Photoactive Cements: A Review
Abstract
:1. Introduction
2. Mechanism of Photocatalysis, Types of Photoactive Cements and Their Preparation
- (a)
- Photocatalytic mechanisms of TiO2Suitable semiconductors are photocatalysts capable of carrying out the photocatalysis process. The most famous semiconductor in the world is titanium dioxide. The supply of energy in the form of light to the semiconductor causes the electrons from the base band to jump to the conduction band, and oxidation and reduction reactions take place in both bands [1]. The mechanism of photocatalytic oxidation is well understood and generally comprises four major steps [6,7,8,9]:
- (1)
- Adsorption of reagents on the surface of the photocatalyst,
- (2)
- Excitation of the photocatalyst with UV radiation and photo-generation of e--h+ pairs (photo-inducted electrons and holes),
- (3)
- Generation of hydroxyl radicals from water molecules adsorbed on the semiconductor surface,
- (4)
- Generated hydroxyl radicals and other structures take part in decomposition of such compounds as organic compounds, nitrogen oxides and other compounds,
- (b)
- Types of photoactive cements.
2.1. Obtaining Photoactive Cements by Incorporation Method
- (a)
- Examples of preparation of the cements by intercalation method using TiO2
- (b)
- Examples of preparation of the cements with modified TiO2
- (c)
- Examples of the preparation of cements with the addition of another type of photocatalyst
2.2. Preparation of Photoactive Cements by Surface Modification
- (a)
- Formation of thin TiO2 films with/without a separation layer
- (b)
- Forming thin films with use of modified TiO2
- (c)
- The formation of coatings using a different type of photocatalyst
2.3. Installation of the Photocatalyst Only in the Top Layer of Photoactive Cement
- (a)
- Examples using TiO2 and modified TiO2
- (b)
- Example using a different type of photocatalyst
3. Test Methods Used for the Evaluation of the Photocatalytic Activity of Cements
- (a)
- Photoactive tests used for determining the photocatalytic efficiency by air purification
- (b)
- Photoactive tests used for determining the self-cleaning properties
- (c)
- Photoactive tests used for determining the antimicrobial activity
4. Results of Mechanical Properties of Modified Cement Mortars
4.1. Effect of Additives on Fresh Properties of Cement-Based Composite Materials—Results
- (a)
- Effect on the workability of modified cement
- (b)
- Effect on the initial and final setting time of modified cement
- (c)
- Effect on hydration process of modified cement
4.2. Effect of Additives on the Properties of Hardened-Cement-Based Composite Materials—Results
4.3. Influence of Introduced Additives on Carbonation of Cement Materials
Author | Material | Conditions | Photocatalyst Dose (wt.%) | Time of Exposure to Conditions in the Chamber | Results |
---|---|---|---|---|---|
Rao et al. [155] | Mortars with the addition of 30 wt.% fly ash, binder: sand ratio 1:1 and 1:2 | 5 ± 1% CO2, RH = 60 ± 5% T = 23 ± 3 °C | 0.5; 0.75, 1% nano-TiO2 (NT) or 0.75%, 1.5%, 3% nano-SiO2 (NS) | At 14, 28, 56, and 91 days, the samples were taken from the chamber, broken into four parts, and the depth of carbonation was measured using the colorimetric method (with 0.1% phenolphthalein content) | 1: 1 blends with 0.5 wt.%, 0.75 wt.%, and 1 wt.%. NT and 0.75% NS show total resistance to carbonation. Mixtures with nano-TiO2 generally showed a lower carbonation depth than blends with nano-SiO2. Similarly, mortars from the 1: 1 family showed a lower depth of carbonation than the mortars from the 1: 2 family. |
Duan et al. [156] | Geopolymer paste based on fly ash activated in an alkaline sodium silicate solution | 20% CO2, RH = 65 ± 5% T = 24 ± 5 °C | 1, 3, 5% n-TiO2 | At 3, 7, 28, 90, and 180 days, the depth of carbonation was measured along the exposed surface of the split specimens 40 mm long at 12 points using the phenolphthalein spray test | The improvement of the resistance to carbonation was observed only after 28 days, after 180 days, the sample with 1% TiO2 showed the highest resistance |
Hernandez et al. [42] | Cement mortar | Normal carbonation | Addition of P25 in the amount of 5 and 10 wt.% in the surface layer | Determined with a 1% solution of phenolphthalein in ethanol after 28 days and 365 days | No significant carbonation was observed after 28 days, despite the detection of Ca(OH)2 by thermal analysis. Carbonation was more significant after 365 days, although mortars with/ without an additive of TiO2 were affected to the same extent. |
Diamanti et al. [159] | Cement mortar w/c = 0.52 or w/c = 0.69 | After 3 days of curing, the samples were moved to the carbonation room: 4% CO2, RH = 65% T = 20 °C | P25 addition in the amount of 2.5 and 5 wt.% | Determined with a solution of phenolphthalein with a concentration of 1% in ethanol after 28 days and 70 days in four points | An increase in the depth of carbonation with an increase in the w/c proportion, the addition of titanium dioxide caused a slight increase in the depth of carbonation, for example, in mixtures with a w/c of 0.69, after 70 days of exposure, the average depth of carbonation increased from about 9 mm to 11 mm and 11, 5 mm in concrete with content of 2.5 and 5% compared to cement TiO2. |
4.4. Influence of TiO2 on Abrasion Resistance
5. Examples of Investments with the Use of Photoactive Composite Materials
6. Conclusions and Future Prospects
- The presented research shows that the prepared concretes show photocatalytic activity and can clean the air, e.g., removing nitrogen oxides or volatile organic compounds. What is more, they have the ability to degrade soot and microorganisms, maintaining the lasting appearance of the building during its use.
- Photoactive cements used in the production of concrete products are mainly activated by UV radiation; scientists tried to find a photocatalyst active in visible light. Additional studies are needed to demonstrate durability in the field of photocatalysts other than TiO2.
- The procedure for introducing the photocatalytic active ingredient influences the surface concentration of the catalytic active sites, giving preference to the surface coating method over the bulk application of mortar when discussing only the photocatalytic efficiency, but without changing the nature of the active sites. However, the introduction of the active phase of the catalyst to the mass, even with a lower but still acceptable photocatalytic activity, results in a more stable system in terms of mechanical properties of the surface and CSH distribution. Given the need to balance the different photocatalyst performance requirements with the expected overall product yields, the incorporation of the active catalyst phase into the bulk appears to be more promising for sustainable long-term applications.
- 4.
- The issue that cannot be ignored in the research is the place, terrain conditions, and climate where the photocatalytic building, road, pavement, etc. will be located.
- 5.
- The presented research has shown that when designing a photocatalytic mortar, the type of binder, final texture, and microstructure of the material should be carefully selected to meet the performance requirements. Research is also needed to check the performance of the technology in the field.
Author Contributions
Funding
Institutional Review Board Statement
Conflicts of Interest
References
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Type of Method | Short Description |
---|---|
(A) Incorporation method. | Adding a photocatalyst during the manufacture of cement; cement replacement by mass with photocatalytic TiO2 particles (micro- or nanosized). |
(B) Photocatalyst coating technology—cement coating with a thin layer of TiO2 materials with (I) or without (II) a separation layer. | Creating coatings (generally 200 nm thick) by sprinkling with powder, applying paints, enamels, TiO2 suspensions, or special composites, e.g., TiO2/ZnAl. The coatings are applied by techniques such as direct painting on the surface of the cement matrix—by wet coating method; by immersion, spraying, spray pyrolysis, electrodeposition, or chemical vapor deposition (CVD). |
(C) Addition of the photocatalyst only to the top of the cement mortar layer. | Addition of TiO2 or modified TiO2 to the surface layer; lower layer is unmodified concrete; the top part of concrete consists of cement with photocatalyst. |
Gas concentration [ppm] | 1.0 |
Gas flow rate [dm3/min] | 3.0 |
Duration of the test | 5 h |
Radiation intensity [mV/cm2] | 1 |
Sample surface [cm2] | 50 |
Pretreatment of the sample | 16–24 h of UV irradiation with a power of ≥1.5 mW/cm2 without gas flow |
Temperature | 25 °C |
Analytical method | NOx chemiluminescence analyzer |
Author and Used Photocatalytic Material | Building Material | Age (Days) | Exemplary Dose (wt.%) | Flexural Strength (MPa) | |
---|---|---|---|---|---|
Photocatalytic Sample—Description of the Change or Value of the Bending Strength Respective Dose | Reference Sample | ||||
Wang et al. [130] n-TiO2 (10–25 nm, 200 m2/g) | Cement mortar | 56 | 1, 2, 3 | 12.3, 13.8, 13.6 | 10.7 |
Meng et al. [114] nano-TiO2 (20–50 nm) 39.91 m2/g | Cement paste, cement + fly ash 20 wt.% | 30 min during ball milling | 1 | increasing bending strength by 37.74% | 9.99 |
Han et al. [151] nano-SiO2 coated by TiO2 | Reactive concrete powder, w/c = 0.3 | 28 | 1, 3, 5 | 9.60, 12.45, 14.38 | 6.69 |
Hernandez [42] Aeroxide TiO2 P25 | White and grey cement mortar w/c in layer =1.3 | 28 | 5, 10 | G-8.21 (5%) 8.29 (10%) W-8.70 i 7.53 | G = 9.05 W = 8.65 |
365 | G-11.20 (5%) 10.91 (10%) W-10.69 i 10.32 | G = 12.26 W = 12.01 | |||
Yang et al. [153] TiO2 (20–100 nm) | slag paste activated with alkali | 3 | 0.5 | 7.71 | 6.17 |
7 | 12.46 | 10 | |||
28 | 17.32 | 12.58 | |||
Zhang et al. [122] n-TiO2 or n-SiO2 | Concrete | 28 | 1 | n-TiO2: 6.02 n-SiO2: 5.69 | 5.46 |
Nazari i Riahi [118] nano-TiO2 (15 nm) 155 m2/g | Cement mortar, 1 wt.% superplasticizer, w/c = 0.4 | 28 | 1–5 | increase in bending strength to 4 wt.%, the highest value after 28 days | 4.2 |
Nazari i Riahi [129] nano-TiO2 (15 nm) | Concrete with 15, 30.45.60 wt.% replacement with blast furnace slag | 28 | 1–4 | up to 3 wt.% TiO2 and 45 wt.% slag bending strength increased | 4.2 |
90 | 5.6 | ||||
Feng et al. [143] nano-TiO2 (20–50 nm) | Cement paste, w/c = 0.4 | 28 | 0.1 | 12.05 | 11.53 |
0.5 | 12.45 | ||||
1 | 12.48 | ||||
5 | 12.30 | ||||
Lucas et al. [14] P25 (85% anatase, 15% rutile) (21 nm) | Cement, cement-lime, gypsum, or gypsum-lime mortar | 28 | 0.5–5 | Cement and lime-cement mortars show a loss of bending strength in addition to more than 1 wt.%; the gypsum plaster showed a 60% reduction in strength at 0.5% wt., which indicates a greater difficulty for incorporation of nanoparticles | 8.0 |
Guo et al. [10] nano-TiO2 (100 nm) | Cement mortar modified with epoxy resin TiO2 | 7, 28 | 0, 1, 3 or 5 wt.%. in admixture with pure epoxy resin | increase with increasing dose and curing period | 8.8 9.5 |
Ma et al. [147] smoky nano-TiO2 50 m2/g | Cement mortar and concrete | 3 28 90 | 1–5 | increase with increasing dose up to 4 wt.% and curing period | 2.82 4.42 6.28 |
Rahim and Nair [154] nano-TiO2, nano-Al2O3 or nano-SiO2 | Cement mortar partially replaced by fly ash and blast furnace slag | 28 | 2, 3, 4, 5, 6 | After 28 days of hardening to 4 wt.%. nano-TiO2, 3 wt.% Al2O3, and nano-SiO2, an increase in flexural strength was observed | 9.0 |
Sikora et al. [69] TiO2 P25 (21 nm) n-SiO2 mSiO2/TiO2 (mesoporous silica nanospheres modified with titanium dioxide) | Cement mortar | 28 | 3 | TiO2 P25: 7.0 n-SiO2: 7.0 mSiO2/TiO2: 7.3 | 7.1 |
Ng et al. [116] TiO2 (15 nm) NT Fe2O3 (20–40 nm) NF SiO2 (20–30 nm) NS | Cement mortar with an admixture of 30 wt.% fly ash w/b = 0.485 | 28 | 1,3,5 | The increase is 19%, 11%, and 10%, respectively, in the NS, NT, and NF samples compared to the control sample. The optimal dose is 3 wt.% for each additive in terms of mechanical properties | NS- circa 4.8 NT- 4.9 NF- circa 4.4 |
Cerro-Prada et al. [80] TiO2/100% Anataz (20–30 nm) | Cement mortar | 1, 7, 28, 90 | 0.1, 0.2, 0.5, 1—without and with replacement of cement | For samples with cement replacement, in the early and middle age of the mortar (2, 7, and 28), slightly reduced strength is obtained for the substitute content of nano-TiO2 of 0.1%, 0.5%, and 1%. By replacing TiO2 in cement with 0.2%, however, a slight improvement in bending strength (13.7%) is achieved in the long term. In the case of the mortar prepared with the addition of TiO2 without cement replacement, no improvement can be clearly observed for the TiO2 content of 0.2%, 0.5%, and 1% | [80] |
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Dudek, D.; Janus, M. Photoactive Cements: A Review. Materials 2022, 15, 5407. https://doi.org/10.3390/ma15155407
Dudek D, Janus M. Photoactive Cements: A Review. Materials. 2022; 15(15):5407. https://doi.org/10.3390/ma15155407
Chicago/Turabian StyleDudek, Dominika, and Magdalena Janus. 2022. "Photoactive Cements: A Review" Materials 15, no. 15: 5407. https://doi.org/10.3390/ma15155407