Polycarboxylic Acids Research Articles

Remediation of heavy-metal-contaminated soil with two organic acids: Washing efficiency, recovery performance, and benefit analysis

There remains a need to develop efficient and recoverable washing reagents to repair heavy metal-contaminated soil. However, the past study of recovery only considered conventional chelating agents, hindering the sustainable development of new reagents. In this study, two new-reagents, organic phosphonic acid (DTPMPA) and polycarboxylic acid (AA/AMPS/HPA), simultaneously investigated their ability to remove heavy metal and recover by electrochemical to improve reagent sustainability. Results indicated that the metal removals were influenced by the washing solution concentrations, pH, and contact time. The maximum removal by DTPMPA was 72% Cd and 33% Zn, were higher than those of AA/AMPS/HPA (concentration, 5%; pH, 3.0; and contact time, 120 min). The strong chelation of the phosphonic acid group of DTPMPA binds more metal ions. Characterization results demonstrated that both reagents were successfully recovered using electrochemical methods. While AA/AMPS/HPA had a better recovery performance because of electrostatic adsorption interactions with the metal ions, the rewashing ability of Cd and Zn was 88% and 64% of the fresh solution. Moreover, in benefit analysis, AA/AMPS/HPA showed better circular economy and long-term sustainability properties. Therefore, AA/AMPS/HPA is a feasible remediation reagents of the heavy-metal-contaminated soil with both efficiency and sustainability. The development of reagent takes into account efficiency and reuseable simultaneously, showing great economic benefits.

The effect mechanism and properties of poplar wood cross-linking modified with polyols and polycarboxylic acid

ABSTRACT Although cross-linking modification by polycarboxylic acid greatly improves dimensional stability and decay resistance, it causes severe brittleness and rigidity in wood. Introducing polyols into the cross-linking network could improve the flexibility of the modified wood, however, the related research is limited, especially the relationship between the strength and the reaction. In this study, poplar wood was modified by cross-linking with 1,2,3,4-butanetetracarboxylic acid (BTCA). D-sorbitol (SO) and sucrose (SU) used as the polyols were introduced to the modification system to esterify with BTCA. The physical and mechanical properties of the resulting wood were investigated. The effect mechanism and microstructure of the wood were also examined. The findings demonstrated that a cross-linked structure was formed in wood with increased ester bonds and ample polymer filling in the lumens. SU has lower leachability than SO. Although the incorporation of polyols has lowered anti-swelling efficiency, the reduction of modulus of rupture caused by BTCA treatment could be redeemed by reducing the degree of cross-linking between BTCA and wood components, especially SO-BTCA treatment. The addition of polyols has slight impact on the modulus of elasticity of BTCA treated wood.

Inducing Inorganic Carbon Accrual in Subsoil through Biochar Application on Calcareous Topsoil

Biochar amendments add persistent organic carbon to soil and can stabilize rhizodeposits and existing soil organic carbon (SOC), but effects of biochar on subsoil carbon stocks have been overlooked. We quantified changes in soil inorganic carbon (SIC) and SOC to 2 m depth 10 years after biochar application to calcareous soil. The total soil carbon (i.e., existing SOC, SIC, and biochar-C) increased by 71, 182, and 210% for B30, B60, and B90, respectively. Biochar application at 30, 60, and 90 t ha-1 rates significantly increased SIC by 10, 38, and 68 t ha-1, respectively, with accumulation mainly occurring in the subsoil (below 1 m). This huge increase of SIC (mainly CaCO3) is ∼100 times larger than the inorganic carbon present in the added biochar (0.3, 0.6, or 0.9 t ha-1). The benzene polycarboxylic acid method showed that the biochar-amended soil contained more black carbon particles (6.8 times higher than control soil) in the depth of 1.4-1.6 m, which provided the direct quantitative evidence for biochar migration into subsoil after a decade. Spectral and energy spectrum analysis also showed an obvious biochar structure in the biochar-amended subsoil, accompanied by a Ca/Mg carbonate cluster, which provided further evidence for downward migration of biochar after a decade. To explain SIC accumulation in subsoil with biochar amendment, the interacting mechanisms are proposed: (1) biochar amendment significantly increases subsoil pH (0.3-0.5 units) 10 years after biochar application, thus forming a favorable pH environment in the subsoil to precipitate HCO3-; and (2) the transported biochar in subsoil can act as nuclei to precipitate SIC. Biochar amendment enhanced SIC by up to 80%; thus, the effects on carbon stocks in subsoil must be understood to inform strategies for carbon dioxide removal through biochar application. Our study provided critical knowledge on the impact of biochar application to topsoil on carbon stocks in subsoil in the long term.

Experimental Research on the Microstructure and Strength Characteristics of Tailings Paste Containing Wate Reducer

In order to study the effect of polycarboxylate superplasticizer (PCE) on the microstructure and strength characteristics of tailings paste, a total of 6 tailings paste combinations including 2 cement-sand ratios (20%, 40%) and 3 water reducer dosages (0, 0.40%, 0.80%) were investigated based on the indoor microstructure test (porosity measurement, XRD test, and SEM observation) and mechanical properties method. The strength of test blocks at different ages was obtained by numerical simulation. The results showed that: 1) The water reducer can effectively reduce the porosity of the tailings paste, and the reduction effect was more significant in the condition of high cement-sand ratios. Meanwhile, high cement-sand ratio is conductive to generate more beneficial hydrates such as portlandite; 2) Compared with the significant effect of cementitious agent on the tensile strength σt of the paste, the effect of water reducer on σt is weak. Accordingly, the σt of the tailings paste is much more sensitive to cementitious agent than water reduce; 3) SEM images show that the better ratio of slurry containing polycarboxylic acid superplasticizer has more C-S-H cementitious content, smaller pore size and shorter molecular chain between particles, indicating that the particles are more encapsulated and the early strength is improved. 4) The incorporation of water reducer enhancement was particularly significant under the condition of triaxial compression. However, the presence of water reducer did not change its deformation characteristics, when the confining pressure is low, the strain softening appears; and when the confining pressure is high, it transforms to strain hardening. The peak strain ε0 and the confining pressure σ3 had a linear relationship; 5) The strength of the paste was significantly affected by the confining pressure σ3 under different conditions. The peak intensity σ1 and the confining pressure σ3 satisfied a linear relationship, while the residual strength σr and the confining pressure σ3 satisfied a quadratic polynomial fitting relationship. The strength parameters cohesion c and internal friction angle ϕ were both positively correlated with the water reducer dosage.

Interactions in plasticizer mixtures used for sugar replacement

In our quest for novel ingredients to be used in sugar replacement strategies, we have investigated the thermodynamics of polycarboxylic acids, such as citric acid. We have demonstrated the applicability of the Flory-Huggins (FH) theory to describe the thermodynamics of polycarboxylic acids solutions. Moreover, for citric acid we can describe the complete phase diagram with the theory. It shows that polycarboxylic acids have similar plasticizing and hygroscopic properties as sugars and polyols.Regarding mixtures of polycarboxylic acids and carbohydrates, the FH theory is able to describe a) the water activity of the mixtures, b) the solubility of ternary mixtures of acids and sugars, c) the lowering of the deliquescence point for binary mixtures of crystals, and d) the melting point depression in eutectic mixtures. Unexpectingly, our investigations show there is a strong non-zero FH interaction parameter between carboxylic acids and carbohydrates. In our prior sugar replacement strategy we have assumed zero interactions between plasticizers. Here, we will readdress this assumption. Carefull investigations of solid-liquid equilibrium of eutectic mixtures involving polycarboxylic acids and/or carbohydrates, shows nearly zero interaction in eutectic mixtures consisting only of two carbohydrates or two polycarboxylic acids. We now hold the hypothesis that there is strong non-zero interaction if the mixture contains plasticizers strongly differing in the amount of hydrogen bonding groups. This strong interaction explains why these mixtures, like polycarboxylic acids and carbohydrates, are excellent candidates as deep eutectic solvents. Furthermore, we conclude that polycarboxylic acids are useful additions to the toolbox of sugar replacers, albeit that there are some limitations to their amounts used.

Ruthenium ion catalytic oxidation depolymerization of lignite under ultra-low dosage of RuCl3 catalyst and separation of the organic products with inorganic salts.

Depolymerization of lignite into valuable chemicals via ruthenium ion catalytic oxidation (RICO) is a potential route for the non-energy utilization of lignite. However, the high cost of the Ru catalyst during depolymerization and the high content of inorganic salts in the product solution limit the development of this route. In this work, RICO depolymerization of lignite was conducted under an ultra-low dosage of RuCl3 catalyst to decrease the usage of the catalyst during the RICO process. Different approaches were attempted to fulfill the separation of benzene polycarboxylic acids (BPCAs) products with the inorganic salts derived from the oxidant NaIO4, including butanone extraction and desalting via crystallization under different temperatures. The results show that lignite can be efficiently depolymerized under the mass ratio of RuCl3/lignite as low as 1/1000 by prolonging the reaction time without decreasing the depolymerization degree and BPCAs yields compared to the commonly used mass ratio of 1/10. Butanone can extract ca. 91% of the total BPCAs in the product solution, and the inorganic salts content (mainly NaIO3) in the extraction solution was as low as 0.19 mg mL-1. A new strategy of first acidification of depolymerization aqueous solution by HCl and then extraction by butanone is proved to be efficient for the separation of BPCAs with inorganic salts. Salting out via crystallization under lower temperature can remove ca. half content of the salts, and the efficiency is inferior to butanone extraction. The low usage of RuCl3 can efficiently decrease the catalyst cost of the RICO process, and butanone extraction can fulfill the enrichment of BPCAs and the separation of BPCAs with inorganic salts. This work is meaningful for the potential application of RCIO depolymerization of lignite for the production of valuable chemicals.

Study on Carbonation Resistance of Polymer-Modified Sulphoaluminate Cement-Based Materials

The use of tricyclic copolymer latex (AMPS) can effectively improve the carbonation resistance of sulphoaluminate cement. This paper investigated polymer AMPS and polycarboxylic acid to modify sulphoaluminate cement materials by exploring the carbonation level of sulphoaluminate cement paste and mortar and the strength before and after carbonation. Then, the optimal dosage of polymer and polycarboxylic acid was obtained so that the carbonation resistance of sulphoaluminate cement reached the best state. The compressive strength was significantly improved by adding AMPS for sulphoaluminate cement paste and mortar. After carbonation, the strength decreased and combined with the carbonation level; it was concluded that the carbonation resistance of sulphoaluminate cement materials was the best when the optimal dosage of AMPS and polycarboxylic acid was 5% and 1.8%, respectively. Due to the addition of AMPS, the hydrated calcium aluminosilicate (C-A-S-H) and hydrated calcium silicate (C-S-H) gels, generated by the hydration of sulphoaluminate cement and the surface of unreacted cement particles, are wrapped by AMPS particles. The water is discharged through cement hydration. The polymer particles on the surface of the hydration product merge into a continuous film, which binds the cement hydration product together to form an overall network structure, penetrating the entire cement hydration phase and forming a polymer cement mortar with excellent structural sealing performance. To prevent the entry of CO2 and achieve the effect of anti-carbonation, adding polycarboxylic acid mainly improves the sample's internal density to achieve the anti-carbonation purpose.

Differentiation of qualified tea beverages from spoiled ones by the LC-MS–based analysis of their polycarboxylic acids

Abstract Polycarboxylic acids (PACs) are important metabolic products in almost all living bodies, yet current analytical methods for detection of PACs in tea beverages are still unsatisfactory due to the complex matrix and physicochemical properties of PACs. In this work, a rapid method was developed for the simultaneous determination of 7 PACs, including tartaric acid, α-ketoglutaric acid, malic acid, malonic acid, cis-aconitic acid, succinic acid, and fumaric acid, in beverages, based on selective removal of the matrix in combination with liquid chromatography–mass spectrometry (LC-MS) analysis. By stirring with activated carbon and the Na2CO3 solution, the matrix in beverages was selectively removed, and PACs were almost retained in the supernatant of diluted Na2CO3 solution. Under optimized parameters, the limit of quantitation for the PACs was in the range of 1–50 ng/mL, and the content of the PACs in 8 beverages was determined with the recovery range of 72.2%–122.5%. The contents of malic acid, malonic acid, and succinic acid in tea beverages were found to be greater than those in non-tea beverages. Moreover, the concentration of these PACs in beverages was found to be multiplied many times in their deterioration period, especially for fumaric acid and α-ketoglutaric acid. These results indicated that PACs can be selected as a criterion to differentiate qualified tea beverages from spoiled beverages.

Binder derived semi-conductive graphite/alumina composites via novel one-step pulsed electric current sintering

Semi-conductive graphite/Al2O3 ceramic composites were successfully fabricated via a novel and facile approach by pulsed electric current sintering of binder embedded Al2O3 powders, which were prepared by a simple ball-milling assisted mixing of Al2O3 powder with polyvinyl alcohol solution. By altering the sintering conditions with respects to temperature and pressure controlling and concentration of binder, relative density, and microstructure of fabricated graphite/Al2O3 ceramic composites, and the electrical properties were schematically investigated in this study. The fabricated graphite/Al2O3 ceramic composites exhibit superior semi-conductive properties. Moreover, the carrier type in fabricated semi-conductive graphite/Al2O3 composites was successfully modified by adding polycarboxylic acid as a dispersant in binder embedded Al2O3 powders. The contents in this work present a new strategy for the design and development of functional ceramic composites.

Bubble Evolution under the Action of Polycarboxylate and Air-Entraining Agent and Its Effects on Concrete Properties-A Review.

In order to improve the performance of concrete, it is of great significance to have a better understanding the mechanism and main influencing factors of concrete bubble evolution under the action of polycarboxylate and air-entraining agents. In the present review, with respect to the generation, growth, stability, and rupture of concrete bubbles under the action of polycarboxylate and air-entraining agents, this paper discusses the influence of bubble characteristics on concrete performance and studies bubble regulation by air-entraining agents and polycarboxylate (PCE) superplasticizer. The results show that the acid-to-ether ratio, sulfonic acid group, ester group, and the type of air entraining agent of the polycarboxylate acid structure have a significant impact on the bubbles. The bubble size, specific area, spacing factor, and bubble content have a significant impact on the rheological properties and related mechanical properties of fresh concrete and also affect the appearance quality of concrete. The problems with the experimental methods and theoretical models of concrete bubble research were analyzed, and future research ideas were put forward.

Phytoextraction of mercury-contaminated soils

Mercury is a naturally occurring element that has become an extremely hazardous pollutant as a result of exceeding natural levels in the environment due to intense human activity. Considered the safest and most economical technology, phytoremediation of soils contaminated with heavy metals has been actively studied by scientists in many countries since the end of the last century. This article presents a study of the vegetation of mercury-contaminated soils using a culture of white mustard (Sinapis alba), a new complexing agent. This is a study of a new chelating agent representing the class of polycarboxylic acids. The monoethanolamine salt of bitiodioacetic acid, in which the sulfur atom enters into the structure of the molecule and acts as a coordination partner for mercury, creates a high selectivity of the interaction. Studies have shown a pronounced effect of the chelating agent on the efficiency of mercury phytoextraction. In such cases, white mustard seedlings showed a good physiological state, increased development of biomass. The monoethanolamine salt of bitiodioacetic acid can be characterized as a highly effective reagent; however, more extensive testing is still needed to understand various aspects of its action.

Hybrid water adsorption and solubility partitioning for aerosol hygroscopicity and droplet growth

Abstract. In this work, we studied the cloud condensation nuclei (CCN) activity and subsaturated droplet growth of phthalic acid (PTA), isophthalic acid, (IPTA) and terephthalic acid (TPTA), significant benzene polycarboxylic acids and structural isomers found in the atmosphere. Köhler theory (KT) can be effectively applied for hygroscopicity analysis of PTA due to its higher aqueous solubility compared to IPTA and TPTA. As with other hygroscopicity studies of partially water-soluble and effectively water-insoluble species, the supersaturated and subsaturated hygroscopicity derived from KT principles do not agree. To address the disparities in the sub- and supersaturated droplet growth, we developed a new analytical framework called the Hybrid Activity Model (HAM). HAM incorporates the aqueous solubility of a solute within an adsorption-based activation framework. Frenkel–Halsey–Hill (FHH) adsorption theory (FHH-AT) was combined with the aqueous solubility of the compound to develop HAM. Analysis from HAM was validated using laboratory measurements of pure PTA, IPTA, TPTA and PTA–IPTA internal mixtures. Furthermore, the results generated using HAM were tested against traditional KT and FHH-AT to compare their water uptake predictive capabilities. A single hygroscopicity parameter was also developed based on the HAM framework. Results show that the HAM-based hygroscopicity parameter can successfully simulate the water uptake behavior of the pure and internally mixed samples. Results indicate that the HAM framework may be applied to atmospheric aerosols of varying chemical structures and aqueous solubility.

Structural evolution of lignite from heterogeneous particles to homogeneous products during ruthenium ion catalytic oxidation depolymerization

Disclosing the structure evolution of lignite from heterogeneous particles to homogeneous products during depolymerization is of great significance to understand the depolymerization process of lignite. In this work, the structure evolution of lignite during ruthenium ion catalytic oxidation (RICO) depolymerization was studied. Special attention was paid on the changes of the size of lignite particles and molecular weight of the soluble products. The results showed that the depolymerization of lignite into benzene polycarboxylic acids (BPCAs) involved the conversion of lignite from microparticles into nanoparticles, which can be further depolymerized and released the soluble products into the solution. Around 93% of the organic matter in lignite can be converted from heterogeneous particles to homogeneous products. The molecular weight of the soluble products had a wide distribution from dozens of thousand Dalton to several hundred Dalton, indicating that the macromolecules released from lignite particles were gradually decomposed and formed a series of intermediate products. These results explain that why the composition of the depolymerization products is complex. Finally, the microstructural evolution process of lignite during depolymerization was speculated. Lignite particles mainly experienced the microparticles, nanoparticles, macromolecules, and then small molecules such as BPCAs. The formation of macromolecules proceeded fast and the subsequent formation of BPCAs from macromolecules was the rate-determining step. This work contributes deep insights into the structural evolution process of lignite during RICO depolymerization, and provides basic data for the regulation and control of the depolymerization process.

Embedding of biochar in soil mineral fractions: Evidence from benzene polycarboxylic acids molecular biomarkers

Investigators are debating on the positive and negative priming effects of biochar on native soil organic carbon (SOC), which is largely attributed to the technical barrier of identifying biochar contribution to the apparently measured SOC or mineralized CO2. We combined benzene polycarboxylic acids (BPCAs) molecular biomarkers and soil particle density fractionation to identify biochar contributions to the carbon content in three representative allitic soils in Yunnan. The soil-biochar mixture was incubated for one-month to avoid significant biodegradation of biochar. The results showed that BPCAs were mainly distributed in free light fractions (fLF) up to 87 % of the total BPCAs contents after one month incubation. Recognition of BPCAs in occluded light fractions (oLF) and heavy fractions (HF) suggested a significant interaction between biochar and soil mineral particles. In addition, the percentage of B6CA is comparable or even higher in HF than in fLF or oLF. Thus, biochar-mineral interactions may be an additional stabilization mechanism besides the condensed aromatic structures in biochar. The apparently measured carbon contents increased after biochar application, and both positive and negative priming effects to native SOC were observed after deducting biochar contents based an accurate calculation from BPCAs. The most native SOC depletion (positive priming effects) was noted for the soil with the most favored biochar embedding in soil mineral compositions. This study emphasized that combining BPCAs molecular biomarkers and soil particle density fractionation could accurately quantify different carbon pools, and thus facilitate a comprehensive understanding on the stabilization and turnover of biochar in soils.

Effect of Polycarboxylic Grinding Aid on Cement Chemistry and Properties.

In view of the disadvantages of polycarboxylic acid grinding aids, such as poor reinforcement effect and cumbersome synthesis process, a new type of polycarboxylic acid grinding aid was prepared to meet the requirements of multifunctional admixture for cement concrete. The polycarboxylate grinding aid (PC) was prepared using acrylic acid, sodium allyl sulfonate, and isoprenol polyoxyethylene ether (TPEG) as raw materials, and ammonium persulfate as initiator in the nitrogen atmosphere. The effect of PC and its compound with triethanolamine (TEA) and triisopropanolamine (TIPA) on cement particle size and strength, and hydration process and structures of hydrated products were investigated. Moreover, the grinding mechanism of grinding aids was also proposed. The results indicate that the PC has good performance in both grinding and high-efficiency water-reducing. The average particle diameter of cement was reduced by 3.65 μm when 0.03 wt% of PC was added as grinding aid. Moreover, a high initial fluidity of the cement paste, 290 mm, could be reached when 0.08 wt% of PC was added. The fluidity loss of cement paste after 30 min and 60 min was 265 mm and 260 mm, respectively. After PC compounding with TEA and TIPA, 4.07 μm and 4.7 μm of the average particle size of the cement can be reduced, respectively. Based on the investigations on the hydration rate of cement hydration, the phases, and the microstructures of the hardened slurry, it could be concluded that grinding aids can change the hydration process of cement and improve the morphologies and structures of hydration products without influence on the type of hydrated products. Note that the compounded grinding aids, such as PC with TEA or PC with TIPA, can more effectively enhance the early and late strength of cement. This shows excellent comprehensive performance. In this study, a new type of polycarboxylic acid grinding aid was prepared to meet the requirements of the versatility of cement concrete additives, and to simplify the synthesis process, reduce production costs, improve the grinding effect, and improve the performance of cement concrete.

Synthesis of novel poly-carboxylic acids via click reaction and their application for easy-care treatment of cotton fabrics

Synthesis of novel poly-carboxylic acids via click reaction and their application for easy-care treatment of cotton fabrics

Significance of Ionic Character Induced by Ga-Doped γ-Al2O3 on Polyethylene Degradation to the Precursors of Gasoline and Diesel Oil with a Trace Amount of Wax.

Polyethylene degradation has a significant ecological impact but is also economically beneficial because it generates fuels and useful chemical products. Our study mainly describes the cleavage of C-C and C-H bonds when polyethylene (dispersed in 1-octadecene) was low-temperature heat-treated in two steps, at 180 and 250 °C, for 24 h for each step. Finally, it was converted to a mixture of the precursors of gasoline and diesel oil with a trace amount of wax. A series of reactions resulted in cracking, dehydrogenation and oxidation, hence producing polycarboxylic acids and saturated and unsaturated hydrocarbons. ESI-MS analysis revealed that mixed oil consisted of low carbon number hydrocarbons and their derivatives of carboxylic acids, with the carbon number ranging from C-6 to C-18. In the trace amount of wax, complicated carboxylic acids and hydrocarbons with carbon number C-22 to C-58 were also identified. FT-IR analysis further confirmed the presence of carboxylic acid derivatives and double bonds in the degradation products. γ-Al2O3 nanorods effectively catalyzed the degradation process by enhancing the C-C chain length in the products. Lewis acid (Al) and Lewis base (oxygen) in the γ-Al2O3 induced ionic character of the C-C bond chain, which led to the efficient cracking of the C-C bond. Poor shielding effect, smaller atomic size and greater ionization energy made Ga a stronger Lewis acid compared to Al; hence, Ga-doped γ-Al2O3 catalyzed the degradation process even more effectively.

Effects of red mud on workability and mechanical properties of autoclaved aerated concrete (AAC)

Red mud poses a severe threat to the local environment that needs to be disposed of properly. This study investigated the feasibility of using red mud in autoclave aerated concrete (AAC), whose performances were systematically assessed, and the performances were further interpreted by microstructural analyses. The initial results reveal the negative impacts of using red mud in AAC concerning workability and strength, which could be assigned to the low activity of red mud as well as its small particle size, and the process of gas generation inside AAC was inhibited. In addition, the worse pore structure and the excessive content of tobermorite in AAC with a higher amount of red mud could also account for its reduced strength. Further, 22.5% of red mud to replace fly ash in AAC could be the optimal ratio considering several indexes of AAC involving red mud, and the use of polycarboxylic acid in AAC or adjusting the water-solid ratio of AAC can greatly improve the overall performance of AAC with red mud, which satisfies the requirements stipulated by the standard.

Preliminarily evaluation of poly (AA-co-AMPS) on the properties of sulphoaluminate cement

• Comparing the effect of structural parameters on the rheology and hydration of SAC. • Stronger effect of degree of polymerization on its properties. • Long-term strength reduction of SAC caused by poly (AA- co -AMPS). • Changes in hydration rates leading the paste shrinkage and strength reduction. The previous article reported the effect of poly (AA- co -AMPS) on the rheology of sulphoaluminate cement (SAC), but the effect of structural parameters of the copolymer on the properties, especially the mechanical properties, would decide the value for SAC as a superplasticizer. To further evaluate their effect on SAC, a series of copolymers were synthesized, and their effects on the rheology, hydration, and mechanical properties were tested. Copolymers could control the fluidity and the setting as reported, but the degree of polymerization would be a stronger factor than the ratio of carboxyl to sulfonyl groups. Meanwhile, flocculation structure destruction and particle dispersion are the main reasons for rheology properties changing, while inhibiting the formation of AFt would significantly retard the hydration. However, the polycarboxylic acid segments in this copolymer might cause or enhance the inherent shrinkage of SAC leading to the compressive strength of 28 d decreasing.

Cage Bismuth Metal–Organic Framework Materials Based on a Flexible Triazine–Polycarboxylic Acid: Subgram Synthesis, Application for Sensing, and White Light Tuning

Bismuth-based metal-organic frameworks (MOFs) have always attracted the attention of many researchers. Here, we first report a crystalline Bi-MOF (Bi-TDPAT) based on a flexible triazine-polycarboxylic linker 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (H6TDPAT) and bismuth nitrate; its crystallite quality is adequately good and the diffraction data can be collected directly by single crystal X-ray diffraction rather than 3D electron diffraction. The structure of Bi-TDPAT belongs to a novel topology type btt. Notably, the synthesis scale of Bi-TDPAT can be expanded, and sub-gram synthesis can be realized. At the same time, we synthesized a microcrystalline material Bi-TATAB utilizing 2,4,6-tris(4-carboxylphenylamino)-1,3,5-triazine (H3TATAB). The structures of the two materials were characterized by several microanalysis tools. Considering that Bi-TDPAT is a blue light-emitting material with a broad emission peak, we prepared a white light emitting composite material Eu/Tb@Bi-TDPAT by encapsulating Eu(III)/Tb(III) in Bi-TDPAT. In addition, the fluorescence sensing functions of Bi-TDPAT and Bi-TATAB were explored. The results showed that they could detect and recognize various nitrophenols, and the optimal limit of detection is as low as 0.21 μM, which can be reused even after five cycles. Energy competitive absorption (CA) and photo-induced electron transfer are the main sensing mechanisms. By comparing and analyzing the properties of these two bismuth-based crystalline materials, we believe that this work also provides inspiration for the synthesis and development of bismuth-based MOF in the future.