Article

Photocatalytic Activity of Silver‐Based

Biomimetics Composites
Abniel Machín 1,*, Loraine Soto‐Vázquez 2, Carla Colón‐Cruz 3, Carlos A. Valentín‐Cruz 3,
Gerardo J. Claudio‐Serrano 3, Kenneth Fontánez 4, Edgard Resto 2, Florian I. Petrescu 5,
Carmen Morant 6 and Francisco Márquez 3,*

1 Arecibo Observatory, Universidad Ana G. Méndez‐Cupey Campus, San Juan 00926, Puerto Rico
2 Materials Characterization Center Inc., Molecular Sciences Research Center, University of Puerto Rico,
San Juan 00926, Puerto Rico; [email protected] (L.S.‐V.); [email protected] (E.R.)
3 Nanomaterials Research Group, School of Natural Sciences and Technology, Universidad Ana G. Méndez‐

Gurabo Campus, Gurabo 00778, Puerto Rico; [email protected] (C.C.‐C.);

[email protected] (C.A.V.‐C.); [email protected] (G.J.C.‐S.)
4 Department of Chemistry, University of Puerto Rico‐Río Piedras, San Juan 00925, Puerto Rico;

[email protected]
5 IFToMM‐ARoTMM, Bucharest Polytechnic University, 060042 Bucharest, Romania; [email protected]

6 Department of Applied Physics, Autonomous University of Madrid and Instituto de Ciencia de Materiales

Nicolas Cabrera, 28049 Madrid, Spain; [email protected]

* Correspondence: [email protected] (A.M.); [email protected] (F.M.)

Abstract: Different Ag@TiO2 and Ag@ZnO catalysts, with nanowire (NW) structure, were
synthesized containing different amounts of silver loading (1, 3, 5, and 10 wt.%) and characterized
by FE‐SEM, HRTEM, BET, XRD, Raman, XPS, and UV–vis. The photocatalytic activity of the
composites was studied by the production of hydrogen via water splitting under UV–vis light and
Citation: Machín, A.; Soto‐V, L.; the degradation of the antibiotic ciprofloxacin. The maximum hydrogen production of all the silver‐
Colón, C.; Valentín, C.A.; Claudio‐ based catalysts was obtained with a silver loading of 10 wt.% under irradiation at 500 nm. Moreover,
Serrano, G.J.; Fontánez, K.; Resto, E.; 10%Ag@TiO2 NWs was the catalyst with the highest activity in the hydrogen production reaction
Petrescu, F.I.; Morant, C.; Márquez, (1119 μmol/hg), being 18 times greater than the amount obtained with the pristine TiO2 NW catalyst.
F.; et al. Photocatalytic Activity of The most dramatic difference in hydrogen production was obtained with 10%Ag@TiO2‐P25, 635
Silver‐Based Biomimetics μmol/hg, being 36 times greater than the amount reported for the unmodified TiO2‐P25 (18
Composites. 2021, 6, 4. μmol/hg). The enhancement of the catalytic activity is attributed to a synergism between the silver
https://doi.org/10.3390/biomimetics6
nanoparticles incorporated and the high surface area of the composites. In the case of the
010004
degradation of ciprofloxacin, all the silver‐based catalysts degraded more than 70% of the antibiotic
in 60 min. The catalyst that exhibited the best result was 3%Ag@ZnO commercial, with 99.72% of
Received: 14 October 2020
degradation. The control experiments and stability tests showed that photocatalysis was the route
Accepted: 30 December 2020
Published: 4 January 2021
of degradation and the selected silver‐based catalysts were stable after seven cycles, with less than
1% loss of efficiency per cycle. These results suggest that the catalysts could be employed in
Publisher’s Note: MDPI stays additional cycles without the need to be resynthesized, thus reducing remediation costs.
neutral with regard to jurisdictional
claims in published maps and Keywords: photocatalysis; hydrogen production; ciprofloxacin; silver nanoparticles; TiO2; ZnO
institutional affiliations.

1. Introduction
Copyright: © 2021 by the authors.
During the last decade, there has been a significant increase in discussions related to
Licensee MDPI, Basel, Switzerland.
the production of energy from renewable sources [1,2]. This is mainly due to the increase
This article is an open access article
in global temperatures and climate change, caused by the burning of fossil fuels and
distributed under the terms and
release of greenhouse gases such as carbon dioxide (CO2) [2]. For this reason, countless
conditions of the Creative Commons
Attribution (CC BY) license
efforts around the world have focused on developing technologies that allow the
(http://creativecommons.org/licenses production of energy from renewable sources in a cost‐effective way. Within these efforts,
/by/4.0/). inspiration and answers are sought in nature. Materials that can mimic what nature has

Biomimetics 2021, 6, 4. https://doi.org/10.3390/biomimetics6010004 www.mdpi.com/journal/biomimetics

Biomimetics 2021, 6, 4 2 of 22

perfected over thousands or millions of years are investigated in the hope that they can
be manufactured, used, developed, and employed upscale.
Developing active and robust water oxidation catalysts is the key to constructing
efficient artificial photosynthetic systems [3–6]. The oxidation of water is the primary and
key reaction of overall water splitting, but it requires the transfer of 4 electrons (e−) and
4H+ with continuous formation of O‐O bonds, leading to high energy barriers and slow
kinetics [6]. Therefore, great efforts have been devoted to developing efficient catalysts,
including homogeneous, heterogeneous, and especially biomimetic catalysts, to facilitate
the oxygen evolution reaction (OER) in the past few decades [6].
In terms of biomimetics catalysts, water oxidation occurs in nature at the so‐called
CaMn4O5 oxygen evolution complexes surrounded by many amino acid residues in
photosystem (II) (PSII) [5,6]. To date, water oxidation catalysts have been integrated into
photocatalytic and photoelectrocatalytic (PEC) systems to construct artificial
photosynthetic systems [4–6]. Selective deposition on special sites of light‐harvesting
semiconductors and interface engineering with charge transfers are some of the
modifications that have been implemented to improve the efficiency of photosystems [6].
Semiconductors such as TiO2 and ZnO have been extensively used, mainly due to
their nontoxicity, low cost, and high chemical stability [7–10]. One of the main
disadvantages of using TiO2 and ZnO as photocatalysts is their wide band gap energy
(i.e., 3.2 eV for TiO2 anatase; 3.37 eV for ZnO wurtzite). With these energy gaps, only UV
light can be used [8,9]. This fact must be taken into consideration since only 4% of the total
radiation that comes from the sun is in the UV region, whereas 50% is in the visible region
of the electromagnetic spectrum [10]. It is for this reason that recent investigations have
focused on modifying the band gap of the catalysts. Some of the chemical modifications
include the doping of TiO2 and ZnO with metal and non‐metal elements [7–10]. The
incorporation of noble metals, such as silver (Ag), on the surfaces of these
semiconductors has gained substantial interest in recent years due to the ability of the
noble metal nanoparticles to reduce the fast recombination of the photogenerated
charge carriers, enabling the use of visible light [11–18]. By reducing the photogenerated
charge carriers, the UV activity is increased due to the electron transfer from the
conduction band (CB) of TiO2 or ZnO to the noble metal nanoparticles [12]. The
photoactivity in the visible spectral range can be explained due to the surface plasmon
resonance effect and charge separation by the transfer of photoexcited electrons from the
metal nanoparticles to the CB of TiO2 or ZnO [11–18].
The development of silver‐based catalysts (Ag@TiO2 and Ag@ZnO) for hydrogen
production via water splitting and the degradation of organic pollutants have been
attracting attention in recent years. For example, Saravanan et al. [12] synthesized
Ag@TiO2 photocatalysts for the production of hydrogen and degradation of methyl
orange dye (MO). The catalysts exhibited good visible light activity and excellent stability
over three cycles for the aqueous phase photocatalytic degradation of MO (38 μmol/h g)
and excellent hydrogen production from water splitting (910 μmol/h g). The results were
justified by the incorporation of Ag onto TiO2, which improved the photophysical
properties, narrowing the band gap and suppressing the charge carrier recombination. On
the other hand, Mao et al. [14] synthesized Ag@TiO2 with different structures
(nanoparticles, nanoflakes, and nanorods). The as‐synthesized Ag@TiO2 compounds were
employed as catalysts for the photodegradation of MO under visible light irradiation,
showing that Ag@TiO2 compounds display a catalytic performance superior to pure TiO2.
The catalyst with 20 wt.% Ag exhibited the best photocatalytic activity after 120 min of
treatment, with photodegradations of ca. 98.9% for MO under visible light irradiation.
This was explained by the fact that a suitable amount of Ag could restrain the
recombination of the photoproduced charges and extend the range of the light absorption.
Meanwhile, Mou et al. [15] developed three‐dimensional (3D) Ag@ZnO assemblies with
porous nanosheets as building blocks to produce hydrogen via water splitting and the
degradation of 4‐nitrophenol, demonstrating superior sunlight‐driven photocatalytic
Biomimetics 2021, 6, 4 3 of 22

activities, with nearly 100% degradation of 10 ppm 4‐nitrophenol and 0.4436 mmol g−1 h−1
of hydrogen production. The authors attribute these results to the synergistic effect
between 2D ZnO porous single crystalline nanosheets and silver, which could not only
accelerate the separation and migration efficiency of charge carriers but also enhance the
charge collection efficiency. Other authors [16] synthesized Ag@ZnO composites for the
degradation of rhodamine B and the production of hydrogen by water splitting. Under
ultraviolet, visible‐light, simulated sunlight, and microwave‐assisted irradiation, the
composite exhibited better photocatalytic properties for the photocatalytic degradation of
rhodamine B compared to that of P25 and ZnO. Moreover, the composite was investigated
as a catalyst for the degradation of four dyes with different structures under UV
conditions, exhibiting good degradation performance. In addition, the photocatalytic
hydrogen production experiments showed that Ag@ZnO had some ability to produce
photocatalytic hydrogen.
Ciprofloxacin is a fluoroquinolone which constitutes one of the major families of
antibiotics [19]. Ciprofloxacin is employed for treating infectious diseases and is effective
against both Gram‐positive and Gram‐negative bacteria. During their use in humans,
these antibiotics are incompletely metabolized and are excreted mostly through urine and
stool. Ciprofloxacin has been detected in appreciable quantities in continental waters and
reservoirs, as it is a compound which is highly resistant to degradation. Antibiotics, and
particularly ciprofloxacin, enter the body through drinking water, allowing bacteria to
become resistant to these compounds. For these reasons, the purposes of this investigation
were twofold: (1) to synthesize different weight percentages (1, 3, 5, and 10 wt.%) of silver‐
based catalysts (Ag@TiO2 and Ag@ZnO); and (2) to study the photocatalytic activity of the
as‐synthesized composites in two processes of current relevance—the production of
hydrogen via water splitting and the photodegradation of ciprofloxacin.

2. Materials and Methods

2.1. Reagents
All reagents were used as received and all the experimental solutions were prepared
using ultra‐pure water (Milli‐Q water, 18.2 MΩcm−1 at 25 °C). Acetone, isopropyl alcohol
+99.9%, and HCl 37% (ACS Reagent) were provided by Acros Chemicals (Newark, NJ,
USA). TiCl4 99.9% was obtained from Fisher Scientific (Pittsburgh, PA, USA). Degussa P25
(Degussa, nanopowder with 21‐nm particle size, 35–65 m2∙g−1 surface area, +99.5%),
AgNO3 (99.99+%, trace metal basis), Zn(C2H3O2)2 (98+%, ACS Reagent), and NaBH4
+99.9% were provided by Sigma Aldrich (Milwaukee, WI USA). The commercial zinc
oxide (99.99%) was obtained from Alfa Aesar (Ward Hill, MA, USA). Si <100> substrates,
p‐type boron‐doped, provided by El‐CAT (Ridgefield Park, NJ, USA), were used as
substrates for the hydrothermal growth of TiO2 nanowires (TiO2 NWs). Finally, for the
photocatalytic experiments, ciprofloxacin (C17H18FN3O3, ≥98% HPLC), Na2S 99.9%, and
Na2SO3 + 98% were also obtained from Sigma Aldrich (Milwaukee, WI, USA).

2.2. Synthesis of TiO2 and ZnO Nanowires

The synthesis of TiO2 NWs was carried out following the method described by Cotto
et al. (2013) [20]. In a typical synthesis, 50 mL of concentrated hydrochloric acid and 50
mL of deionized water were mixed in a 200 mL Erlenmeyer flask. After this, 3 mL of the
titanium precursor was added by dripping, under agitation, at room temperature. The
mixture was magnetically stirred until all solid particles were dissolved (approximately
10 min). Then, the solution was placed into 30‐mL Teflon‐lined stainless‐steel autoclaves.
Next, single crystal silicon substrates, Si<100>, were introduced inside the autoclaves.
Autoclaves were maintained at 180 °C for 24 h. The resulting TiO2 NWs, grown on the
surfaces of the silicon wafers, were thoroughly washed with deionized water and dried
overnight at 60 °C.
Biomimetics 2021, 6, 4 4 of 22

In the case of the ZnO NWs, the synthesis consisted of the thermal decomposition of
zinc acetate, according to the procedure used by Lin and Li (2009) [21]. For this, 0.5 g of
zinc acetate dihydrate was heat‐treated at 300 °C for 3 h in an alumina crucible. After the
reaction time, the crucible was left to cool down and the product was then collected and
sealed at room temperature.

2.3. Incorporation of Silver Nanoparticles (Ag NPs)

The incorporation of Ag NPs onto the surfaces of TiO2 NWs, TiO2‐P25, ZnO NWs,
and ZnO commercial catalysts consisted of a modification of the method described by
Naldoni et al. [22]. A typical synthesis consisted of dispersing 500 mg of the desired
catalyst in 40 mL of H2O and subsequent treatment with ultrasound for 20 min. After this,
the desired amount of the silver precursor was added to the reaction mixture and stirred
for 30 min. Finally, a NaBH4 solution (10 mg in 10 mL of H2O) was added dropwise, under
stirring, and allowed to react for 10 min at room temperature. The reaction product was
centrifuged, washed three times with deionized water, and dried overnight at 60°C. The
different silver‐based composites were identified as x%Ag@TiO2 NWs, x%Ag@TiO2‐P25,
x%Ag@ZnO NWs, x%Ag@ZnO commercial. The numbers (x%) correspond to the weight
percentage of Ag NPs in the sample.

2.4. Characterization of the Catalysts

The catalysts were fully characterized by electron microscopy, using field‐emission
scanning electron microscopy (FE‐SEM, Philips XL30 S‐FEG) and high‐resolution
transmission electron microscopy (HRTEM, JEOL 3000F). XPS measurements were
obtained on an ESCALAB 220i‐XL spectrometer, by using the non‐monochromated Mg
Kα (1253.6 eV) radiation of a twin‐anode, operating at 20 mA and 12 kV in the constant
analyzer energy mode, with a PE of 50 eV. Brunauer–Emmett–Teller (BET) specific surface
areas were measured using a Micromeritics ASAP 2020, according to N2 adsorption
isotherms, at 77 K. Raman measurements were acquired using a DXR Thermo Raman
Microscope, employing a 532‐nm laser source at 5‐mW power and a nominal resolution
of 5 cm−1. X‐ray diffraction (XRD) patterns were obtained in theta/2theta configuration in
the range of 20–80° at 2° min−1, using a Bruker D8 Advance X‐Ray Diffractometer,
operating at 40 kV and 40 mA. The UV–vis spectra were measured using a Shimadzu UV‐
1800PC spectrophotometer.

2.5. Photocatalytic Experiments

The hydrogen production via water splitting experiments consisted of the following:
100 mL of deionized water was added to a 200 mL quartz reactor flask. Then, 50 mg of the
silver‐based catalyst was added to the flask containing the water. Solutions of 0.5 M Na2S
and 0.03 M Na2SO3 were added as sacrificial reagents to promote photocatalytic activity
and increase H2 production, due to their action as hole scavengers [23,24]. The reaction
mixture was thermostatized at 20 °C, magnetically stirred at 20 rpm, and purged with
nitrogen for at least 20 min. Then, the solution was exposed to UV–vis radiation for 120
min using different filters to select the appropriate irradiation wavelength. The produced
hydrogen was collected, using nitrogen as gas carrier, and was identified and quantified
by Gas Chromatography with a Thermal Conductivity Detector (GC‐TCD, Perkin‐Elmer
Clarus 600).
For the photocatalytic degradation experiments, a solar simulator composed of two
annular white bulb lights with a total irradiation power of 60 watts was used. A solution
of 1 × 10−5 M of ciprofloxacin was prepared and then the desired catalyst was added. After
adding the catalyst and adjusting the pH to 7, the system was kept in the dark for 30 min
to let the system reach adsorption–desorption equilibrium. Then, a small amount of H2O2
(3 mL, 0.005%) was added; additional oxygen was provided to the system by constant air‐
bubbling. The white bulb lights were switched on, and the photocatalytic system was
Biomimetics 2021, 6, 4 5 of 22

maintained under constant stirring and irradiation. The reaction was monitored for a
period of 60 min, and the kinetics of photodegradation was studied by taking aliquots
every 10 min. After filtering the aliquots with 0.45‐μm membrane filters, the samples were
analyzed with a Shimadzu UV‐1800PC spectrophotometer.

3. Results and Discussion

3.1. Characterization of Catalysts
Figure 1 shows different FE‐SEM images of TiO2 NWs and ZnO NWs at different
magnifications. The as‐synthesized TiO2 NWs consist of homogeneous and highly
branched structures (Figure 1A). At higher magnifications (Figure 1B), TiO2 NWs have a
square‐like form and are composed of smaller units with the same shape. The specific
surface area of the catalyst obtained by BET measurements was 403 m2 g−1, a large area
that may be justified by the highly branched structures and could have relevant effects on
the catalytic properties of this material. The FE‐SEM images of ZnO catalysts are shown
in Figure 1C. ZnO NWs consisted of non‐homogenous wires, with differences in size and
length. The BET surface area of ZnO NWs (160 m2 g−1) was clearly less than that observed
for TiO2 NWs.

Figure 1. Field emission scanning electron microscopy (FE‐SEM) images of the as‐synthesized TiO2 Nanowires (NWs) at
5000× (A), 20,000× (B), and ZnO NWs at 5000× (C).

After the synthesis of TiO2 NWs and ZnO NWs catalysts, different amounts of Ag
NPs (1%, 3%, 5%, and 10% wt.%) were deposited onto the surfaces of the as‐synthesized
catalysts and their commercial forms (TiO2‐P25 and commercial ZnO) for comparison
purposes, using a chemical reduction method. Figure 2 shows the high‐resolution
transmission electron microscopy (HRTEM) images of the catalysts containing 10 wt.% of
Biomimetics 2021, 6, 4 6 of 22

Ag. All silver‐based catalysts showed a non‐homogenous distribution of the metal on the
surface, with diameters of ca. <10 nm (Figure 2). This is a normal characteristic when using
sodium borohydride (NaBH4) as a reducing agent, and it has been documented in
previous works [25–27]. The 10%Ag@TiO2‐P25 (Figure 2A) and 10%ZnO commercial
(Figure 2C) composites consisted of supports of different shapes and sizes, of micrometers
in length, and both the 10%Ag@TiO2 NWs (Figure 2B) and 10%ZnO NWs (Figure 2D)
showed significant changes in their morphology compared to the bare catalysts shown in
Figure 1. These changes were expected and are also attributed to the synthesis process.

Figure 2. High‐resolution transmittance electron microscopy (HRTEM) images of 10%Ag@TiO2‐P25 (A), 10%Ag@TiO2
NWs (B), 10%Ag@ZnO commercial (C), and 10%Ag@ZnO NWs (D) catalysts. The red arrows indicate the presence of Ag
Nanoparticles (NPs).

The BET surface areas of the silver‐based catalysts with different Ag loadings were
analyzed and the results are shown in Table 1. Before the silver deposition, the average
surface areas of the as‐synthesized TiO2 NWs and ZnO NWs were 403 and 160 m2∙g−1,
respectively, whereas the surface areas of the commercial ones (TiO2‐P25 and ZnO) were
53 and 18 m2∙g−1, respectively. These results clearly show that the synthesis processes used
to obtain TiO2 NWs and ZnO NWs allowed us to obtain high‐surface supports.
Unexpectedly, the addition of silver nanoparticles on the pristine catalysts resulted in an
increase in surface area. This effect is much more significant in composites with the
highest percentage of silver on the surface (see Table 1). As was determined by HRTEM,
these nanoparticles are dispersed on the surfaces of the catalysts, suggesting that the
chemical reduction approach is an efficient method for synthesizing these composites.
Biomimetics 2021, 6, 4 7 of 22

Table 1. Brunauer, Emmett and Teller (BET) surface area of the silver‐based catalysts.

TiO2‐P25 ZnO Commercial TiO2 NWs ZnO NWs

(m2∙g−1) (m2∙g−1) (m2∙g−1) (m2∙g−1)
0% (Bare) 53 18 403 160
1%Ag 63 78 417 167
3%Ag 72 81 426 179
5%Ag 81 99 438 194
10%Ag 89 112 443 202

The XRD patterns of pristine catalysts and catalysts with 10 wt.% Ag are shown in
Figure 3. Figure 3A, corresponding to TiO2 NWs (pristine or with 10 wt.% Ag), shows
intense peaks at 27° (110), 36° (101), and 55° (211), which have been unambiguously
ascribed to the rutile phase (JCPDS 88‐1175) [28]. The 10% Ag @ TiO2 NW diffractogram,
as well as the rest of the catalysts with other percentages of silver, showed a small shift
towards lower angles compared to the pure TiO2 NWs. This displacement has been
attributed to the incorporation of the silver nanoparticles on the surface of the support
[29]. No silver peak was observed at low silver loading (1%Au@TiO2 NWs and
3%Au@TiO2 NWs). Only 10%Ag@TiO2 NWs presented two peaks at ca. 38° (111) and 46°
(200), ascribed to the presence of silver nanoparticles with fcc unit cell.
TiO2‐P25 is a mixture of 70% anatase and 30% rutile. The characteristic peaks of
anatase (JCPDS 21‐1272) can be found at ca. 25° (101), 38° (004), 48° (220), 54° (105), and
55° (211) [28], while the rutile crystalline phase has its characteristic peaks at ca. 27° (110),
36° (101), 41° (111), and 54° (211) (JCPDS 34‐180) [28]. All the peaks corresponding to both
anatase and rutile are present in the diffraction pattern of Figure 3B–D. The characteristic
peak of rutile (ca. 27°) was not present in any silver loadings. Only the 10%Ag@TiO2‐P25
showed one peak assigned to the face‐centered cubic (fcc) structure of the adsorbed Ag
metal nanoparticles corresponding to the h k l parameters (200) at ca. 46° [30].
The XRD patterns of silver‐based ZnO NWs and commercial ZnO did not show major
differences (Figure 3C,D). Peaks shown at ca. 32° (100), 34.8° (002), 36° (101), 47.5° (102),
56.2° (110), 62.8° (103), 66° (200), 67.5° (112), and 68.8° (201) were ascribed to the ZnO
wurtzite phase (JCPDS 396‐1451) [31]. The presence of silver nanoparticles was only
detected in 10%Ag@ZnO commercial and 10%Ag@ZnO NWs at ca. 38° (111) and not in
catalysts with lower silver percentages.
Biomimetics 2021, 6, 4 8 of 22

A B

C D

Figure 3. X‐ray diffraction patterns (XRD) of TiO2 NW (A,a), 10%Ag@TiO2 NW (A,b), TiO2‐P25 (B,c), 10%Ag@TiO2‐P25
(B,d), ZnO commercial (C,e), 10%Ag@ZnO commercial (C,f), ZnO NW (D,g), and 10%Ag@ZnO NW (D,h) catalysts.

Figure 4 shows the Raman spectra of pristine catalysts and catalysts with 10 wt.% Ag.
The anatase phase shows major bands at ca. 150, 395, 515, and 638 cm−1 [32] that can be
observed in the bare TiO2‐P25 and 10%Ag@TiO2‐P25 (Figure 4A, a,b) catalysts, being
attributed to the five Raman‐active modes of the anatase phase, corresponding to Eg(1),
B1g(1), A1g + B1g(2), and Eg(2) vibrational modes. The typical Raman bands resulting from the
rutile phase appear at ca. 143 cm−1 (superimposed with the 145 cm−1 band from the
anatase), 235, 455, and 612 cm−1 and have been ascribed to the B1g, Eg, and A1g vibrational
modes [32]. In the case of the 10%Ag@TiO2‐P25 (Figure 4A,b), and in catalysts with lower
percentages of silver, the peak corresponding to the presence of silver nanoparticles was
not detected. The only change observed by increasing the silver loading of the samples
was a slight decrease in the intensity of the characteristic peaks. This effect has been
attributed directly to the presence of silver [33]. In TiO2 NWs (Figure 4B,c), the
characteristic Raman bands of TiO2 rutile can be found at ca. 275 and 475 cm−1 [34]. As can
be seen in Figure 4B,c, these bands are present, confirming that rutile is the only crystalline
phase identified in the as‐synthesized TiO2 NWs. As already shown before for catalysts
based on P25, no peaks corresponding to the presence of silver nanoparticles were
detected (see Figure 4B,d).
In the case of commercial ZnO and ZnO NWs, no relevant differences were observed
(Figure 4C,D). The wurtzite phase shows main bands at ca. 327, 378, 437, and 1050 cm−1
[35]. The 1150 cm−1 band, observed in both the commercial catalyst (Figure 4C,e) and the
as‐synthesized ZnO NWs (Figure 4D,g), has been attributed to overtones and/or
combination bands [36]. The narrow strong band at 437 cm−1 was assigned to the E2 modes,
Biomimetics 2021, 6, 4 9 of 22

involving mainly Zn motion, corresponding to the band characteristic of the wurtzite

phase [34]. The band at 378 cm−1 was ascribed to the A1T mode, indicating some degree of
structural disorder in the ZnO lattice [36]. No bands associated with Ag NPs were
detected in 10%Ag@ZnO commercial (4C,f), 10%ZnO NWs (4D,h), or in catalysts with
lower percentages of silver.

A B

C D

Figure 4. Raman spectra of TiO2‐P25 (A,a), 10%Ag@TiO2‐P25 (A,b), TiO2 NWs (B,c), 10%Ag@TiO2 NWs (B,d), ZnO
commercial (C,e), 10%Ag@ZnO commercial (C,f), ZnO NWs (D,g), and 10%Ag@ZnO NWs (D,h) catalysts.

The two catalyst systems were also characterized by XPS. Figure 5 shows the most
relevant transitions of each system, considering the catalysts with the highest silver load
(10%Ag@ZnO NWs and 10%Ag@TiO2NWs). Figure 5A shows the transitions
corresponding to Ti2p of the 10%Ag@TiO2NW catalyst. The peaks observed at 464.5 and
458.8 eV have been unambiguously assigned to Ti4+, typical of rutile TiO2, as identified by
XRD [36,37]. In this catalyst, the O1s clearly shows two components at 530.1 and 531.4 eV.
The lowest bond energy peak has been assigned to O2− ions in the Ti–O bonds. The
shoulder around 531.4 eV has been assigned to O2− ions in the oxygen‐deficient regions,
as previously referenced in the literature [36,37]. Figure 5C shows the transitions
corresponding to Ag3d, with peaks at 374 and 368 eV, and a characteristic spin‐orbit
splitting of 6.0 eV, which have been clearly assigned to metallic Ag [36,37]. In the case of
the 10%Ag@ZnONWs catalyst, the result obtained was also as expected. Figure 5D shows
a peak at 1022.1 eV, corresponding to the Zn 2p3/2 transition, which has been assigned to
Zn2+ in ZnO [36,37]. As was the case with the rutile‐based catalyst, the peak corresponding
to the O1s transition also shows two components: a main component at 530.1 eV, assigned
to oxygen in Zn‐O bonds, and a shoulder at ca. 531.3 eV that has been assigned to O2− ions
in the oxygen‐deficient regions [17,38]. In this catalyst, and as can be deduced from the
Biomimetics 2021, 6, 4 10 of 22

deconvolution carried out (see Figure 5B,E), the ratio corresponding to the shoulder/main
peak is lower than in the case of the rutile‐based catalyst, which undoubtedly has
implications for the catalytic behavior [36,37]. Finally, as with the rutile‐based catalyst, the
Ag nanoparticles on the surface are found as metallic silver (see Figure 5F).

A B C

D E F

Figure 5. X‐ray photoelectron spectroscopy (XPS) spectra of Ti 2p1/2, O 1s, Ag3d3/2, Ag3d5/2 taken from the 10%Ag@TiO2
NW catalyst (A–C), and Zn 2p1/2, O 1s, Ag3d3/2, and Ag3d5/2 taken from the 10%ZnO NW composite (D–F).

The pristine catalysts and catalysts with 10 wt.% were also characterized by UV–vis
spectroscopy (see Figure 6). The main absorption of TiO2 (Figure 6A) was observed at ca.
300 nm, showing low absorption efficiency in the visible range. No additional absorption
peaks were detected for any of the Ag@TiO2‐P25 (Figure 6A,b) and Ag@TiO2 NW (Figure
6A,c) catalysts. This result is justified by the limited sensitivity of the spectrophotometer
and the small size of the Ag NPs [39].
In the case of ZnO catalysts, the maximum absorption was observed at ca. 360 nm
(Figure 6B,d,e,f), with very low absorption efficiency in the visible region. As with TiO2‐
based catalysts, no peaks associated with the presence of Ag NPs were observed.
Biomimetics 2021, 6, 4 11 of 22

Figure 6. UV–vis spectra of TiO2 NW (A,a), 10%Ag@TiO2‐P25 (A,b), 10%Ag@TiO2 NW (A,c), ZnO NW (B,d), 10%Ag@ZnO
commercial (B,e), and 10%Ag@ZnO NW (B,f) catalysts. The region in which the presence of Ag NPs should be observed
is indicated.

3.2. Photocatalytic Hydrogen Production via Water Splitting

The photocatalytic hydrogen production of the unmodified and silver‐based
catalysts at wavelengths of 300, 400, and 500 nm is shown in Figure 7. At 320 nm, the
highest hydrogen production was obtained with the 10%Ag@ZnO NWs (795 μmol/hg),
followed by 10%Ag@TiO2 NWs (758 μmol/hg), 10%Ag@TiO2‐P25 (575 μmol/hg), and
10%Ag@ZnO commercial (483 μmol/hg), respectively. When compared with the
production of the unmodified catalysts, all the silver‐based catalysts increased their
hydrogen production over 420 μmol/hg, with the 10%Ag@TiO2 NWs catalyst being the
one with the highest difference, 702 μmol/hg. This represented an increase that was 13.5
times greater than bare TiO2 NWs. More details can be found in Table 2.

Table 2. Silver‐based catalysts with the highest hydrogen production and their difference from the
unmodified supports at a wavelength of 320 nm *.

Maximum H2
Maximum H2
Production; Difference in Times Greater than
Production;
Catalyst Silver‐Based H2 Production Unmodified
Unmodified
Catalysts (μmol/gh) Catalyst
Catalyst (μmol/gh)
(μmol/gh)
10%AgTiO2 NWs 758 TiO2 NWs; 56 702 13.53
10%AgTiO2‐P25 575 TiO2‐P25; 103 389 5.58
10%AgZnO NWs 795 ZnO NWs; 365 430 2.18
10%AgZnO comm ** 483 ZnO Comm * 66 417 7.32
* Only the highest hydrogen production from all the silver‐based catalysts is shown, ** Commercial.
Biomimetics 2021, 6, 4 12 of 22

Figure 7. Photocatalytic hydrogen production of the different silver‐based catalysts under irradiation at 320 (A), 400 (B),
and 500 nm (C).

In all cases, the highest amount of hydrogen was obtained with a silver load of 10%
by weight, indicating that even higher hydrogen production could be obtained with
higher silver loadings. Another important aspect is that the highest hydrogen production
was obtained with the catalyst of higher surface area. Different studies [34,40–43] have
found that a key factor in the photocatalytic activity of semiconductors, such as TiO2 and
ZnO, is their high surface area. A high surface area leads to a higher density of localized
states [34], which involve electrons with energies between the conduction and valence
bands. These electrons are present due to terminated and unsaturated bonds on the
surfaces, providing beneficial charge separation in the form of trapping sites for photo‐
generated charge carriers [34]. Although the 10%Ag@TiO2 NW catalyst has a higher
surface area compared to 10%Ag@ZnO NWs (see Table 1), the 10%Ag@ZnO NW catalyst
obtained higher hydrogen production. In fact, the amount of hydrogen obtained by the
unmodified ZnO NWs was not expected and it is unusual for ZnO. Zhang et al. [43] have
reported that one‐dimensional nanostructures, such as nanowires, may have greater
photocatalytic activity due to their large surface‐to‐volume ratio, as compared to other
morphologies. Additionally, different studies [43–45] reveal that surface properties such
as surface defects and oxygen vacancies of photocatalysts play a significant role in
photocatalytic activity. These studies argue that the crystalline defects of ZnO nanowires
exist primarily due to oxygen vacancies and that nanoparticles with crystalline defects can
exhibit visible light photocatalysis even without doping with transitional metals.
At 320 nm (UV light), direct photoexcitation of TiO2 or ZnO with photons of energy
greater than the bandgap (λ < 380 nm) is assumed, leading to the generation of electrons
Biomimetics 2021, 6, 4 13 of 22

in the semiconductor conduction band and electron holes in the valence band [46]. The
electrons in the conduction band will move to the silver nanoparticles, acting as electron
buffers and catalytic sites for hydrogen generation [46]. The electron holes will be
quenched by the sacrificial electron donors (SO32−/SO42−) [23,24].
At 400 nm, the highest hydrogen production values were 1065, 963, 648, and 516
μmol/hg, obtained by 10%Ag@TiO2 NWs, 10%Ag@ZnO NWs, 10%Ag@TiO2‐P25, and
10%Ag@ZnO commercial, respectively (Figure 7B). The highest difference in hydrogen
production between silver‐based and unmodified catalysts was obtained by the
10%Ag@TiO2 NWs and bare TiO2 NWs (990 μmol/hg). This amount was 14 times higher
than that reported by the pristine catalyst. Details of the other maximum amounts and
differences can be found in Table 3.

Table 3. Silver‐based catalysts with the highest hydrogen production and their difference from the
unmodified supports at a wavelength of 400 nm *.

Maximum H2 Maximum H2
Difference
Production; Production Times Greater
in H2
Catalyst Silver‐Based Unmodified than Unmodified
Production
Catalysts Catalyst Catalyst
(μmol/gh)
(μmol/gh) (μmol/gh)
10%AgTiO2 NWs 1065 TiO2 NWs; 75 990 14.20
10%AgTiO2‐P25 648 TiO2‐P25; 71 577 9.13
10%AgZnO NWs 963 ZnO NWs; 427 430 2.26
10%AgZnO comm. ** 516 ZnO Comm * 45 471 11.47
* Only the highest hydrogen production from all the silver‐based catalysts is shown, **
Commercial.

As it was seen at 320 nm, the highest hydrogen production at 400 nm was obtained
with the catalysts of 10 wt.% of silver loadings and higher surface areas. This is an
indication that it could be possible to increase the amount of hydrogen at higher silver
loadings. At 400 nm, the Ag@TiO2 NW catalysts produced more hydrogen than the
Ag@ZnO NW composites. This could be attributed to the marked difference in surface
area between the catalysts (see Table 1) and the band gap energies of the supports. ZnO
has a bandgap energy of 3.37 eV, while for TiO2, the bandgap is somewhat lower (3.2 eV,
anatase); therefore, with a wavelength of 400 nm, it would be easier to promote the
excitation of the electrons in the valence band of TiO2 than those of ZnO [42].
It is assumed that when irradiated with visible light (λ > 400 nm), photoexcitation of
Ag NPs due to plasmon resonance occurs, and electrons from Ag are injected into the TiO2
or ZnO conduction band, leading to the generation of holes in the Ag NPs [46]. The water
molecule gains the electrons in the conduction band and hydrogen is produced.
At 500 nm, the catalysts with a silver loading of 10% by weight (see Figure 7C)
obtained their highest hydrogen production, as seen at other irradiation wavelengths. The
highest hydrogen production of the 10%Ag@TiO2 NWs, 10%Ag@ZnO NWs,
10%Ag@TiO2‐P25, and 10%Ag@ZnO commercial was 1119, 921, 653, and 466 μmol/hg,
respectively, representing an increase in hydrogen production of ca. 18, 2, 36, and 12 times
compared to the bare TiO2 NWs, ZnO NWs, TiO2‐P25, and ZnO commercial catalysts,
respectively (see Table 4). Furthermore, as seen at other wavelengths, the larger the
surface area, the greater the hydrogen production. This is an indication of the synergism
between the deposited Ag NPs and the surface area of the catalysts. As previously
mentioned, at wavelengths above 400 nm (λ > 400 nm), the hydrogen production will
depend mainly on the Ag NPs and their ability to inject photoexcited electrons into the
conduction band of semiconductors.
Biomimetics 2021, 6, 4 14 of 22

Table 4. Silver‐based catalysts with the highest hydrogen production and their difference from the
unmodified supports at a wavelength of 500 nm *.

Maximum H2
Maximum H2 Difference
Production Times Greater
Production Silver‐ in H2
Catalyst Unmodified than Unmodified
Based Catalysts Production
Catalyst Catalyst
(μmol/gh) (μmol/gh)
(μmol/gh)
10%AgTiO2 NWs 1119 TiO2 NWs; 62 1057 18.05
10%AgTiO2‐P25 653 TiO2‐P25; 18 635 36.28
10%AgZnO NWs 921 ZnO NWs; 349 572 2.64
10%AgZnO comm. ** 466 ZnO Comm *; 38 428 12.26
* Only the highest hydrogen production from all the silver‐based catalysts is shown, **
Commercial.

Table 5 shows recent research on photocatalytic hydrogen production using silver‐

based catalysts (Ag@TiO2 and Ag@ZnO). These investigations consider different
parameters such as Ag loading, crystalline structure, morphology of the support and
nanoparticles, reaction mixture, and reaction time, among others, when experiments are
carried out. Considering the previous scientific literature (see Table 5), the catalysts
synthesized in this research gave rise to the highest hydrogen production values achieved
by water splitting. However, it is important to note that the experimental parameters used
in the literature were not exactly the same as those used in this research.

Table 5. Recent works for photocatalytic hydrogen production using Ag@TiO2 and Ag@ZnO catalysts.

TiO2 or ZnO
H2 Production Irradiation Reaction
Reference Source (nm) Crystal Ag (wt.%)
(μmol) Time (h) Mixture
Structure *
[12] 910 λ > 400 2 TiO2; A Water: Methanol 14
Water: 0.1 M
[47] 90 λ = 457 8 TiO2; A 2
Na2S
Water: 0.25 M
[15] 443.6 λ > 400 4 ZnO; W Na2S, 0.35 M 3.12
Na2SO3
Water: 3.0 g
[16] 55 λ > 400 8 ZnO; W Na2S, 2.2 g 0.5
Na2SO3
Water: 0.5 M
This work 1119 λ = 500 2 TiO2 NWs; R Na2S, 0.03 M 10
Na2SO3
Water: 0.5 M
This work 653 λ = 500 2 TiO2‐P25; A, R Na2S, 0.03 M 10
Na2SO3
Water: 0.5 M
This work 963 λ = 400 2 ZnO NWs; W Na2S, 0.03 M 10
Na2SO3
Water: 0.5 M
ZnO comm. **
This work 516 λ = 400 2 Na2S, 0.03 M 10
W
Na2SO3
* A = anatase, R = rutile, W = wurtzite; ** commercial.
Biomimetics 2021, 6, 4 15 of 22

3.3. Photocatalytic Degradation of Ciprofloxacin

The photocatalytic activity of the silver‐based catalysts was also studied by the
degradation of the antibiotic ciprofloxacin (see Figure 8 and Table 6). The incorporation
of Ag NPs increased the percentage of degradation in comparison with the unmodified
catalysts. The superior performance of the silver‐based catalysts is attributed to the
combination of its smaller bandgap and plasmonic effects, which allow visible light
energy harvesting and improved charge carrier lifetimes [12]. For the Ag@TiO2‐P25
system (Figure 8A), the higher degradation was obtained with 5%Ag@TiO2‐P25.
However, it should be noted that with 3%Ag@TiO2‐P25, the degradation obtained was
only ~3% below the maximum, which means that there is no significant difference
between 3%Ag@TiO2‐P25 and 5%Ag@TiO2‐P25. In addition, 10%Ag@TiO2‐P25 degraded
approximately 70% of the ciprofloxacin within the first 10 min of the reaction. After that
time, less than 15% degradation was observed, possibly due to the lack of active sites on
the catalyst’s surface [48]. Moreover, 3%Ag@TiO2‐P25 showed ca. 85% degradation after
40 min of reaction and increased to only 87% at 60 min. According to these results, the
water treatment could be stopped at 40 min. After this reaction time, 10% Ag@TiO2‐P25
did not show a significant increase in degradation, which could indicate that a saturation
point was reached.

Table 6. Degradation percentages of all silver‐based catalysts after 60 min of reaction.

Ag TiO2‐P25
TiO2 NWs (%) ZnO NWs (%) ZnO Commercial (%)
Loading(wt.%) (%)
0 69.12 71.36 68.26 94.83
1 76.11 80.11 73.37 95.60
3 83.09 87.09 78.26 99.72
5 85.92 89.92 71.11 98.39
10 81.26 82.26 70.65 92.31

The Ag@TiO2 NW system (Figure 8B) yielded similar results to those mentioned
above. The highest degradation percentage, 86%, was obtained with 5%Ag@TiO2NWs and
showed a continuous degradation pattern, suggesting that there is no saturation point.
Similar results have been reported by other authors [19]. Although all the Ag@TiO2NWs
catalysts have a higher surface area than Ag@TiO2‐P25, the degradation percentages were
better for Ag@TiO2‐P25 catalysts. Some authors [49] have reported similar results and
have justified them as due mainly to the crystalline structure of the catalysts and not so
much to the surface area, since it is well known that anatase exhibits better photocatalytic
performance than the rutile‐type structure. In this regard, TiO2‐P25 is composed of 70%
anatase and 30% rutile, while TiO2 NWs are 100% rutile (see Figure 3A).
The Ag@ZnO commercial catalysts (bare ZnO commercial, 1%Ag@ZnO commercial,
and 10%Ag@ZnO commercial) showed minor efficiency during the first 10 min of reaction
(see Figure 8C). However, after completing the 60 min of reaction, they showed better
performance compared to TiO2 catalysts. This behavior could be attributed to pH, since
TiO2 works better in an acidic environment due to the zero‐point charge of this material
[50]. With 3%Ag@ZnO commercial, ~90% degradation was achieved only after 20 min of
reaction. No significant difference was observed between 3%Ag@ZnO commercial and
5%Ag@ZnO commercial catalysts. Moreover, these samples degrade +60% of the
ciprofloxacin in the first 10 min of reaction, while the bare ZnO took 30 min to reach this
point, clearly indicating that the best performance is achieved when the material is doped
with Ag.
Ag@ZnO NW (Figure 8D) catalysts showed lower efficiency compared to the
commercial catalyst. All catalysts showed a constant increase over time, suggesting that
the catalyst still has active sites available, even after 60 min of reaction, and no saturation
Biomimetics 2021, 6, 4 16 of 22

point is expected to occur. The highest degradation percentage (ca. 78%) was obtained
with 3%Ag@ZnO NWs.
In the case of ZnO commercial and ZnO NWs, both exhibited the same wurtzite
crystalline phase (see Figure 3C,D) but demonstrated a significant difference in
degradation percentages. These differences are attributed to the agglomeration of
particles; the ZnO commercial consists of a finer powder compared to the as‐synthesized
material. This might cause agglomeration of the as‐synthesized catalyst, enhancing the
catalyst–catalyst contact instead of the catalyst–antibiotic contact, reducing the
degradation efficiency of the system.

Figure 8. Percentage of degradation of ciprofloxacin using Ag@TiO2‐P25 (A), Ag@TiO2 NW (B), Ag@ZnO commercial (C),
and Ag@ZnO NW (D) catalysts.

To further study the photocatalytic activity of the silver‐based catalysts, control

experiments and stability tests were conducted for the two catalysts with the highest
percentage of degradation (5%Ag@TiO2‐P25, 3%Ag@ZnO commercial) (Figure 9). The
control experiments for both catalysts were similar (see Figure 9A,B). After 60 min of
reaction, it was observed that ciprofloxacin is highly recalcitrant and stable under normal
or environmental conditions. This is evidenced by the fact that no degradation or
significant changes in ciprofloxacin concentration are observed over time without the
catalyst or radiation source. From the control experiments, it is shown that photocatalysis
is the primary degradation route; this means that neither catalysis nor photolysis are
enough to degrade the contaminant. Instead, degradation occurs due to a synergistic effect
between the catalyst and the radiation source.
Biomimetics 2021, 6, 4 17 of 22

The stability tests (Figure 9C,D) for both catalysts were also very similar. The results
showed that even after 60 min of reaction, the catalysts were demonstrated to be highly
stable and that no significant chemical change occurred that endangered the efficiency of
the materials. After seven cycles, the degradation efficiency decreased by ~7%, which can
be estimated as 1% per cycle of use. This rough estimate suggests that these catalysts could
be employed for several more cycles without the need for resynthesizing. This means that
these materials could decrease the environmental remediation costs if used in
contaminated settings.

Figure 9. Control experiments and stability tests for the 5%Ag@TiO2‐P25 (A,C) and 3%Ag@ZnO commercial (B,D)
catalysts.

The results obtained have made it possible to establish the possible mechanisms
involved in the two processes studied in this research. Figure 10 shows a possible
mechanism for the production of hydrogen via water splitting using Ag@TiO2 or Ag@ZnO
catalysts under visible and ultraviolet light. When irradiated with ultraviolet light (Figure
10A), direct photoexcitation of TiO2 or ZnO with photons with energy larger than the
bandgap (λ < 380 nm) is assumed, leading to the generation of electrons in the
semiconductor conduction band and electron holes in the valence band [46]. The electron
in the conduction band will move to the silver nanoparticles, acting as electron buffers
and catalytic sites for hydrogen generation [11,12]. The electron holes will be quenched
by the sacrificial electron donors (SO32−/SO42−). When irradiated with visible light (λ > 400
nm) (Figure 10B), photoexcitation of Ag NPs occurs and electrons from the Ag are injected
into the TiO2 or ZnO conduction band, leading to the generation of holes in the Ag NPs
and electrons in the TiO2 or ZnO conduction band [11,12,46]. The water molecule gains
the electrons in the conduction band and hydrogen is produced. Holes in the Ag NPs will
Biomimetics 2021, 6, 4 18 of 22

be quenched by the sacrificial electron donors (SO32−/SO42−). This proposed mechanism is

an oversimplification since different studies [11–13] have determined that, due to the
silver/titania or silver/zinc oxide interfacial contact, the conduction band of the
semiconductor undergoes a shift toward more negative potentials. Thus, the charge
distribution between the Ag NPs and the semiconductor causes a shift in the Fermi level
toward more negative potentials [13].

Figure 10. Mechanism for the production of hydrogen via water splitting using Ag@TiO2 or Ag@ZnO catalysts under
ultraviolet (A) and visible light (B).

The mechanism for the degradation of ciprofloxacin using the silver‐based catalysts
is shown in Figure 11. Under ultraviolet light (Figure 11A), electrons from the valence
band of TiO2 or ZnO migrate to the conduction band of the semiconductors and holes in
the valence band are formed. The electrons in the conduction band move to the Ag NPs,
acting as an electron buffer, and these electrons may react with adsorbed molecular
oxygen to generate superoxide anions, which in turn can react with water molecules to
form hydroxyl radicals. These free radicals are very efficient in the photodegradation of
organic pollutants such as ciprofloxacin [12]. The holes formed in the valence band of the
semiconductors then will promote the oxidation of ciprofloxacin and therefore lead to
degradation. When irradiated with visible light (Figure 11B), Ag NPs form an interface
with semiconducting materials and a Schottky barrier is formed, resulting in a new Fermi
level and a high number of electrons due to the presence of metallic Ag [12]. Additionally,
free electrons are stimulated through the silver surface plasmon resonance mechanism
and can move into the conduction band of the partially reduced TiO2 or ZnO [12]. These
conduction band electrons may react with adsorbed molecular oxygen to generate
superoxide anions, then react with water molecules and form hydroxyl radicals that will
eventually oxidize the ciprofloxacin. In future research, already under development, the
different intermediate compounds generated during the ciprofloxacin degradation
Biomimetics 2021, 6, 4 19 of 22

process will be analyzed, which will allow us to establish the catalytic photodegradation
mechanisms that, eventually, will allow the process to be improved.

Figure 11. Mechanism for the degradation of ciprofloxacin using the silver‐based catalysts under ultraviolet (A) and visible
light (B).

4. Conclusions
Silver‐based catalysts were synthesized to study their ability to mimic natural
processes such as the splitting of water and the degradation of pollutants. The
photocatalytic activity of the composites was studied by the production of hydrogen via
water splitting using UV–vis light and the degradation of the antibiotic ciprofloxacin.
The catalyst with the highest hydrogen production was 10%Ag@TiO2 NW (1119
μmol/hg), being 18 times greater than the amount obtained with the pristine TiO2 NW
catalyst. The most dramatic difference in hydrogen production was obtained with
10%Ag@TiO2‐P25 (635 μmol/hg), being 36 times greater than the amount reported for the
unmodified TiO2‐P25 (18 μmol/hg). The enhancement of the catalytic activity is attributed
to a synergism between the silver nanoparticles incorporated and the high surface area of
the composites.
In the case of the degradation of ciprofloxacin, all the silver‐based catalysts degraded
more than 70% of the antibiotic in 60 min. The catalyst that exhibited the best result was
3%Ag@ZnO commercial with 99.72% of degradation. The control experiments and
stability tests showed that photocatalysis was the route of degradation and the selected
silver‐based catalysts were stable after seven cycles, with less than 1% loss of efficiency
per cycle. These results suggest that the catalysts could be employed in several more cycles
without the need for resynthesizing, thus reducing remediation costs.
The results obtained in this research introduce an immense field of possibilities for
the development of high‐performance photocatalysts. The systems studied have proven
to be very active in the production of hydrogen and in the degradation of ciprofloxacin,
so perhaps it is towards the development of multi‐application systems that we will have
to redouble our efforts in the future.

Author Contributions: Conceptualization, A.M., F.M., L.S.‐V.; methodology, A.M.; formal

analysis, A.M., F.M., L.S.‐V.; investigation, A.M., C.C.‐C., C.A.V.‐C., G.J.C.‐S., K.F., L.S.‐V., E.R.,
C.M.; resources, F.M., C.M., F.I.P.; writing—original draft preparation, A.M.; writing—review and
editing, A.M., F.M., L.S.‐V.; supervision, A.M., F.M.; project administration, A.M., F.M.; funding
Biomimetics 2021, 6, 4 20 of 22

acquisition, F.M., C.M., F.I.P. All authors have read and agreed to the published version of the
manuscript.
Funding: Financial support provided by the US DoE, through the Massie Chair project at
University of Turabo, US Department of Defense, under contract W911NF‐14‐1‐0046, from the
Ministerio de Economía y Competitividad (MINECO) of Spain, through the grant ENE2014‐57977‐
C2‐1‐R, and from NSF Center for the Advancement of Wearable Technologies‐CAWT (Grant
1849243) are gratefully acknowledged.
Institutional Review Board Statement: In this section, you should add the Institutional Review
Board Statement and approval number, if relevant to your study. You might choose to exclude this
statement if the study did not require ethical approval. Please note that the Editorial Office might
ask you for further information. Please add “The study was conducted according to the guidelines
of the Declaration of Helsinki, and approved by the Institutional Review Board (or Ethics
Committee) of NAME OF INSTITUTE (protocol code XXX and date of approval).” OR “Ethical
review and approval were waived for this study, due to REASON (please provide a detailed
justification).” OR “Not applicable” for studies not involving humans or animals.
Informed Consent Statement: Please add “Informed consent was obtained from all subjects
involved in the study.” OR “Patient consent was waived due to REASON (please provide a detailed
justification).” OR “Not applicable” for studies not involving humans.
Data Availability Statement: please refer to suggested Data Availability Statements in section
“MDPI Research Data Policies” at https://www.mdpi.com/ethics.
Acknowledgments: Technical assistance of I. Poveda from “Servicio Interdepartamental de
Investigacion, SIdI” at UAM, is gratefully acknowledged. The facilities provided by the National
Center for Electron Microscopy at Complutense University of Madrid (Spain) and the Materials
Characterization Center at University of Puerto Rico are gratefully acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Zafar, M.W.; Shahbaz, M.; Hou, F.; Sinha, A. From Nonrenewable to Renewable Energy and Its Impact on Economic Growth:
The role of Research and Development Expenditures in Asia‐Pacific Economic Cooperation Countries. J. Clean. Prod. 2018, 212,
1166–1178., doi:10.1016/j.jclepro.2018.12.081.
2. Skovgaard, J.; van Asselt, H. The politics of fossil fuel subsidies and their reform: Implications for climate change mitigation.
Wiley Interdiscip. Rev. Clim. Chang. 2019, 10, 1–12, doi:10.1002/wcc.581.
3. Zhang, H.; Carey, A.M.; Jeon, K.W.; Liu, M.; Murrell, T.D.; Locsin, J.; Lin, S.; Yan, H.; Woodbury, N.; Seo, D.K. Highly Stable
and Scalable Photosynthetic Reaction Center‐Graphene Hybrids Electrode System for Biomimetic Solar Energy Transduction.
J. Mater. Chem. A 2017, 5, 6038–6041, doi:10.1039/C6TA10458D.
4. Martín‐Palma, R.J.; Lakhtakia, A. Progress on bioinspired, biomimetic, and bioreplication routes to harvest solar energy. App.
Phys. Rev. 2017, 4, 1–7, doi:10.1063/1.4981792.
5. Ye, S.; Ding, C.; Chen, R.; Fan, F.; Fu, P.; Yin, H.; Wang, X.; Wang, Z.; Du, P.; Li, C. Mimicking the Key functions of Photosystem
II in Artificial Photosynthesis for Photoelectrocatalytic Water Splitting. J. Am. Chem. Soc. 2018, 140, 3250–3256,
doi:10.1021/jacs.7b10662.
6. Ye, S.; Ding, C.; Liu, M.; Wang, A.; Huang, Q.; Li, C. Water Oxidation for Artificial Photosynthesis. Adv. Mater. 2019, 31, 1–33,
doi:10.1002/adma.201902069.
7. Li, Q.; Xia, Y.; Yang, C.; Lv, K.; Lei, M.; Li, M. Building a direct Z‐scheme heterojunction photocatalyst by Znln2S4 nanosheets
and TiO2 hollowspheres for highly‐efficient artificial photosynthesis. Chem. Eng. J. 2018, 349, 287–296,
doi:10.1016/j.cej.2018.05.094.
8. Ji, Y.; Luo, Y. Direct Dontation of Proton from H2O to CO2 in Artificial Photosynhtesis on the Anatase TiO2(101) Surface. J. Phys.
Chem. 2019, 123, 3019–3023, doi:10.1021/acs.jpcc.8b11936.
9. Wang, X.; Li, Q.; Zhou, C.; Cao, Z.; Zhang, R. ZnO Rod/Reduced Graphene Oxide Sensitized by α‐Fe2O3 nanoparticles for
effective visible‐light photoreduction of CO2. J. Colloid Interface Sci. 2019, 554, 335–343, doi:10.1016/j.jcis.2019.07.014.
10. Liang, S.; Han, B.; Liu, X.; Chen, W.; Peng, M.; Guan, G.; Deng, H.; Lin, Z. 3D spatially branched hierarchical Z‐scheme CdS‐Au
nanoclusters‐ZnO hybrids with boosted photocatalytic hydrogen evolution. J. Alloys Compd. 2018, 754, 105–113,
doi:10.1016/j.jallcom.2018.04.202.
11. Geng, R.; Yin, J.; Zhou, J.; Jiao, T.; Feng, Y.; Zhang, L.; Chen, Y.; Bai, Z.; Peng, Q. In Situ Construction of Ag/TiO2/g‐C3N4
Heterojunction Nanocomposite Based on Hierarchical Co‐Assembly with Sustainable Hydrogen Evolution. Nanomaterials 2020,
10, 1, doi:10.3390/nano10010001.
Biomimetics 2021, 6, 4 21 of 22

12. Saravanan, R.; Manoj, D.; Qin, J.; Naushad, M.; Gracia, F.; Lee, A.F.; Khan, M.M.; Gracia‐Pinilla, M. Mechanothermal synthesis
of Ag/TiO2 for photocatalytic Methyl Orange degradation and hydrogen production. Process Saf. Environ. Prot. 2018, 120, 339–
347, doi:10.1016/j.psep.2018.09.015.
13. Zhang, Y.; Fu, Y.; Zhang, D.; Chen, Y. One‐Step Synthesis of Ag@TiO2 Nanoparticles for Enhanced Photocatalytic Performance.
Nanomaterials 2018, 8, 32, doi:10.3390/nano8121032.
14. Mao, H.; Fei, Z.; Bian, C.; Yu, L.; Chen, S.; Qian, Y. Facile synthesis of high‐performance photocatalysts based on Ag/TiO2
composites. Ceram. Int. 2019, 45, 12586–12589, doi:10.1016/j.ceramint.2019.03.109.
15. Mou, H.; Song, C.; Zhou, Y.; Zhang, B.; Wang, D. Design and synthesis of porous Ag/ZnO nanosheets assemblies as super
photocatalysts for enhanced visible‐light degradation of 4‐nitrophenol and hydrogen evolution. Appl. Catal. B 2018, 221, 565–
573, doi:10.1016/j.apcatb.2017.09.061.
16. Xin, Z.; Li, L.; Zhang, X.; Zhang, W. Microwave‐assisted hydrothermal synthesis of chrysanthemum‐like Ag/ZnO prismatic
nanorods and their photocatalytic properties with multiple modes for dye degradation and hydrogen production. RSC Adv.
2018, 8, 6027–6038, doi:10.1039/C7RA12097D.
17. Liu, H.; Liu, H.; Yang, J.; Zhai, H.; Liu, X.; Jia, H. Microwave‐assisted one‐pot synthesis of Ag decorated flower‐like ZnO
composites photocatalysts for dye degradation and NO removal. Ceram. Int. 2019, 45, 20133–20140,
doi:10.1016/j.ceramint.2019.06.279.
18. Trang, T.N.Q.; Phan, T.B.; Nam, N.D.; Thu, V.T.H. In situ charge transfer at the Ag@ZnO photoelectrochemical interface toward
the high photocatalytic performance of H2 evolution and RhB degradation. ACS Appl. Mater. Interfaces 2020, 12, 12195–122206,
doi:10.1021/acsami.9b15578.
19. Malakootian, M.; Nasiri, A.; Amiri Gharaghani, M. Photocatalytic degradation of ciprofloxacin antibiotic by TiO2 nanoparticles
immobilized on a glass plate. Chem. Eng. Commun. 2019, 207, 1–17, doi:10.1080/00986445.2019.1573168.
20. Cotto, M.; Campo, T.; Elizalde, E.; Gómez, A.; Morant, C.; Márquez, F. Photocatalytic degradation of rhodamine‐B under UV‐
visible light irradiation using different nanostructured catalyst. Am. Chem. Sci. J. 2013, 3, 178–202, doi:10.9734/ACSJ/2013/2712.
21. Lin, C.C.; Li, Y.Y. Synthesis of ZnO nanowires by thermal decomposition of zinc acetate dihydrate. Mater. Chem. Phys. 2009, 113,
334–337, doi:10.1016/j.matchemphys.2008.07.070.
22. Naldoni, A.; D’Arienzo, M.; Altomare, M.; Marelli, M.; Scotti, R.; Morazzoni, F.; Selli, E.; Dal Santo, V. Pt and Au/TiO2
photocatalysts for methanol reforming: Role of metal nanoparticles in tuning charge trapping properties and photoefficiency.
Appl. Catal. B 2013, 130, 239–48, doi:10.1016/j.apcatb.2012.11.006.
23. Jafari, T.; Moharreri, E.; Amin, A.S.; Miao, R.; Song, W.; Suib, S.L. Photocatalytic Water Splitting‐The Untamed Dream: A Review
of Recent Advances. Molecules 2016, 21, 900, doi:10.3390/molecules21070900.
24. Clarizia, L.; Spasiano, D.; Di Somma, I.; Marotta, R.; Andreozzi, R.; Dionysiou, D.D. Copper modified‐TiO2 catalysts for
hydrogen generation through photoreforming of organics. A short review. Int. J. Hydrogen Energy 2014, 39, 16812,
doi:10.1016/j.ijhydene.2014.08.037.
25. Machín, A.; Cotto, M.; Duconge, J.; Arango, J.C.; Morant, C.; Pinilla, S.; Soto‐Vázquez, L.; Resto, E.; Márquez, F. Hydrogen
production via water splitting using different Au@ZnO catalysts under UV–vis irradiation. J. Photochem. Photobiol. A Chem. 2018,
353, 385–394, doi:10.1016/j.jphotochem.2017.11.050.
26. Pinilla, S.; Machín, A.; Park, S.H.; Arango, J.C.; Nicolosi, V.; Márquez, F.; Morant, C. TiO2‐Based Nanomaterials for the
Production of Hydrogen and the Development of Lithium‐Ion Batteries. J. Phys. Chem. B 2017, 122, 972–983,
doi:10.1021/acs.jpcb.7b07130.
27. Machín, A.; Arango, J.C.; Fontánez, K.; Cotto, M.; Duconge, J.; Soto‐Vázquez, L.; Resto, E.; Petrescu, F.I.T.; Morant, C.; Márquez,
F. Biomimetic Catalysts Based on Au@ZnO–Graphene Composites for the Generation of Hydrogen by Water Splitting.
Biomimetics 2020, 5, 39, doi:10.3390/biomimetics5030039.
28. Uddin, M.J.; Cesano, F.; Chowdhury, A.R.; Trad, T.; Cravanzola, S.; Martra, G.; Lorenzo, M.; Zecchina, A.; Scarano, D. Surface
Structure and Phase Composition of TiO2 P25 Particles After Thermal Treatments and HF Etching. Front. Mater. 2020, 7, 1–12,
doi:10.3389/fmats.2020.00192.
29. Kowalska, E.; Rau, S.; Ohtani, B. Plasmonic Titania Photocatalysts Active under UV and Visible‐Light Irradiation: Influence of
Gold Amount, Size, and Shape. J. Nanotechnol. 2012, 2012, 1–11, doi:10.1155/2012/361853.
30. Das, J.; Velusamy, P. Biogenic Synthesis of Antifungal Silver Nanoparticles Using Aqueous Stem Extract Banana. Nano. Biomed.
Eng. 2013, 5, 34–38, doi:10.5101/nbe.v5i1.p34‐38.
31. Varadaveenkatesan, T.; Lyubchik, E.; Pai, S.; Pugazhendhi, A.; Vinayagam, R.; Selvaraj, R. Photocatalytic degradation of
Rhodamine B by zinc oxide nanoparticles synthesized using the leaf extract of Cyanometra ramiflora. J. Photochem. Photobiol. B
2019, 199, 1–8, doi:10.1016/j.jphotobiol.2019.111621.
32. Han, E.; Vijayarangamuthu, K.; Youn, J.; Park, Y.K.; Jung, S.C.; Jeon, K.J. Degussa P25 TiO2 modified with H2O2 under
microwave treatment to enhance photocatalytic properties. Catal. Today 2018, 303, 305–312, doi:10.1016/j.cattod.2017.08.057.
33. Wang, Y.; Zhang, M.; Fang, L.; Yange, H.; Zuo, Y.; Gao, J.; He, G.; Sun, Z. A Multifunctional Ag/TiO2/Reduced Graphene Oxide
with Optimal Surface‐Enhanced Raman Scattering and Photocatalysis. J. Am. Ceram. Soc. 2019, 102, 4000–4013,
doi:10.1111/jace.16273.
34. Hanaor, D.A.H.; Sorrell, C.C. Review of the anatase to rutile phase transformation. J. Mater. Sci. 2010, 46, 855–874,
doi:10.1007/s10853‐010‐5113‐0.
Biomimetics 2021, 6, 4 22 of 22

35. Korepanov, V.I.; Chan, S.Y.; Hsu, H.C.; Hamaguchi, H. Phonon confinement and size effect in Raman spectra of ZnO
nanoparticles. Heliyon 2019, 5, 1–14, doi:10.1016/j.heliyon.2019.e01222.
36. Liu, J.; Liu, Z.; Piao, C.; Li, S.; Tang, J.; Fang, D.; Zhang, Z.; Wang, J. Construction of fixed Z‐scheme Ag|AgBr/Ag/TiO2
photocatalyst composite film for malachite green degradation with simultaneous hydrogen production. J. Power Sources 2020,
469, 228430, doi:10.1016/j.jpowsour.2020.228430.
37. Lu, L.; Wang, G.; Xiong, Z.; Hu, Z.; Liao, Y.; Wang, J.; Li, J. Enhanced photocatalytic activity under visible light by the synergistic
effects of plasmonics and Ti3+‐doping at the Ag/TiO2‐x heterojunction. Ceram. Int. 2020, 46, 10667–10677,
doi:10.1016/j.ceramint.2020.01.073.
38. Zhu, X.; Liang, X.; Wang, P.; Dai, Y.; Huang, B. Porous Ag‐ZnO microspheres as efficient photocatalyst for methane and ethylene
oxidation: Insight into the role of Ag particles. Appl. Surf. Sci. 2018, 456, 493–500, doi:10.1016/j.apsusc.2018.06.127.
39. Tanaka, A.; Sakaguchi, S.; Hashimoto, K.; Kominami, H. Preparation of Au/TiO2 exhibiting strong surface plasmon resonance
effective for photoinduced hydrogen formation from organic and inorganic compounds under irradiation of visible light. Catal.
Sci. Technol. 2012, 2, 907–909, doi:10.1039/C2CY20108A.
40. Li, R.; Weng, Y.; Zhou, X.; Wang, X.; Mi, Y.; Chong, R.; Han, H.; Li, C. Achieving overall water splitting using titanium dioxide‐
based photocatalysts of different phases. Energy Environ. Sci. 2015, 8, 2377–2382, doi:10.1039/C5EE01398D.
41. Xu, Y.; Mao, N.; Zhang, C.; Wang, X.; Zeng, J.; Chen, Y.; Wang, F.; Jiang, J.X. Rational design of donor‐π‐acceptor conjugated
microporous polymers for photocatalytic hydrogen production. Appl. Catal. B 2018, 228, 1–9, doi:10.1016/j.apcatb.2018.01.073.
42. Sachs, M.; Sprick, R.S.; Pearce, D.; Hillman, S.A.J.; Monti, A.; Guilbert, A.A.Y.; Brownbill, N.J.; Dimitrov, S.; Shi, X.; Blanv, F.; et
al. Understanding structure‐activity relationships in linear polymer photocatalysts for hydrogen evolution. Nat. Commun. 2018,
9, 4968, doi:10.1038/s41467‐018‐07420‐6.
43. Zhang, Y.; Ram, M.K.; Stefanakos, E.K.; Goswami, D.Y. Synthesis, Characterization, and Applications of ZnO Nanowires. J.
Nanomater. 2012, 2012, 1–22, doi:10.1155/2012/624520.
44. Baruah, S.; Mahmood, M.A.; Myint, M.T.Z.; Bora, T.; Dutta, J. Enhanced visible light photocatalysis through fast crystallization
of zinc oxide nanorods. Beilstein J. Nanotechnol. 2010, 1, 14–20, doi:10.3762/bjnano.1.3.
45. Baruah, S.; Dutta, J. Effect of seeded substrates on hydrothermally grown ZnO nanorods. J. Sol Gel Sci. Technol. 2009, 50, 456–
464, doi:10.1007/s10971‐009‐1917‐2.
46. Dosado, A.G.; Chen, W.T.; Chan, A.; Sun‐Waterhouse, D.; Waterhouse, G.I.N. Novel Au/TiO2 photocatalysts for hydrogen
production in alcohol‐water mixtures based on hydrogen titanate nanotube precursors. J. Catal. 2015, 330, 238–254,
doi:10.1016/j.jcat.2015.07.014.
47. Rather, R.A.; Singh, S.; Pal, B. Visible and direct sunlight induced H2 production from water by plasmonic Ag‐TiO2 nanorods
hybrid interface. Sol. Energy Mater. Sol. Cells 2017, 160, 463–469, doi:10.1016/j.solmat.2016.11.017.
48. Imam, S.S.; Adnan, R.; Kaus, N.H.M. Photocatalytic degradation of ciprofloxacin in aqueous media: A short review. Toxicol.
Environ. Chem. 2018, 100, 1–30, doi:10.1080/02772248.2018.1545128.
49. Soto‐Vázquez, L.; Cotto, M.; Ducongé, J.; Morant, C.; Márquez, F. Synthesis and photocatalytic activity of TiO2 nanowires in the
degradation of p‐aminobenzoic acid: A comparative study with a commercial catalyst. J. Environ. Manag. 2016, 167, 23–28,
doi:10.1016/j.jenvman.2015.11.006.
50. Hu, X.; Hu, X.; Peng, Q.; Zhou, L.; Tan, X.; Jiang, L.; Tang, C.; Wang, H.; Liu, S.; Wang, Y.; et al. Mechanisms underlying the
photocatalytic degradation pathway of ciprofloxacin with heterogeneous TiO2. Chem. Eng. J. 2020, 380, 1–11,
doi:10.1016/j.cej.2019.122366.