Porous carbon materials with developed porosity,high surface area and good thermal-and chemicalresistance are advantageous for gas adsorption and separation.However,most carbon adsorbents are in powder form which exhi...Porous carbon materials with developed porosity,high surface area and good thermal-and chemicalresistance are advantageous for gas adsorption and separation.However,most carbon adsorbents are in powder form which exhibit high pressure drop when deployed in practical separation bed.While monolithic carbons have largely addressed the pulverization problem and preserved kinetics and usually suffer from abrasion during multiple adsorption-desorption cycles.Herein,we proposed the designed synthesis of mechanically robust carbon monoliths with hierarchical pores,solid nitrogen-containing framework.The synthesis started with the polymerization of resorcinol and formaldehyde under weakly acidic conditions generated from cyanuric acid,and then an appropriate amount of hexamethylenetetramine(HMTA)was added as a crosslinker to prompt the formation of three dimensional frameworks.After carbonization process,the as-obtained porous carbon monoliths have a high radial compressive strength of 886 N/cm as well as a BET specific surface area of up to 683 m2/g.At approximately 1 bar,the CO2 equilibrium capacities of the monoliths are in the range of 3.1–4.0 mmol/g at 273 K and of 2.3–3.0 mmol/g at 298 K,exhibiting high selectivity for the capture of CO2 over N2 from a stream which consists of 16.7%(v%)CO2 in N2.Meanwhile,they undergo a facile CO2 release in an argon stream at 298 K,indicating a good regeneration capacity.After cycle testing,sieving and regeneration,the adsorbent has no mass loss,compared to that of its fresh counterpart.展开更多
Binary oxide systems（Cu Cr2O4, Cu Co2O4）, deposited onto cordierite monoliths of honeycomb structure with a second support（finely dispersed Al2O3）, were prepared as filters for catalytic combustion of diesel soot ...Binary oxide systems（Cu Cr2O4, Cu Co2O4）, deposited onto cordierite monoliths of honeycomb structure with a second support（finely dispersed Al2O3）, were prepared as filters for catalytic combustion of diesel soot using internal combustion engine’s gas exhausts（O2, NOx, H2 O, CO2） and O3 as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO2. Oxidants used can be arranged with reference to decreasing their activity in a following series： O3 NO2〉 H2 O 〉 NO 〉 O2〉 CO2. Ozone proved to be the most efficient oxidizing agent： the diesel soot combustion by O3 occurs intensively（in the presence of copper chromite based catalyst） even at closing to ambient temperatures.Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the ＂cold start＂ problem.展开更多
Metal-organic frameworks(MOFs)have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials,thanks to their large specific surface area,high porosity,tailora...Metal-organic frameworks(MOFs)have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials,thanks to their large specific surface area,high porosity,tailorable structures and compositions,diverse functionalities,and well-controlled pore/size distribution.However,most developed MOFs are in powder forms,which still have some technical challenges,including abrasion,dustiness,low packing densities,clogging,mass/heat transfer limitation,environmental pollution,and mechanical instability during the packing process,that restrict their applicability in industrial applications.Therefore,in recent years,attention has focused on techniques to convert MOF powders into macroscopic materials like beads,membranes,monoliths,gel/sponges,and nanofibers to overcome these challenges.Three-dimensional(3D)printing technology has achieved much interest because it can produce many high-resolution macroscopic frameworks with complex shapes and geometries from digital models.Therefore,this review summarizes the combination of different 3D printing strategies with MOFs and MOF-based materials for fabricating 3D-printed MOF monoliths and their environmental applications,emphasizing water treatment and gas adsorption/separation applications.Herein,the various strategies for the fabrication of 3D-printed MOF monoliths,such as direct ink writing,seed-assisted in-situ growth,coordination replication from solid precursors,matrix incorporation,selective laser sintering,and digital light processing,are described with the relevant examples.Finally,future directions and challenges of 3D-printed MOF monoliths are also presented to better plan future trajectories in the shaping of MOF materials with improved control over the structure,composition,and textural properties of 3D-printed MOF monoliths.展开更多
A series of monolithic MnO_(2)/iron mesh (IM) catalysts for oxidation of toluene were successfully prepared by using in situ hydrothermal growth.MnO_(2)can grow firmly on the IM substrates surface with a shedding rate...A series of monolithic MnO_(2)/iron mesh (IM) catalysts for oxidation of toluene were successfully prepared by using in situ hydrothermal growth.MnO_(2)can grow firmly on the IM substrates surface with a shedding rate of only 0.14%.Due to the highest O_(ads) and high-valent Mn^(4+) and Fe^(3+) elements,the temperature at 50% and 90% toluene conversion (T_(50%) and T_(90%)) was 252 and 265℃,respectively for the best performance catalyst (hydrothermal temperature of 80℃,hydrothermal time of 12 h,and precursor manganese ion concentration of 0.03 mol/L).The catalysts also presented good water resistance and cycle performance.In-situ DRIFTS results suggesting that toluene was first rapid transformed into the reaction intermediate species (benzoate species) and then converted to CO_(2)and H_(2)O.Therefore,this work provides a new direction for the research and application of IM-based monolithic catalysts.展开更多
With a particular focus on the connection between liquid flow distribution and gas-liquid mass transfer in monolithic beds in the Taylor flow regime, hydrodynamic and gas-liquid mass transfer experiments were carriedo...With a particular focus on the connection between liquid flow distribution and gas-liquid mass transfer in monolithic beds in the Taylor flow regime, hydrodynamic and gas-liquid mass transfer experiments were carriedout in a column with a monolithic bed of cell density of 50 cpsi with trio different distributors （nozzle and packed bed distributors）. Liquid saturation in individual channels was measured by using self-made micro-conductivity probes. A mal-distribution factor was used to evaluate uniform degree of phase distribution in monoliths. Overall bed pressure drop and mass transfer coefficients were measured. For liquid flow distribution and gas-liquid masstransfer, it is found that the superficial liquid velocity is a crucial factor and the packed bed distributor is better than the nozzle distributor. A semi-theoretical analysis using single channel models shows that the packed bed distributor always yields shorter and uniformly distributed liquid slugs compared to the nozzle distributor, which in turn ensures a better mass transfer performance. A bed scale mass transfer model is proposed by employing the single channel models in individual channels and incorporating effects of non-uniform liquid distribution along the bedcross-section. The model predicts the overall gas-liquid mass transfer coefficient wig a relative error within ＋30%.展开更多
The novel and facile preparation of magnetically interconnected micro/macroporous structure of monolithic porous carbon adsorbent(MPCA)were designed and presented herein.The synthesis was achieved via conventional fre...The novel and facile preparation of magnetically interconnected micro/macroporous structure of monolithic porous carbon adsorbent(MPCA)were designed and presented herein.The synthesis was achieved via conventional freezedrying and pyrolysis processes.In this study,sodium alginate and wasted black liquor were employed as starting precursors.Sodium alginate acts as a template of materials,whereas black liquor,the wasted product from the paper industry with plentiful of lignin content and alkaline solution,played an essential role in the reinforcement and activation of porosity for the resulting materials.Moreover,both the precursors were well dissolved in Fe^(3+) solution,providing a simple addition of a magnetic source in a one-pot synthesis.The interconnected micro/macroporous structures were generated through freeze-drying and,subsequently the pyrolysis process.The obtained cylindricalshaped monolithic porous carbon adsorbent(MPCA-700)showed high mechanical stability,a high BET specific surface area(902 m^(2)/g).Such aforementioned features were considered suitable to make the synthesized monolith as an adsorbent for the removal of heavy metal ions.The maximum adsorption capacity of MPCA-700 towards Pb^(2+) ions was 76.34 mg/g at pH 5.The adsorption studies illustrated that adsorption kinetics and isotherm perfectly fitted with the pseudo-second-order kinetics model and Langmuir isotherm,respectively.This work presents a promising protocol to reduce the overall costs in the preparation of renewable adsorbents with good adsorption efficiency and regeneration.展开更多
Utilizing solar energy for sorbent regeneration during the CO_(2)swing adsorption process could potentially reduce CO_(2)capture costs.This study describes a new technique—solar thermal swing adsorption(STSA)for CO_(...Utilizing solar energy for sorbent regeneration during the CO_(2)swing adsorption process could potentially reduce CO_(2)capture costs.This study describes a new technique—solar thermal swing adsorption(STSA)for CO_(2)capture based on application of intermittent illumination onto porous carbon monolith(PCM)sorbents during the CO_(2)capture process.This allows CO_(2)to be selectively adsorbed on the sorbents during the light-off periods and thereafter released during the light-on periods due to the solar thermal effect.The freestanding and mechanically strong PCMs have rich ultramicropores with narrow pore size distributions,displaying relatively high CO_(2)adsorption capacity and high CO_(2)/N_(2) selectivity.Given the high CO_(2)capture performance,high solar thermal conversion efficiency,and high thermal conductivity,the PCM sorbents could achieve high CO_(2)capture rate of up to 0.226 kg·kgcarbon^(-1)·h^(-1)from a gas mixture of 20 vol.%CO_(2)/80 vol.%N_(2) under STSA conditions with a light intensity of 1000 W·m^(-2).In addition,the combination of STSA with the conventional vacuum swing adsorption technique further increases the CO_(2)working capacity.展开更多
Nanocellulose harvested from biomass has attractive properties that have promoted research on its practical applications.Herein,we investigated nanocellulose-based porous monoliths with oriented microchannels that can...Nanocellulose harvested from biomass has attractive properties that have promoted research on its practical applications.Herein,we investigated nanocellulose-based porous monoliths with oriented microchannels that can be fabricated via a unidirectional freezing method.In this method,water-dispersed cellulose nanofibers(CNFs)were immersed into a cold source at a controlled speed,followed by subsequent freeze-drying.The structure of porous cellulose monoliths mainly depends on two factors:the freezing conditions and properties of the dispersed CNFs.The former has been investigated previously.However,the effects of the latter remain unclear.In this study,CNF suspensions prepared by 2,2,6,6-tetramethylpiperidine-1-oxylmediated oxidation cellulose nanofibers(TOCNs)with different aspect ratios and concentrations were used.The effects of these variables on the resulting structure,including the pore shape,size,wall thickness,were examined.Based on the results,the impact of TOCNs on the structure of porous cellulose monoliths was investigated.Our findings suggested that depending on their structure,the porous cellulose monoliths exhibit different mechanical strengths and mass transport properties.In particular,porous cellulose monoliths synthesized from 5.1 wt.%short TOCNs exhibited a low density(55.9 mg∙cm^(−3)),high mechanical strength(8687 kPa),fast mass transport.展开更多
Surfactant template synthesis of mesoporous silica monolith was carried out via modified fast sol gel process. It was easy to obtain crack free silica monolith due to low volume shrinkage during the gelation. The morp...Surfactant template synthesis of mesoporous silica monolith was carried out via modified fast sol gel process. It was easy to obtain crack free silica monolith due to low volume shrinkage during the gelation. The morphology of the titled silica was characterized by transmission electron microscopy and X ray diffraction. The results showed that the pores were worm like and the pore size was about 4 nm. Further nitrogen isothermal absorption experiment indicated that the specific area of the titled material was 391 m 2/g, which was comparable with the reported value 306 m 2/g in literature.展开更多
基金financially supported by a Joint Sino-German Research Project(21761132011)the National Natural Science Foundation of China(No.21776041)the Cheung Kong Scholars Programme of China(T2015036).
文摘Porous carbon materials with developed porosity,high surface area and good thermal-and chemicalresistance are advantageous for gas adsorption and separation.However,most carbon adsorbents are in powder form which exhibit high pressure drop when deployed in practical separation bed.While monolithic carbons have largely addressed the pulverization problem and preserved kinetics and usually suffer from abrasion during multiple adsorption-desorption cycles.Herein,we proposed the designed synthesis of mechanically robust carbon monoliths with hierarchical pores,solid nitrogen-containing framework.The synthesis started with the polymerization of resorcinol and formaldehyde under weakly acidic conditions generated from cyanuric acid,and then an appropriate amount of hexamethylenetetramine(HMTA)was added as a crosslinker to prompt the formation of three dimensional frameworks.After carbonization process,the as-obtained porous carbon monoliths have a high radial compressive strength of 886 N/cm as well as a BET specific surface area of up to 683 m2/g.At approximately 1 bar,the CO2 equilibrium capacities of the monoliths are in the range of 3.1–4.0 mmol/g at 273 K and of 2.3–3.0 mmol/g at 298 K,exhibiting high selectivity for the capture of CO2 over N2 from a stream which consists of 16.7%(v%)CO2 in N2.Meanwhile,they undergo a facile CO2 release in an argon stream at 298 K,indicating a good regeneration capacity.After cycle testing,sieving and regeneration,the adsorbent has no mass loss,compared to that of its fresh counterpart.
文摘Binary oxide systems（Cu Cr2O4, Cu Co2O4）, deposited onto cordierite monoliths of honeycomb structure with a second support（finely dispersed Al2O3）, were prepared as filters for catalytic combustion of diesel soot using internal combustion engine’s gas exhausts（O2, NOx, H2 O, CO2） and O3 as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO2. Oxidants used can be arranged with reference to decreasing their activity in a following series： O3 NO2〉 H2 O 〉 NO 〉 O2〉 CO2. Ozone proved to be the most efficient oxidizing agent： the diesel soot combustion by O3 occurs intensively（in the presence of copper chromite based catalyst） even at closing to ambient temperatures.Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the ＂cold start＂ problem.
文摘Metal-organic frameworks(MOFs)have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials,thanks to their large specific surface area,high porosity,tailorable structures and compositions,diverse functionalities,and well-controlled pore/size distribution.However,most developed MOFs are in powder forms,which still have some technical challenges,including abrasion,dustiness,low packing densities,clogging,mass/heat transfer limitation,environmental pollution,and mechanical instability during the packing process,that restrict their applicability in industrial applications.Therefore,in recent years,attention has focused on techniques to convert MOF powders into macroscopic materials like beads,membranes,monoliths,gel/sponges,and nanofibers to overcome these challenges.Three-dimensional(3D)printing technology has achieved much interest because it can produce many high-resolution macroscopic frameworks with complex shapes and geometries from digital models.Therefore,this review summarizes the combination of different 3D printing strategies with MOFs and MOF-based materials for fabricating 3D-printed MOF monoliths and their environmental applications,emphasizing water treatment and gas adsorption/separation applications.Herein,the various strategies for the fabrication of 3D-printed MOF monoliths,such as direct ink writing,seed-assisted in-situ growth,coordination replication from solid precursors,matrix incorporation,selective laser sintering,and digital light processing,are described with the relevant examples.Finally,future directions and challenges of 3D-printed MOF monoliths are also presented to better plan future trajectories in the shaping of MOF materials with improved control over the structure,composition,and textural properties of 3D-printed MOF monoliths.
基金supported by the Fundamental Research Funds for the Central Universities (No. 2021ZY79)Beijing Municipal Education Commission through the Innovative Transdisciplinary Program "Ecological Restoration Engineering” (No. GJJXK210102)+2 种基金National Natural Science Foundation of China (Nos. 42075169, U1810209)National Key R&D Program of China (No. 2021YFE0110800)Chinese-Serbian collaboration project (No. 451-03-1205/2021-09)。
文摘A series of monolithic MnO_(2)/iron mesh (IM) catalysts for oxidation of toluene were successfully prepared by using in situ hydrothermal growth.MnO_(2)can grow firmly on the IM substrates surface with a shedding rate of only 0.14%.Due to the highest O_(ads) and high-valent Mn^(4+) and Fe^(3+) elements,the temperature at 50% and 90% toluene conversion (T_(50%) and T_(90%)) was 252 and 265℃,respectively for the best performance catalyst (hydrothermal temperature of 80℃,hydrothermal time of 12 h,and precursor manganese ion concentration of 0.03 mol/L).The catalysts also presented good water resistance and cycle performance.In-situ DRIFTS results suggesting that toluene was first rapid transformed into the reaction intermediate species (benzoate species) and then converted to CO_(2)and H_(2)O.Therefore,this work provides a new direction for the research and application of IM-based monolithic catalysts.
基金Supported by the State Key Development Program for Basic Research of China (2006CB202503)
文摘With a particular focus on the connection between liquid flow distribution and gas-liquid mass transfer in monolithic beds in the Taylor flow regime, hydrodynamic and gas-liquid mass transfer experiments were carriedout in a column with a monolithic bed of cell density of 50 cpsi with trio different distributors （nozzle and packed bed distributors）. Liquid saturation in individual channels was measured by using self-made micro-conductivity probes. A mal-distribution factor was used to evaluate uniform degree of phase distribution in monoliths. Overall bed pressure drop and mass transfer coefficients were measured. For liquid flow distribution and gas-liquid masstransfer, it is found that the superficial liquid velocity is a crucial factor and the packed bed distributor is better than the nozzle distributor. A semi-theoretical analysis using single channel models shows that the packed bed distributor always yields shorter and uniformly distributed liquid slugs compared to the nozzle distributor, which in turn ensures a better mass transfer performance. A bed scale mass transfer model is proposed by employing the single channel models in individual channels and incorporating effects of non-uniform liquid distribution along the bedcross-section. The model predicts the overall gas-liquid mass transfer coefficient wig a relative error within ＋30%.
基金This work was funded by Development and Promotion of Science Technology Talents(DPST)Research Grant(Grant No.017/2559)the Institute for the Promotion of Teaching Science and Technology(IPST),Thailand.
文摘The novel and facile preparation of magnetically interconnected micro/macroporous structure of monolithic porous carbon adsorbent(MPCA)were designed and presented herein.The synthesis was achieved via conventional freezedrying and pyrolysis processes.In this study,sodium alginate and wasted black liquor were employed as starting precursors.Sodium alginate acts as a template of materials,whereas black liquor,the wasted product from the paper industry with plentiful of lignin content and alkaline solution,played an essential role in the reinforcement and activation of porosity for the resulting materials.Moreover,both the precursors were well dissolved in Fe^(3+) solution,providing a simple addition of a magnetic source in a one-pot synthesis.The interconnected micro/macroporous structures were generated through freeze-drying and,subsequently the pyrolysis process.The obtained cylindricalshaped monolithic porous carbon adsorbent(MPCA-700)showed high mechanical stability,a high BET specific surface area(902 m^(2)/g).Such aforementioned features were considered suitable to make the synthesized monolith as an adsorbent for the removal of heavy metal ions.The maximum adsorption capacity of MPCA-700 towards Pb^(2+) ions was 76.34 mg/g at pH 5.The adsorption studies illustrated that adsorption kinetics and isotherm perfectly fitted with the pseudo-second-order kinetics model and Langmuir isotherm,respectively.This work presents a promising protocol to reduce the overall costs in the preparation of renewable adsorbents with good adsorption efficiency and regeneration.
基金This study was supported byÅForsk research grant and Anhui Provincial Natural Science Foundation(No.2108085QB72)。
文摘Utilizing solar energy for sorbent regeneration during the CO_(2)swing adsorption process could potentially reduce CO_(2)capture costs.This study describes a new technique—solar thermal swing adsorption(STSA)for CO_(2)capture based on application of intermittent illumination onto porous carbon monolith(PCM)sorbents during the CO_(2)capture process.This allows CO_(2)to be selectively adsorbed on the sorbents during the light-off periods and thereafter released during the light-on periods due to the solar thermal effect.The freestanding and mechanically strong PCMs have rich ultramicropores with narrow pore size distributions,displaying relatively high CO_(2)adsorption capacity and high CO_(2)/N_(2) selectivity.Given the high CO_(2)capture performance,high solar thermal conversion efficiency,and high thermal conductivity,the PCM sorbents could achieve high CO_(2)capture rate of up to 0.226 kg·kgcarbon^(-1)·h^(-1)from a gas mixture of 20 vol.%CO_(2)/80 vol.%N_(2) under STSA conditions with a light intensity of 1000 W·m^(-2).In addition,the combination of STSA with the conventional vacuum swing adsorption technique further increases the CO_(2)working capacity.
基金JSPS KAKENHI(No.22K18047)JST SICORP(No.JPMJSC2112)the New Energy and Industrial Technology Development Organization(NEDO)(No.JPNP20004)。
文摘Nanocellulose harvested from biomass has attractive properties that have promoted research on its practical applications.Herein,we investigated nanocellulose-based porous monoliths with oriented microchannels that can be fabricated via a unidirectional freezing method.In this method,water-dispersed cellulose nanofibers(CNFs)were immersed into a cold source at a controlled speed,followed by subsequent freeze-drying.The structure of porous cellulose monoliths mainly depends on two factors:the freezing conditions and properties of the dispersed CNFs.The former has been investigated previously.However,the effects of the latter remain unclear.In this study,CNF suspensions prepared by 2,2,6,6-tetramethylpiperidine-1-oxylmediated oxidation cellulose nanofibers(TOCNs)with different aspect ratios and concentrations were used.The effects of these variables on the resulting structure,including the pore shape,size,wall thickness,were examined.Based on the results,the impact of TOCNs on the structure of porous cellulose monoliths was investigated.Our findings suggested that depending on their structure,the porous cellulose monoliths exhibit different mechanical strengths and mass transport properties.In particular,porous cellulose monoliths synthesized from 5.1 wt.%short TOCNs exhibited a low density(55.9 mg∙cm^(−3)),high mechanical strength(8687 kPa),fast mass transport.
基金Supported by National Natural Science Foundation of China(50802064,51072137,and 11074189)New Century Excellent Talents in University of China(NCET-08-0405)National Science and Technology Support Program(2009BAC62B02)
基金National Basic Research Program(973 Program,2011CBA00504)National Natural Science Foundation of China(21203214,21133010,21261160487,50921004,21203215)~~
文摘Surfactant template synthesis of mesoporous silica monolith was carried out via modified fast sol gel process. It was easy to obtain crack free silica monolith due to low volume shrinkage during the gelation. The morphology of the titled silica was characterized by transmission electron microscopy and X ray diffraction. The results showed that the pores were worm like and the pore size was about 4 nm. Further nitrogen isothermal absorption experiment indicated that the specific area of the titled material was 391 m 2/g, which was comparable with the reported value 306 m 2/g in literature.
