null,"abstract":"Removal of double-stranded RNA (dsRNA) is a critical part of production processes for mRNA vaccines and therapeutics, due to the high immunogenicity of this impurity. dsRNA contaminants are produced during in vitro transcription reaction, and typically removed using ion-pair reverse-phase or cellulose based chromatography. However, removal is challenging because of dsRNA's intrinsically similar physicochemical properties with single stranded RNA (ssRNA). We report a novel approach to remove dsRNA which targets hydrogen bonding as the physico-chemical stabiliser of dsRNA: breaking these hydrogen bonds increases chromatographic differentiation, and can be achieved with pH modulation in a cheap, non-hazardous and scalable technique. We demonstrate that incubation of mRNA at pH ≤3.5 denatures dsRNA within seconds for mRNA/saRNA constructs spanning 1–10 kb, without compromising mRNA integrity. Coupling in-line pH 3 treatment with Oligo dT capture reduced dsRNA from various mRNAs from 0.14 to 0.77% to 0.02–0.09% while achieving ≥90% recovery irrespective of column loading, and improving integrity by concomitantly removing short RNA fragments. This purification approach increased mRNA cellular potency 5-fold in A549 cells and markedly reduced type I interferon signalling, while maintaining cellular viability. This simple, aqueous, and scalable method establishes a new purification paradigm for producing high-quality mRNA drug substance with high recovery, compatible with clinically validated Oligo dT technology.","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"17 1","pages":"136864"},"PeriodicalIF":8.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145969004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-10DOI: 10.1016/j.seppur.2026.136861
Xianshuai Niu , Yingchao Li , Xiaobo Wang , Guiping Jiang , Yanan Tan , Chengjun Sun , Haiwen Wei , Peng Ju
Urgent remediation of antibiotic-contaminated nearshore waters and sediments and derived harmful algal blooms from marine aquaculture is a pressing environmental issue. This study presents a novel sulfur vacancy-rich molybdenum-doped biochar (SV-MoS2@BC) synthesized via a simple co-pyrolysis of marine green algae Enteromorpha prolifera. SV-MoS2@BC demonstrated an exceptional catalytic performance without light or added oxidants, achieving complete removal of tetracycline (TC) from seawater within 60 min. Besides, SV-MoS2@BC exhibited a remarkable stability over a broad pH range (1–9) and maintained above 85% efficiency during five cycles. The TOC analysis suggested that SV-MoS2@BC enabled a TC mineralization efficiency exceeding 80% within 60 min. In 7-day sediment remediation, SV-MoS2@BC significantly reduced TC in both pore water and overlying water. The excellent catalytic capacity can be ascribed to the synergy between sulfur vacancies in MoS2 and biochar functional groups. This synergy can activate dissolved oxygen to generate dominant reactive species (∙OH, ∙O2− and 1O2) via radical and non-radical pathways, while functional groups acted as electron donors to sustain the Mo4+/Mo5+ redox cycle. This study not only presents a novel strategy for in-situ remediation of antibiotic-contaminated seawater and sediments but also enables the high-value utilization of Enteromorpha prolifera waste, realizing dual environmental and economic benefits.
{"title":"Enteromorpha prolifera biochar enhanced MoS2 for remediating antibiotics in seawater-sediment systems: Synergistic mechanism of biochar adsorption with sulfur vacancy catalysis","authors":"Xianshuai Niu , Yingchao Li , Xiaobo Wang , Guiping Jiang , Yanan Tan , Chengjun Sun , Haiwen Wei , Peng Ju","doi":"10.1016/j.seppur.2026.136861","DOIUrl":"10.1016/j.seppur.2026.136861","url":null,"abstract":"<div><div>Urgent remediation of antibiotic-contaminated nearshore waters and sediments and derived harmful algal blooms from marine aquaculture is a pressing environmental issue. This study presents a novel sulfur vacancy-rich molybdenum-doped biochar (S<sub>V</sub>-MoS<sub>2</sub>@BC) synthesized via a simple co-pyrolysis of marine green algae <em>Enteromorpha prolifera</em>. S<sub>V</sub>-MoS<sub>2</sub>@BC demonstrated an exceptional catalytic performance without light or added oxidants, achieving complete removal of tetracycline (TC) from seawater within 60 min. Besides, S<sub>V</sub>-MoS<sub>2</sub>@BC exhibited a remarkable stability over a broad pH range (1–9) and maintained above 85% efficiency during five cycles. The TOC analysis suggested that S<sub>V</sub>-MoS<sub>2</sub>@BC enabled a TC mineralization efficiency exceeding 80% within 60 min. In 7-day sediment remediation, S<sub>V</sub>-MoS<sub>2</sub>@BC significantly reduced TC in both pore water and overlying water. The excellent catalytic capacity can be ascribed to the synergy between sulfur vacancies in MoS<sub>2</sub> and biochar functional groups. This synergy can activate dissolved oxygen to generate dominant reactive species (∙OH, ∙O<sub>2</sub><sup>−</sup> and <sup>1</sup>O<sub>2</sub>) via radical and non-radical pathways, while functional groups acted as electron donors to sustain the Mo<sup>4+</sup>/Mo<sup>5+</sup> redox cycle. This study not only presents a novel strategy for in-situ remediation of antibiotic-contaminated seawater and sediments but also enables the high-value utilization of <em>Enteromorpha prolifera</em> waste, realizing dual environmental and economic benefits.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"389 ","pages":"Article 136861"},"PeriodicalIF":9.0,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-10DOI: 10.1016/j.seppur.2026.136865
Xiao Zhang , Wenxin Liu , Feng Shen , Boxiong Shen , Shuhao Li
The development of high-entropy oxide (HEO) catalysts is often limited by high synthesis temperatures and low surface areas, which restrict their effectiveness in volatile organic compound (VOC) oxidation. In this study, we propose a novel coordination-assembly method for synthesizing Pt-based HEO catalysts, where organic ligands serve dual functions: (i) reducing the formation energy barrier for HEO crystallization and (ii) anchoring Pt precursors during synthesis. This dual effect enables the formation of spinel-phase HEO (HEOC) at a relatively low synthesis temperature (600 °C), with a significantly enhanced BET surface area of 22.8 m2/g, markedly higher than that of conventionally synthesized HEOs (<5 m2/g). The resulting Pt@HEO-C catalyst exhibits excellent catalytic performance for o-xylene oxidation, achieving a T90 at 231 °C, significantly lower than those of Pt catalysts supported on conventional HEOs and mixed oxides. In-situ DRIFTS and GC–MS analyses confirm that the Pt@HEO-C catalyst facilitates the further oxidation of ring-opening intermediates, improving reaction selectivity. Density functional theory calculations reveal enhanced Pt dispersion, uniform adsorption energetics, and stronger Pt-support charge transfer in the Pt@HEO-C catalyst. The catalyst also shows remarkable sulphur tolerance and long-term stability. This work demonstrates the potential of ligand-directed coordination-assembly strategies in constructing high-surface-area HEOs at low temperatures for advanced VOC oxidation applications.
{"title":"Coordination-assembly synthesis of Pt-based high-entropy oxide catalysts for VOC oxidation: dual role of ligands in reducing formation barrier and anchoring active sites","authors":"Xiao Zhang , Wenxin Liu , Feng Shen , Boxiong Shen , Shuhao Li","doi":"10.1016/j.seppur.2026.136865","DOIUrl":"10.1016/j.seppur.2026.136865","url":null,"abstract":"<div><div>The development of high-entropy oxide (HEO) catalysts is often limited by high synthesis temperatures and low surface areas, which restrict their effectiveness in volatile organic compound (VOC) oxidation. In this study, we propose a novel coordination-assembly method for synthesizing Pt-based HEO catalysts, where organic ligands serve dual functions: (i) reducing the formation energy barrier for HEO crystallization and (ii) anchoring Pt precursors during synthesis. This dual effect enables the formation of spinel-phase HEO (HEO<img>C) at a relatively low synthesis temperature (600 °C), with a significantly enhanced BET surface area of 22.8 m<sup>2</sup>/g, markedly higher than that of conventionally synthesized HEOs (<5 m<sup>2</sup>/g). The resulting Pt@HEO-C catalyst exhibits excellent catalytic performance for o-xylene oxidation, achieving a T<sub>90</sub> at 231 °C, significantly lower than those of Pt catalysts supported on conventional HEOs and mixed oxides. In-situ DRIFTS and GC–MS analyses confirm that the Pt@HEO-C catalyst facilitates the further oxidation of ring-opening intermediates, improving reaction selectivity. Density functional theory calculations reveal enhanced Pt dispersion, uniform adsorption energetics, and stronger Pt-support charge transfer in the Pt@HEO-C catalyst. The catalyst also shows remarkable sulphur tolerance and long-term stability. This work demonstrates the potential of ligand-directed coordination-assembly strategies in constructing high-surface-area HEOs at low temperatures for advanced VOC oxidation applications.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"389 ","pages":"Article 136865"},"PeriodicalIF":9.0,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-09DOI: 10.1016/j.seppur.2026.136844
Xiaoyu Mu , Jun Ma , Jinze Du , Haifeng Cong , Xingang Li
As a critical unconventional petroleum resource, shale oil plays a pivotal role in addressing global energy crises. However, water-in-shale oil (W/SO) emulsions formed can significantly reduce shale oil quality, increase production costs and pollute environment in the process of shale oil exploitation. To achieve efficient demulsification of W/SO emulsions. Herein, we have successfully synthesized a novel star-like topological demulsifier (NSTD) containing multiple hydrogen bond sites by esterification and Michael addition reactions. Demulsification tests showed that NSTD (500 ppm) can achieve complete demulsification of W/SO emulsions (100% efficiency) at 50 °C in 20 min. Microscopic visualization combined with molecular dynamics simulations confirmed that the excellent performance of NSTD originates from the molecular topological structure perturbation effect dominated by noncovalent forces formed by NSTD molecules at the shale oil–water interface. It is precisely the interfacial perturbation effect that rupture the asphaltene-stabilized interfacial film in W/SO emulsions, facilitating the aggregation and merging of dispersed water droplets, and thereby realizing efficient demulsification. This study establishes a firm theoretical basis and offers new perspectives for the advancement of low-temperature, energy-efficient separation technologies applicable to shale oil emulsions.
{"title":"Noncovalent forces-governed interfacial perturbation for efficient demulsification of water-in-shale oil emulsions","authors":"Xiaoyu Mu , Jun Ma , Jinze Du , Haifeng Cong , Xingang Li","doi":"10.1016/j.seppur.2026.136844","DOIUrl":"10.1016/j.seppur.2026.136844","url":null,"abstract":"<div><div>As a critical unconventional petroleum resource, shale oil plays a pivotal role in addressing global energy crises. However, water-in-shale oil (W/SO) emulsions formed can significantly reduce shale oil quality, increase production costs and pollute environment in the process of shale oil exploitation. To achieve efficient demulsification of W/SO emulsions. Herein, we have successfully synthesized a novel star-like topological demulsifier (NSTD) containing multiple hydrogen bond sites by esterification and Michael addition reactions. Demulsification tests showed that NSTD (500 ppm) can achieve complete demulsification of W/SO emulsions (100% efficiency) at 50 °C in 20 min. Microscopic visualization combined with molecular dynamics simulations confirmed that the excellent performance of NSTD originates from the molecular topological structure perturbation effect dominated by noncovalent forces formed by NSTD molecules at the shale oil–water interface. It is precisely the interfacial perturbation effect that rupture the asphaltene-stabilized interfacial film in W/SO emulsions, facilitating the aggregation and merging of dispersed water droplets, and thereby realizing efficient demulsification. This study establishes a firm theoretical basis and offers new perspectives for the advancement of low-temperature, energy-efficient separation technologies applicable to shale oil emulsions.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"388 ","pages":"Article 136844"},"PeriodicalIF":9.0,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-09DOI: 10.1016/j.seppur.2026.136850
Junyan Ma , Xingya Huang , Aokun Li , Jingjing Chen , Xiaoli Wu , Jingtao Wang
Nanochannel-molecule interactions are of paramount importance for molecule transport in confined nanochannels. Except for molecular solubility parameter, molecular dipole moment highly affects the electrostatic interactions with charged nanochannels, but its influence on molecule transport has yet been elucidated. The precise molecule separation based on dipole moment difference is therefore rarely reported. Herein, vertically-aligned nanochannel membranes with tunable charge properties were fabricated, the charge intensity of which was adjusted by regulating various functional groups (CH3, NH2, F3). Based on these robust and long-range 2D nanochannels, the influence of molecule dipole moment on its transport behaviors is explored for the first time. We demonstrate that compared with non-polar molecules, polar molecules with obvious dipole are induced to generate an induced dipole moment (Did) in charged nanochannels. Molecules with small intrinsic dipole moments (Din) exhibit a high dipole variation (over 73.5%) caused by the electrostatic interaction, leading to a high dependence of their permeance on the charge intensity of nanochannels. In contrast, molecules with large intrinsic dipole moments display negligible dipole variation (below 7.9%), and their permeance shows weak fluctuations to the charge intensity of nanochannels. Furthermore, we reveal that the total dipole moment (Dt) dominates the electrostatic interaction strength of molecules with the charged nanochannels, which affects the transport permeance. The permeance adheres to the formula: (μ, viscosity; Dt, total dipole moment; r, molecule diameter; V, charge intensity of nanochannel). Accordingly, a high separation factor of 8.36 for ethanol/water is achieved for charged membrane.
{"title":"Dipole moment mediated molecule transport behaviors in charged vertically-aligned 2D nanochannels","authors":"Junyan Ma , Xingya Huang , Aokun Li , Jingjing Chen , Xiaoli Wu , Jingtao Wang","doi":"10.1016/j.seppur.2026.136850","DOIUrl":"10.1016/j.seppur.2026.136850","url":null,"abstract":"<div><div>Nanochannel-molecule interactions are of paramount importance for molecule transport in confined nanochannels. Except for molecular solubility parameter, molecular dipole moment highly affects the electrostatic interactions with charged nanochannels, but its influence on molecule transport has yet been elucidated. The precise molecule separation based on dipole moment difference is therefore rarely reported. Herein, vertically-aligned nanochannel membranes with tunable charge properties were fabricated, the charge intensity of which was adjusted by regulating various functional groups (<img>CH<sub>3</sub>, <img>NH<sub>2</sub>, <img>F<sub>3</sub>). Based on these robust and long-range 2D nanochannels, the influence of molecule dipole moment on its transport behaviors is explored for the first time. We demonstrate that compared with non-polar molecules, polar molecules with obvious dipole are induced to generate an induced dipole moment (D<sub>id</sub>) in charged nanochannels. Molecules with small intrinsic dipole moments (D<sub>in</sub>) exhibit a high dipole variation (over 73.5%) caused by the electrostatic interaction, leading to a high dependence of their permeance on the charge intensity of nanochannels. In contrast, molecules with large intrinsic dipole moments display negligible dipole variation (below 7.9%), and their permeance shows weak fluctuations to the charge intensity of nanochannels. Furthermore, we reveal that the total dipole moment (D<sub>t</sub>) dominates the electrostatic interaction strength of molecules with the charged nanochannels, which affects the transport permeance. The permeance adheres to the formula:<span><math><mspace></mspace><mi>P</mi><mo>=</mo><mi>k</mi><mfrac><mn>1</mn><mrow><mi>μ</mi><msubsup><mi>D</mi><mi>t</mi><mn>2</mn></msubsup><msup><mi>r</mi><mn>0.5</mn></msup><mi>V</mi></mrow></mfrac></math></span> (<em>μ</em>, viscosity; <em>D</em><sub><em>t</em></sub>, total dipole moment; <em>r</em>, molecule diameter; <em>V</em>, charge intensity of nanochannel). Accordingly, a high separation factor of 8.36 for ethanol/water is achieved for charged membrane.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"389 ","pages":"Article 136850"},"PeriodicalIF":9.0,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976021","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-09DOI: 10.1016/j.seppur.2026.136841
Manjusha Passi, Shushil Kumar
Globally, the pulp and paper industry discharges ∼696 million m3 of lignin-rich wastewater annually, posing severe environmental risks. Photocatalysis, an advanced oxidation process, provides a sustainable and efficient treatment while facilitating partial lignin valorisation. Herein, a CoAl2O4/g-C3N4/ZIF-8 S-scheme heterojunction photocatalyst was synthesized to effectively depolymerize lignosulfonate by disrupting its robust CC and CO bonds. Comprehensive characterization of the developed catalyst and its pristine and binary counterparts was carried out using XRD, SEM, TEM, XPS, BET, EIS, UV–vis, PL and Raman techniques. With an energy-efficient LED light excitation, the CoAl2O4/g-C3N4/ZIF-8 depolymerized 88% of lignosulphonate within 210 min, surpassing CoAl2O4, g-C3N4, ZIF-8, and CoAl2O4/g-C3N4 by factors of ∼1.7, 2.4, 3.5, and 1.4 respectively. The synergistic role of g-C3N4 (facilitating charge transfer), CoAl2O4 (visible-light harvesting), and ZIF-8 (structural stability and dispersion support) collectively broadens light absorption and accelerates lignosulfonate depolymerization. TOC assessment evidenced 60.5% reduction in lignosulfonate-derived organic matter. Scavenger experiments and ESR analysis revealed O2•− and •OH as the dominant reactive species driving the depolymerization. HR-MS detected 16 intermediates products, including 3-methoxycatechol, vanillin, guaiacol, ferulic acid, and specifically, the smallest ring opening product, malic acid, affirming the selective breakdown of lignosulfonate. In light of these findings, a probable photocatalytic mechanism and transformation pathways for lignosulfonate were deduced. The material exhibited good recyclability, preserving 61.0% of its activity after five consecutive runs. This work demonstrates that CoAl2O4/g-C3N4/ZIF-8 ternary catalyst, integrating a spinel oxide, a polymeric semiconductor, and a porous MOF, offers an efficient approach for photo-assisted lignin depolymerization, enabling efficient treatment of lignosulfonate-rich wastewater and supporting circular bio-economy practices through waste valorisation.
{"title":"ZIF-8 supported CoAl2O4/g-C3N4 S-scheme heterojunction for visible-light-induced oxidative Depolymerization of industrial lignosulfonate: Kinetics, reaction pathways and mechanistic insights","authors":"Manjusha Passi, Shushil Kumar","doi":"10.1016/j.seppur.2026.136841","DOIUrl":"10.1016/j.seppur.2026.136841","url":null,"abstract":"<div><div>Globally, the pulp and paper industry discharges ∼696 million m<sup>3</sup> of lignin-rich wastewater annually, posing severe environmental risks. Photocatalysis, an advanced oxidation process, provides a sustainable and efficient treatment while facilitating partial lignin valorisation. Herein, a CoAl<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub>/ZIF-8 S-scheme heterojunction photocatalyst was synthesized to effectively depolymerize lignosulfonate by disrupting its robust C<img>C and C<img>O bonds. Comprehensive characterization of the developed catalyst and its pristine and binary counterparts was carried out using XRD, SEM, TEM, XPS, BET, EIS, UV–vis, PL and Raman techniques. With an energy-efficient LED light excitation, the CoAl<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub>/ZIF-8 depolymerized 88% of lignosulphonate within 210 min, surpassing CoAl<sub>2</sub>O<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>, ZIF-8, and CoAl<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> by factors of ∼1.7, 2.4, 3.5, and 1.4 respectively. The synergistic role of g-C<sub>3</sub>N<sub>4</sub> (facilitating charge transfer), CoAl<sub>2</sub>O<sub>4</sub> (visible-light harvesting), and ZIF-8 (structural stability and dispersion support) collectively broadens light absorption and accelerates lignosulfonate depolymerization. TOC assessment evidenced 60.5% reduction in lignosulfonate-derived organic matter. Scavenger experiments and ESR analysis revealed O<sub>2</sub><sup><strong>•</strong>−</sup> and <sup><strong>•</strong></sup>OH as the dominant reactive species driving the depolymerization. HR-MS detected 16 intermediates products, including 3-methoxycatechol, vanillin, guaiacol, ferulic acid, and specifically, the smallest ring opening product, malic acid, affirming the selective breakdown of lignosulfonate. In light of these findings, a probable photocatalytic mechanism and transformation pathways for lignosulfonate were deduced. The material exhibited good recyclability, preserving 61.0% of its activity after five consecutive runs. This work demonstrates that CoAl<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub>/ZIF-8 ternary catalyst, integrating a spinel oxide, a polymeric semiconductor, and a porous MOF, offers an efficient approach for photo-assisted lignin depolymerization, enabling efficient treatment of lignosulfonate-rich wastewater and supporting circular bio-economy practices through waste valorisation.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"388 ","pages":"Article 136841"},"PeriodicalIF":9.0,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-09DOI: 10.1016/j.seppur.2026.136835
Thomas J. Robshaw , Magali Goncalves Rego , Stephen Reid , Alastair Baker , Timothy Hunter , Kathryn George
The fractionation of lithium isotopes is of great importance to the nuclear industry. Solvent extraction (SX) methods using benzo-15-crown-5 ether (B15C5) are one of the more mature and easily scalable technologies to achieve this. However, the isotopic enrichment (α) possible for SX has not been significantly improved for >40 years. Here, we present an investigation into a novel three-phase (liquid-liquid-solid) system, combining B15C5, dissolved in an imidazolium ionic liquid, with two organosilicas with ethyl/butyl phosphonic acid (EBPsil) and sulfonic acid (SULFsil) functional groups. The aqueous Li mass transfer was investigated, initially in two-phase systems, which suggested that Li was favourably extracted as complexes involving two of the extracting ligands. The B15C5 organic phase produced the highest distribution coefficient (KD), followed by SULFsil. In three-phase experiments, it was found that increasing the effective ligand concentration in either the liquid or solid phase increased Li transfer into that phase, but not at the expense of transfer into the other non-aqueous phase. Li extraction could not be well controlled by initial aqueous pH, due to buffering by contact with the ionic liquid in the organic phase. The addition of Mg2+ as a competing ion was strongly suppressive for solid-phase adsorption, but not SX. A maximum α of 1.035 ± 0.004 was achieved for 6Li enrichment in the organic phase, at a Li/B15C5 ether molar ratio of ∼2.5. Surprisingly, increasing the organosilica mass in the system appeared to enhance the α value for the organic phase, which is contrary to almost every other study involving Li isotope fractionation via cation-exchange. This result was believed to be due to the hydrophilicity of the silica-based matrix and suggests that a pathway is possible to significant improvement in isotope fractionation efficiency, using a three-phase methodology.
{"title":"Investigations into a ternary liquid-liquid-solid extraction system for partitioning of lithium, with a view to potential isotopic enrichment applications","authors":"Thomas J. Robshaw , Magali Goncalves Rego , Stephen Reid , Alastair Baker , Timothy Hunter , Kathryn George","doi":"10.1016/j.seppur.2026.136835","DOIUrl":"10.1016/j.seppur.2026.136835","url":null,"abstract":"<div><div>The fractionation of lithium isotopes is of great importance to the nuclear industry. Solvent extraction (SX) methods using benzo-15-crown-5 ether (B15C5) are one of the more mature and easily scalable technologies to achieve this. However, the isotopic enrichment (α) possible for SX has not been significantly improved for >40 years. Here, we present an investigation into a novel three-phase (liquid-liquid-solid) system, combining B15C5, dissolved in an imidazolium ionic liquid, with two organosilicas with ethyl/butyl phosphonic acid (EBPsil) and sulfonic acid (SULFsil) functional groups. The aqueous Li mass transfer was investigated, initially in two-phase systems, which suggested that Li was favourably extracted as complexes involving two of the extracting ligands. The B15C5 organic phase produced the highest distribution coefficient (K<sub>D</sub>), followed by SULFsil. In three-phase experiments, it was found that increasing the effective ligand concentration in either the liquid or solid phase increased Li transfer into that phase, but not at the expense of transfer into the other non-aqueous phase. Li extraction could not be well controlled by initial aqueous pH, due to buffering by contact with the ionic liquid in the organic phase. The addition of Mg<sup>2+</sup> as a competing ion was strongly suppressive for solid-phase adsorption, but not SX. A maximum α of 1.035 ± 0.004 was achieved for <sup>6</sup>Li enrichment in the organic phase, at a Li/B15C5 ether molar ratio of ∼2.5. Surprisingly, increasing the organosilica mass in the system appeared to enhance the α value for the organic phase, which is contrary to almost every other study involving Li isotope fractionation via cation-exchange. This result was believed to be due to the hydrophilicity of the silica-based matrix and suggests that a pathway is possible to significant improvement in isotope fractionation efficiency, using a three-phase methodology.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"389 ","pages":"Article 136835"},"PeriodicalIF":9.0,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-09DOI: 10.1016/j.seppur.2026.136847
Shuangxi Zhu , Zhansheng Wu , Simin Li , Lele He , Xianzhen Li , Diao She
In this study, a series of lignin-based polyporous biochars (LZXB) were successfully prepared via the high-temperature pyrolysis of ZnCl2 modified industrial alkali lignin hydrochar, with the aim of removing norfloxacin (NOR) from water. Among them, LZ5B exhibited the best adsorption performance for NOR, achieving a removal rate of 98.83%. Characterization results revealed that ZnCl2 activation endowed LZ5B with a well-developed porous structure, significantly increasing its specific surface area from 1.91 to 1117.03 m2/g. Variations in surface functional groups and elemental composition were also observed, which collectively enhanced its adsorption capacity for NOR. In batch adsorption experiments, LZ5B exhibited excellent NOR removal performance under various conditions — including in the presence of coexisting ions, organic compounds, or antibiotics, after nine cycles of reuse, and in actual water bodies. Combined with density functional theory calculation and other experimental evidence, it was found that pore filling, electrostatic attraction, hydrogen bonding, π–π interactions, and surface complexation acted synergistically to promote the adsorption of NOR by LZ5B. Furthermore, soil column experiment using yellow loess soil, lou soil, and latosol soil further indicated that LZ5B could not only directly adsorb NOR, but also indirectly immobilize NOR bound to dissolved organic matter in the soil, thereby cooperatively inhibiting the vertical migration of NOR in soil. This study provides new insights into the recycling of industrial alkali lignin and the treatment of contaminants in aquatic and soil environments, achieving the goal of treating waste with waste.
{"title":"ZnCl2 modification enhanced lignin-based biochar for efficient norfloxacin removal from water and the inhibition of vertical migration in soil","authors":"Shuangxi Zhu , Zhansheng Wu , Simin Li , Lele He , Xianzhen Li , Diao She","doi":"10.1016/j.seppur.2026.136847","DOIUrl":"10.1016/j.seppur.2026.136847","url":null,"abstract":"<div><div>In this study, a series of lignin-based polyporous biochars (LZ<sub>X</sub>B) were successfully prepared via the high-temperature pyrolysis of ZnCl<sub>2</sub> modified industrial alkali lignin hydrochar, with the aim of removing norfloxacin (NOR) from water. Among them, LZ<sub>5</sub>B exhibited the best adsorption performance for NOR, achieving a removal rate of 98.83%. Characterization results revealed that ZnCl<sub>2</sub> activation endowed LZ<sub>5</sub>B with a well-developed porous structure, significantly increasing its specific surface area from 1.91 to 1117.03 m<sup>2</sup>/g. Variations in surface functional groups and elemental composition were also observed, which collectively enhanced its adsorption capacity for NOR. In batch adsorption experiments, LZ<sub>5</sub>B exhibited excellent NOR removal performance under various conditions — including in the presence of coexisting ions, organic compounds, or antibiotics, after nine cycles of reuse, and in actual water bodies. Combined with density functional theory calculation and other experimental evidence, it was found that pore filling, electrostatic attraction, hydrogen bonding, π–π interactions, and surface complexation acted synergistically to promote the adsorption of NOR by LZ<sub>5</sub>B. Furthermore, soil column experiment using yellow loess soil, lou soil, and latosol soil further indicated that LZ<sub>5</sub>B could not only directly adsorb NOR, but also indirectly immobilize NOR bound to dissolved organic matter in the soil, thereby cooperatively inhibiting the vertical migration of NOR in soil. This study provides new insights into the recycling of industrial alkali lignin and the treatment of contaminants in aquatic and soil environments, achieving the goal of treating waste with waste.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"389 ","pages":"Article 136847"},"PeriodicalIF":9.0,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-09DOI: 10.1016/j.seppur.2026.136787
Shounak G. Joshi, Allyson L. McGaughey, Amy E. Childress
Membrane wetting remains a critical limitation in membrane distillation (MD), yet contact angle (<span><span><math><mi is="true">θ</mi></math></span><script type="math/mml"><math><mi is="true">θ</mi></math></script></span>) measurements that are commonly used to assess wetting resistance are defined and interpreted inconsistently in the MD literature. In this study, we characterize the surface properties and wetting resistance of three commercially available polytetrafluoroethylene membrane distillation (MD) membranes and clarify the physical meaning of commonly reported contact angles. By adapting an established method to quantify wetting-state transitions, we show that conventional contact angle measurements (<span><span><math><msub is="true"><mi is="true">θ</mi><mrow is="true"><mi is="true">m</mi><mo is="true">,</mo><mi is="true" mathvariant="italic">conv</mi></mrow></msub></math></span><script type="math/mml"><math><msub is="true"><mi is="true">θ</mi><mrow is="true"><mi is="true">m</mi><mo is="true">,</mo><mi mathvariant="italic" is="true">conv</mi></mrow></msub></math></script></span>) correspond to a Cassie-Baxter wetting state. We further demonstrate that the transition to a Wenzel wetting state occurs at applied pressures of ~270–290 Pa, well below typical MD operating pressures, indicating that these hydrophobic membranes operate in a Wenzel wetting state during MD. To more accurately characterize wetting resistance during MD, we introduce methods to calculate a pore-scale Wenzel state contact angle, <span><span><math><msubsup is="true"><mi is="true">θ</mi><mi is="true">W</mi><mo is="true">∗</mo></msubsup></math></span><script type="math/mml"><math><msubsup is="true"><mi is="true">θ</mi><mi is="true">W</mi><mo is="true">∗</mo></msubsup></math></script></span>, based on measured membrane roughness and intrinsic contact angle (<span><span><math><msub is="true"><mi is="true">θ</mi><mn is="true">0</mn></msub></math></span><script type="math/mml"><math><msub is="true"><mi is="true">θ</mi><mn is="true">0</mn></msub></math></script></span>). The resulting <span><span><math><msubsup is="true"><mi is="true">θ</mi><mi is="true">W</mi><mo is="true">∗</mo></msubsup></math></span><script type="math/mml"><math><msubsup is="true"><mi is="true">θ</mi><mi is="true">W</mi><mo is="true">∗</mo></msubsup></math></script></span> values are unique: <span><span><math><msubsup is="true"><mi is="true">θ</mi><mi is="true">W</mi><mo is="true">∗</mo></msubsup></math></span><script type="math/mml"><math><msubsup is="true"><mi is="true">θ</mi><mi is="true">W</mi><mo is="true">∗</mo></msubsup></math></script></span> is significantly greater (by 12–17%) than <span><span><math><msub is="true"><mi is="true">θ</mi><mn is="true">0</mn></msub></math></span><script type="math/mml"><math><msub is="true"><mi is="true">θ</mi><mn is="true">0</mn></msub></math></script></span> and significantly less (by 11–17%) than <span><span><math><msub is="true"><mi is="true">θ</mi><mrow is="t
{"title":"Role of wetting state in improved prediction of wetting resistance in membrane distillation","authors":"Shounak G. Joshi, Allyson L. McGaughey, Amy E. Childress","doi":"10.1016/j.seppur.2026.136787","DOIUrl":"https://doi.org/10.1016/j.seppur.2026.136787","url":null,"abstract":"Membrane wetting remains a critical limitation in membrane distillation (MD), yet contact angle (<span><span><math><mi is=\"true\">θ</mi></math></span><script type=\"math/mml\"><math><mi is=\"true\">θ</mi></math></script></span>) measurements that are commonly used to assess wetting resistance are defined and interpreted inconsistently in the MD literature. In this study, we characterize the surface properties and wetting resistance of three commercially available polytetrafluoroethylene membrane distillation (MD) membranes and clarify the physical meaning of commonly reported contact angles. By adapting an established method to quantify wetting-state transitions, we show that conventional contact angle measurements (<span><span><math><msub is=\"true\"><mi is=\"true\">θ</mi><mrow is=\"true\"><mi is=\"true\">m</mi><mo is=\"true\">,</mo><mi is=\"true\" mathvariant=\"italic\">conv</mi></mrow></msub></math></span><script type=\"math/mml\"><math><msub is=\"true\"><mi is=\"true\">θ</mi><mrow is=\"true\"><mi is=\"true\">m</mi><mo is=\"true\">,</mo><mi mathvariant=\"italic\" is=\"true\">conv</mi></mrow></msub></math></script></span>) correspond to a Cassie-Baxter wetting state. We further demonstrate that the transition to a Wenzel wetting state occurs at applied pressures of ~270–290 Pa, well below typical MD operating pressures, indicating that these hydrophobic membranes operate in a Wenzel wetting state during MD. To more accurately characterize wetting resistance during MD, we introduce methods to calculate a pore-scale Wenzel state contact angle, <span><span><math><msubsup is=\"true\"><mi is=\"true\">θ</mi><mi is=\"true\">W</mi><mo is=\"true\">∗</mo></msubsup></math></span><script type=\"math/mml\"><math><msubsup is=\"true\"><mi is=\"true\">θ</mi><mi is=\"true\">W</mi><mo is=\"true\">∗</mo></msubsup></math></script></span>, based on measured membrane roughness and intrinsic contact angle (<span><span><math><msub is=\"true\"><mi is=\"true\">θ</mi><mn is=\"true\">0</mn></msub></math></span><script type=\"math/mml\"><math><msub is=\"true\"><mi is=\"true\">θ</mi><mn is=\"true\">0</mn></msub></math></script></span>). The resulting <span><span><math><msubsup is=\"true\"><mi is=\"true\">θ</mi><mi is=\"true\">W</mi><mo is=\"true\">∗</mo></msubsup></math></span><script type=\"math/mml\"><math><msubsup is=\"true\"><mi is=\"true\">θ</mi><mi is=\"true\">W</mi><mo is=\"true\">∗</mo></msubsup></math></script></span> values are unique: <span><span><math><msubsup is=\"true\"><mi is=\"true\">θ</mi><mi is=\"true\">W</mi><mo is=\"true\">∗</mo></msubsup></math></span><script type=\"math/mml\"><math><msubsup is=\"true\"><mi is=\"true\">θ</mi><mi is=\"true\">W</mi><mo is=\"true\">∗</mo></msubsup></math></script></span> is significantly greater (by 12–17%) than <span><span><math><msub is=\"true\"><mi is=\"true\">θ</mi><mn is=\"true\">0</mn></msub></math></span><script type=\"math/mml\"><math><msub is=\"true\"><mi is=\"true\">θ</mi><mn is=\"true\">0</mn></msub></math></script></span> and significantly less (by 11–17%) than <span><span><math><msub is=\"true\"><mi is=\"true\">θ</mi><mrow is=\"t","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"24 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-09DOI: 10.1016/j.seppur.2026.136795
Huirong Zhang , Mingjiao Du , Xueer Luo , Yinnan Sun , Bo Wang , Yun Zhang
Immobilizing photocatalysts on robust porous supports can couple reaction and separation while eliminating post-treatment recovery. Here, polydopamine–copper sulfide (PDA-CuS) p-n heterojunctions are grown in-situ on ceramic membranes (CM@PDA@CuS) and deployed for peroxymonosulfate (PMS) photo-activation to remove the antibiotic oxytetracycline (OTC) from water. Under simulated sunlight, CM@PDA@CuS/PMS achieves rapid OTC abatement (≈99.9% within 40–60 min; apparent kobs ≈ 0.10 min−1) and retains high activity over repeated uses. Radical-quenching and electron paramagnetic resonance analyses identify singlet oxygen (1O2) and photogenerated holes (h+) as the dominant oxidants, with •OH/O2•- as auxiliaries and negligible SO4•-, evidencing an electron-transfer–dominated pathway facilitated by PDA-CuS band alignment. Fifteen transformation products are resolved by LC-MS, and toxicity modeling indicates attenuation of acute and developmental toxicity relative to parent OTC. A scalable impeller-driven prototype (400 mL, 10 mg L−1 OTC) equipped with CM@PDA@CuS membranes achieves ≈95% removal within ≈40 min, highlighting process feasibility without catalyst loss. Matrix effects (pH, PMS dose, anions) and tests in real waters are evaluated. Reporting of light intensity, reusability, copper release, residual PMS, and TOC removal enables rigorous benchmarking across photo-PMS systems. This work establishes singlet‑oxygen-dominant photo-PMS on ceramic catalytic membranes as a practical route to antibiotic abatement and offers mechanistic and translational guidance for separation-friendly reactor design.
{"title":"PDA-CuS heterojunction ceramic membranes enable singlet‑oxygen-dominant PMS photo-activation for fast oxytetracycline removal and scalable impeller reactors","authors":"Huirong Zhang , Mingjiao Du , Xueer Luo , Yinnan Sun , Bo Wang , Yun Zhang","doi":"10.1016/j.seppur.2026.136795","DOIUrl":"10.1016/j.seppur.2026.136795","url":null,"abstract":"<div><div>Immobilizing photocatalysts on robust porous supports can couple reaction and separation while eliminating post-treatment recovery. Here, polydopamine–copper sulfide (PDA-CuS) p-n heterojunctions are grown in-situ on ceramic membranes (CM@PDA@CuS) and deployed for peroxymonosulfate (PMS) photo-activation to remove the antibiotic oxytetracycline (OTC) from water. Under simulated sunlight, CM@PDA@CuS/PMS achieves rapid OTC abatement (≈99.9% within 40–60 min; apparent k<sub>obs</sub> ≈ 0.10 min<sup>−1</sup>) and retains high activity over repeated uses. Radical-quenching and electron paramagnetic resonance analyses identify singlet oxygen (<sup>1</sup>O<sub>2</sub>) and photogenerated holes (h<sup>+</sup>) as the dominant oxidants, with •OH/O<sub>2</sub><sup>•-</sup> as auxiliaries and negligible SO<sub>4</sub><sup>•-</sup>, evidencing an electron-transfer–dominated pathway facilitated by PDA-CuS band alignment. Fifteen transformation products are resolved by LC-MS, and toxicity modeling indicates attenuation of acute and developmental toxicity relative to parent OTC. A scalable impeller-driven prototype (400 mL, 10 mg L<sup>−1</sup> OTC) equipped with CM@PDA@CuS membranes achieves ≈95% removal within ≈40 min, highlighting process feasibility without catalyst loss. Matrix effects (pH, PMS dose, anions) and tests in real waters are evaluated. Reporting of light intensity, reusability, copper release, residual PMS, and TOC removal enables rigorous benchmarking across photo-PMS systems. This work establishes singlet‑oxygen-dominant photo-PMS on ceramic catalytic membranes as a practical route to antibiotic abatement and offers mechanistic and translational guidance for separation-friendly reactor design.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"389 ","pages":"Article 136795"},"PeriodicalIF":9.0,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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