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Resumen de materiales

utilizados en el Departamento
de Ecomateriales y Energía para
la fotoconversión de CO2
15.enero.2021
Antecedentes y logros
científicos del grupo EyE

Pirocloros
(Bi2MNbO7, M=Al, Ga, In, Y y
Sm2MTaO7 (M = In, Fe, Ga, Y)).
Tuneles Esquelitas
rectangulares (ABO4, A=Bi, Ca, Mo, B=Mo,
(M2Ti6O12, M=Li, Na, K y W).
Ba3Li2Ti8O20)

Perovskitas
dobles Óxidos
(A2B2O7, A=Sr, Ca, Ba, simples
B=Ta, Nb)

Materiales
Perovskitas estudiados
simples No-óxidos
(MTiO3, M=Ca, Sr, Ba, Ni, Fe)
en EyE-
UANL
Reportes en la reducción de CO2

Productos obtenidos
Material Propiedades Condiciones de reacción
(eficiencias)
 T= 20°C
• Polvos CH3OH: 9 μmol/(g-h)  P = 2 psi
Mg6Al2(OH)16(CO3)·4H2O • aBET: 462 m2/g CH4: 1 μmol/(g-h)  V= 200 mL
• Flake-like morphology CO: 4 μmol/(g-h)  m = 0.1 g
 Lámpara de halógeno
 T= 25°C
• Películas sobre Al2O3 CH3OH: 268 μmol/(g-h)  P = 2 psi
Mg(OH)2 • aBET: 50 m2/g  V= 100 mL
H2: 15 μmol/(g-h) m = 0.1 g
• Spherical porous structures 
 Lámpara de halógeno
 T= 25°C
• Polvos  P = 2 psi
Ba3Li2Ti8O20-CuO • aBET: 24 m2/g HCOH: 11.6 μmol/(g-h  V= 100 mL
• n-p heterostructure  m = 0.1 g
 Lámpara de halógeno
Productos obtenidos
Material Propiedades (eficiencias) Condiciones de reacción

 T= 20°C
 P = 2 psi
• Powders CO: 1.6 μmol/(g-h) V= 1.8 L
Ba2Li2/3Ti16/3O13 
• aBET: 462 m2/g H2: 21.3 μmol/(g-h)  m=1g
• Rod-like morphology  0.5 M of NaHCO3
 Lámpara de mercurio

• Thin films / glass HCOH: 2980 μmol/(g-h)  T= 25°C


TiO2 • Oxygen vacancies CH3OH: 323 μmol/(g-h)  P = 2 psi
• Improved light absorption  Lámpara UV 254 nm

HCOH: 250 μmol/(g-h)  T= 25°C


• Polvos CH3OH: 120 μmol/(g-h)  P = 2 psi
K2Ti6O13 • aBET: 50 m2/g  V= 100 mL
CH4: < 1 μmol/g
• Whiskers  m = 0.1 g
H2: 3281 μmol/g Lámpara UV 254 nm

Productos obtenidos
Material Propiedades Condiciones de reacción
(eficiencias)
 T= 20°C
• Powders P = 2 psi
CH3OH: 29 μmol/(g-h) 
ZnO-doped Cu, Ni • aBET: < 8 m2/g V= 200 mL
H2: 224 μmol/(g-h) 
• Hexagonal truncated-  m = 0.1 g
pyramid morphology Lámpara UV 254 nm

 T= 20°C
• Powders CH3OH: 3.7 μmol/(g-h)  P = 2 psi
CuO • aBET: 351 m2/g CO2: 318 mg/g  V= 250 mL
• Bars-morphology  m = 0.1 g
 Lámpara visible LED
CH3OH: 9050 μmol/(g-h) ó  T= 25°C
18 μmol/(cm2-h)  P = 2 psi
AMoO4 (A=Ca, Sr, Ba) • Thin films / glass V= 250 mL
• Semi-spherical particles H2: 6040 μmol/(g-h) 
 m = 0.1 g
CO2: 14.8 mg / 0.01 g Lámpara UV 254 nm

 T= 25°C
CH3OH: 95 μmol/(g-h)  P = 2 psi
A2Ti6O13 (A=Na and K) • Powders  V= 200 mL
• Rod-like particles HCOH: 93 μmol/(g-h) m = 0.1 g

 Lámpara UV 254 nm
Material Propiedades Productos obtenidos Condiciones de reacción
(eficiencias)
 T= 20°C
• Powders CH3OH: 6 μmol/(g-h)  P = 2 psi
Mg(OH)2/CuO/Cu2O • aBET: 142 m2/g HCOH: 9 μmol/(g-h)  V= 200 mL
• Flake-like particles CO2: 149 mg/g  m = 0.1 g
 Lámpara halógeno

CH3OH: 187 μmol/(g-h)  T= 20°C


• Coatings on glass fibers P = 2 psi
CuO 
• 1D-morphology HCOH: 382 μmol/(g-h)
 V= 250 mL
• Oxygen vacancies CO2: 14 mg/cm2  Lámpara visible LED

• Thin films / glass CH3OH: 1536 μmol/(g-h)  V= 250 mL


CuO • Optimal concentration of HCOH: 6816 μmol/(g-h)  Área = 15 cm2
dislocations H2: 24  Simulador solar

• Powders  T= 20°C
HCOH: 25 μmol/(g-h)  P = 2 psi
Na2Ti6O13/CuO/Cu2O • Z-scheme CH3OH: 4.6 μmol/(g-h)
Belt-morphology  V= 250 mL
• H2: 33 μmol/(g-h) m = 0.1 g
Cu2O enhances the kinetics 
•  Lámpara UV 254 nm

• Polvos  T= 20°C
CH3OH: 38 μmol/(g-h)  P = 2 psi
• aBET: 125 m2/g
Cu2O/Mg(OH)2/SiO2 HCOH: 419 μmol/(g-h)  V= 250 mL
• Microporosity CO2: 180 mg/g  m=0.1 g
• Octehedral-morphology  Lámpara visible LED
Túnel Reportes producción de H2
Material Propiedades Producción Condiciones de reacción
Na2Ti6O13 – 213 µmol h-1 g -1
Na2Ti6O13-CuO -389 µmol h-1 g -1
 200 ml Batch reactor
• Powders: nanobelts modified Na2Ti6O13-NiO – 919 µmol h-1 g -1
 0.1 g catalyst
Na2ZrxTi6-xO13 (x = 0, 1) with metal oxide Na2ZrTi5O13 -1896 µmol h-1 g -1
Na2ZrTi5O13-CuO – 2482 µmol h-1 g -1  Medium:pure water
nanoparticles as cocatalysts
Na2ZrTi5O13-NiO – 2909 µmol h-1 g -1  Pen-lamp of 254 nm

 200 ml Batch reactor


K2ZrxTi6-xO13 (x = 0, 1) • Powders K2ZrTi5O13-72 µmol h g -1 -1
0.1 g catalyst

• Oxygen vacancies due to  Medium: 20% methanol
incorporation of Zr
 Pen-lamp of 254 nm
Ba3Li2Ti8O20 – 30 µmol h-1 g -1
Ba3Li2Ti8O20-CuO-41 µmol h-1 g -1  200 ml Batch reactor
Ba3Li2Ti8O20 • Powders prepared by sol-gel 0.1 g catalyst
and solid state
Ba3Li2Ti8O20 –NiO-54 µmol h-1 g -1 
Na2Ti6O13 Na2Ti6O13 -120 µmol h-1 g -1  Medium:pure water
• Co-catalyst CuO /NiO Na2Ti6O13 –CuO-416 µmol h-1 g -1 Pen-lamp of 254 nm

Na2Ti6O13 –NiO-296 µmol h-1 g -1
 200 ml Batch reactor
K2Ti6O13 • Powders 10 065 µmol h-1 g -1  0.1 g catalyst
• Whiskers morphology  Medium:50% methanol
 Pen-lamp of 254 nm
Laminares
Material Propiedades Producción Condiciones de reacción

 200 ml Batch reactor


MAl2O4 (M = Mg, Sr and Ba) • Powders 7.3 µmol h-1g-1  0.2 g catalyst
• Cube-shape morphology  Medium:pure water
 Pen-lamp of 254 nm
 200 ml Batch reactor
AMoO4 (A = Ca, Sr, Ba) • Powders BaMoO4 -240 µmol h-1 g -1  0.1 g catalyst
• Solid state  Medium:pure water
 Pen-lamp of 254 nm
• Powders  200 ml Batch reactor
[Zn (4,4′-bipy) (OAc)2]}n2 • mechanochemistry and slow 103 μmol g-1 h-1  0.1 g catalyst
evaporation  Medium:pure water
• crystallinity  Pen-lamp of 254 nm
• synthesized by a template-  200 ml Batch reactor
assisted hydrothermal
In2.77S4  0.2 g catalyst
method using leaves of 73 µmol g-1
Mimosa pudica as a  Medium:pure water
 Pen-lamp of 254 nm
template
Pirocloros
Material Propiedades Producción Condiciones de reacción

 400 W high pressure


mercury lamp as the
Sm2GaTaO7 irradiation source. 0.3 g of
• Powders solid state method 137 µmol h-1g-1
photocatalyst was
dispersed into 300 mL of
pure wate
 200 ml Batch reactor
Sm2MTaO7 (M = Y, In, Fe, • Powders  0.1 g catalyst
62 µmol h-1g-1
Ga) • Negative band potential  Medium:pure water
 Pen-lamp of 254 nm
Perovskitas
Material Propiedades Producción Condiciones de reacción

 300 ml Batch reactor


RuO2-La:NaTaO3 • Powders 4108 µmol h-1  1 g catalyst
• RuO2 act like electron trap  Medium:pure water
 Lamp Hg (Uv source)

• Powders synthesized by
solid state, molten salts  200 ml Batch reactor
SrZrO3 and ultrasound assisted 49 µmol h-1 g -1  0.2 g catalyst
method  Medium:pure water
• Effect of crystallinity on  Pen-lamp of 254 nm
the photocatalytic activity
• Powders  200 ml Batch reactor
SrZrO3/ MO (M: Co, Ni, Cu, • Best catalytic activity was  0.2 g catalyst
exhibited by SrZrO3 1156 µmol h-1 g -1
Fe)  Medium:pure water
modified with CuO.  Pen-lamp of 254 nm
 200 ml Batch reactor
• Powders 0.1 g catalyst
BaBIO3 
• Synthesis by solid state 61 µmol h-1 g -1
 Medium:pure water
and hidrotermal
 simulated sun ligth
Material Propiedades Producción Condiciones de reacción

• Powders  200 ml Batch reactor


NaTaO3 • Synthesis by 50 mmol en 5 h  0.1 g catalyst
solvocombustion  Medium:pure water
• 120 m2 g-1  Pen-lamp of 254 nm
 200 ml Batch reactor
BaZrO3–FeS2 • Powders 4490 µmol g−1 h−1  0.1 g catalyst
• Heterostructure type II  Medium:pure water
 Simulated solar ligth
• Powders  200 ml Batch reactor
SrZrO3-Sb2O3 • Band engineering and 330 μmol g-1 h-1  0.1 g catalyst
charge transference  Medium:pure water
mechanism  Pen-lamp of 254 nm
• Powders 200 ml Batch reactor
LaMnO3-103 µmol h-1 g -1 
LaMO3 (M: Co, Mn, Fe) • surface area and high  0.1 g catalyst
concentration of Mn active LaCoO3 -44 µmol h-1 g -1
perovskite  Medium:pure water
ions improve photocatalytic LaFeO3 -17 µmol h-1 g -1 simulated sun ligth
performance. 
Material Propiedades Producción Condiciones de reacción

g-C3N4/ LaMnO3 -40 µmol h-1 g -1  200 ml Batch reactor


g-C3N4/ LaMO3 (M: Co, Mn, • Powders g-C3N4/ LaCoO3-30 µmol h-1 g -1  0.1 g catalyst
Fe) • heteroestructures type II g-C3N4/ LaFeO3-140 µmol h-1 g -1  Medium:pure water
 simulated sun ligth
• Powders prepared by  200 ml Batch reactor
solvocombustion and solid  0.1 g catalyst
ATiO3 (A = Zn, Cd and Pb) 94 µmol en 3 h
state method  Medium:pure water
• TiO2 residual as co-catalyst  Pen-lamp of 254 nm
• Powders  200 ml Batch reactor
• in-situ photodeposition of 0.1 g
AgTaO3 Ag and Cu nanoparticles 1133 µmol m-2 h-1 
 Medium:pure water
• surface plasmon resonance  Pen-lamp of 254 nm
effect of nanoparticles
 200 ml Batch reactor
AgMO3 (M = Ta, Nb, V) • Powders Cd/AgTaO3 4645 µmol g-1  0.1 g
• CdS and NiO as co-catalysts  Medium:pure water
 Pen-lamp of 254 nm
 200 ml Batch reactor
BaBiO3/NaTaO3 • Powders 54 µmol h-1  0.2 g catalyst
• Higher crystallite size  Medium:pure water
 Pen-lamp of 254 nm
Espinelas

Material Propiedades Producción Condiciones de reacción

CuFe2O4 -336 µmol h-1 g -1  200 ml Batch reactor


• Powders prepared by solid  0.1 g catalyst
MFe2O4 (M = Cu, Ni) state, polymer precursor NiFe2O4-234 µmol h-1 g -1  Medium:pure water
and hydrotermal
 Pen-lamp of 254 nm

CuFe2O4 -ZnO -441 µmol h-1 g -1  200 ml Batch reactor


MFe2O4–ZnO (M = Cu , Ni) • Powders, heteroestructures  0.1 g catalyst
type II NiFe2O4- -ZnO-380 µmol h-1 g -1  Medium:pure water
 Pen-lamp of 254 nm
Sulfuros

Material Propiedades Producción Condiciones de reacción

 200 ml Batch reactor


• Powders FeS2 32 µmol h-1 g -1  0.1 g catalyst
FeS2, CuS, NiS2 • hydrothermal method  Medium: sacrificla
• higher crystallite size agents
 simulated sun ligth
Películas
Material Propiedades Producción Condiciones de reacción

 200 ml Batch reactor


• Films Films catalyst 30cm2
ZnO–SnO2 
• Sputtering 1.4 µmol cm2
Medium:pure water

• Structural defects  Pen-lamp of 254 nm

• Films  200 ml Batch reactor


PbS/ZnO • PbS Chemical bath 7.38 µmol cm-2 h-1  Films catalyst 10cm2
deposition  Medium:pure water
• ZnO sputtering  Pen-lamp of 254 nm

NaTaO3- 5672 µmol h-1 g -1  200 ml Batch reactor


NaTaO3 • Films by laser assisted  Films catalyst
SrTiO3 chemical vapor deposition. SrTiO3 -494 µmol h-1 g -1  Medium:pure water
 Pen-lamp of 254 nm

 The electrochemical
experiments were
α-Fe2O3- TiO2:X (X = Co, Cu, • photoanodes were carried out in a
prepared by a spin coating α-Fe2O3- TiO2:Bi - 0.18
Bi) conventional three-
• surface states and mA/cm2 electrode
heterostructure formation
photoelectrochemical
quartz cell
Material Propiedades Producción Condiciones de reacción

 200 ml Batch reactor


Au-Pd/NaTaO3 • Films by screen printing 3305 µmol m-2 h-1  Films
• Au-Pd sputtering target  Medium:pure water
 Pen-lamp of 254 nm

 200 ml Batch reactor


• Films 728 µmol m h -2 -1
 Films
SnS-AuPd • SnS by SILAR
 Medium:pure water
• AuPd by sputerring  Simulated sun ligth

 The electrochemical
• NaTaO3 Films using screen experiments were carried
printing method out in a conventional
three-electrode
RuO2-NaTaO3 • RuO2 was incorporated on 15.7 mmol h-1 g -1 photoelectrochemical
each NaTaO3 film by quartz cell connected to
chronopotentiometry chromatography
technique shimadzu equipment.
 Ligth source Lamp Xe
Bibliografía actualizada de materiales
para la fotoconversión de CO2
Reportes previos con producciones sobresalientes
Material Producción Condiciones de reacción

CH4 (0.673 mmol h-1 g-1)


CH3OH (0.373 mmol h-1 g-1)  Medium:pure water
Cu,Bi-co-doped TiO2
CH3CH2OH (0.05 mmol h-1 g-1)  Xe lamp 300 W

HCHO (0.005 mmol h-1 g-1)  Medium:Steam


Pt/TiO2-, TiO2/Fe2O3
 20 W, Fluo

Cu(X-bpy)2/TiO2 CH4 (0.004 mmol h-1 g-1)  Medium:pure water


 Xe lamp 300 W
CH3OH (0.185 mmol h-1 g-1)  Medium: NaHCO3
Ru/CuxAgyInzZnkSj
 Xe lamp 1000 W
CH3OH (4.6 mmol h-1 g-1)  Medium: NaHCO3
Ag/AgX (X:Cl Br)
 Xe lamp 300 W
 Medium: NaHCO3
Fe3O4@SiO2-Ag/AgI CH3CH2OH 1.5 mmol h-1 g-1
 Xe lamp 300 W
HCHO (0.52 mmol h-1 g-1)  Medium:pure water
Cu2O/RuO2
CH3OH (1.54 mmol h-1 g-1)  Luz Solar

NaNbO3 nanowires CH4 (653 ppm)  Medium:pure water


 400 W Hg

https://pubs.rsc.org/en/content/articlelanding/2014/cp/c4cp02828g#!divAbstract
S. Protti, A. Albini, N. Serpone, Photocatalytic generation of solar fuels from the reduction of H2O and CO2: A look at the
patent literature, Phys. Chem. Chem. Phys. 16 (2014) 19790–19827. https://doi.org/10.1039/c4cp02828g.
Material Propiedades Productos obtenidos Condiciones de reacción

CuO/ZnO • CuO nanowires with ZnO CO: 1.98 mmol/(g-h)  Películas (1 cm2)
islands  Xenon lamp 400W

• 340 m2/g  50 mg de catalizador


ZnS/SiO2 • SiO2 surface was modified HCOOH: 10 mmol  60 mL de agua
J. Photochem. Photobiol. A 1997, 111, 223. by aminopropyl groups  + 8 mL isopropanol
(avowing photocorrosion)  6 h de reacción

 10 mL (1 mg/mL cat).
 AM0 y AM1.5 filter de
ZnS • AM0 filter worked better. HCOOH: 140 mmol/(g-h) 1000 W
Appl. Mater. Interfaces 2015, 7, 44, 24543.
 8 h de reacción
 Glycerol / hole scavenger.

TiN/TiO2 • Photoreduction of  0.3 M NaHCO3


Sol. Energy Mater. Sol. Cells 2019, 200, bicarbonate and oxidation HCOOH: 3000 mmol/(g-h)  Glycerol (2M)
109967. of glycerol.  AM1.5 (1000 W/m2)
• Face-dependent activity:  300 W Xe
Cu2O CH3OH: 1.2 mol/(g-h)
Nat. Energy 2019, 4, 957.
• (110) Active  Quantum yield 72%
• (100) Inactive  0.01 g catalizador
Material Propiedades Productos obtenidos Condiciones de reacción

 100 mL batch reactor


ZnV2O6/RGO/g-C3N4 • Powders (sol gel method) CH3OH: 3 724 µmol g -1
 35 W Xe lamp
• Nanosheets
 0.1 M NaOH solution

• Hierarchical tubular  300 W Xe lamp


ZnIn2S4/In2O3 heterostructure CO: 3 000 µmol g h
-1 -1
 TEOA/Acetronitrile
• Hydrothermal synthesis solution

 20 W white cold LED lamp


 100 mL batch reactor
rGO@CuZnO@Fe3O4 • Microspheres CH3OH: 2500 µmol g-1  DMF/water 45/5 mL
• Hydrothermal synthesis solution
 0.1 g of catalyst

 Batch reactor
• Sonochemical method CH3OH: 16 000 µmol g -1
 TEA solution
rGO/InVO4/Fe2O3
• Nanosheet morphology  Visible-light irradiation

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