RESEARCH ARTICLE

ENERGY RESOURCES 2016 © The Authors, some rights reserved;

exclusive licensee American Association for

Room temperature stable COx-free H2 the Advancement of Science. Distributed

under a Creative Commons Attribution

production from methanol with magnesium NonCommercial License 4.0 (CC BY-NC).
10.1126/sciadv.1501425

oxide nanophotocatalysts
Zhengqing Liu,1* Zongyou Yin,2,3*† Casandra Cox,3 Michel Bosman,4 Xiaofeng Qian,2 Na Li,1 Hongyang Zhao,1
Yaping Du,1† Ju Li,1,2† Daniel G. Nocera3†

Methanol, which contains 12.6 weight percent hydrogen, is a good hydrogen storage medium because it is a liquid at
room temperature. However, by releasing the hydrogen, undesirable CO and/or CO2 byproducts are formed during
catalytic fuel reforming. We show that alkaline earth metal oxides, in our case MgO nanocrystals, exhibit stable pho-
tocatalytic activity for CO/CO2-free H2 production from liquid methanol at room temperature. The performance of
MgO nanocrystals toward methanol dehydrogenation increases with time and approaches ~320 mmol g−1 hour−1 after
a 2-day photocatalytic reaction. The COx-free H2 production is attributed to methanol photodecomposition to form-
aldehyde, photocatalyzed by surface electronic states of unique monodispersed, porous MgO nanocrystals, which

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were synthesized with a novel facile colloidal chemical strategy. An oxygen plasma treatment allows for the removal
of organic surfactants, producing MgO nanocrystals that are well dispersible in methanol.

INTRODUCTION
Because of the high mobility of protons, hydrogen can be efficiently though photodecomposition has been reported at room temperature
converted into electricity by using low-temperature proton exchange with Ti-b and noble metals (Pt, Rh, Ir, Pd, and Au) deposited on
membrane fuel cells. However, it is not easy to store and transport TiO2 as photocatalysts. However, the photocatalytic reactions require
pure hydrogen. A liquid methanol–formaldehyde cycle could be useful methanol vapor, and a Pt-TiO2 catalyst is plagued by low H2 yields
for storing hydrogen (1) (<7 mmol H2 g−1 hour−1) and low stability (13–15).
Here, we show that magnesium oxide (MgO), a stable and cheap
CH3 OH⇌H2 ðgÞ þ CH2 O ð1Þ alkaline earth metal oxide that has been used as a photocatalyst for
CO2 reduction and organic contaminant degradation, an additive in
Methanol (CH3OH) has a boiling point of 64.7°C and is a liquid refractory materials, and an adsorbent for air purification, toxic waste
under ambient conditions. Formaldehyde (CH2O) has a boiling point remediation, and biomedicine (16–25), is also an ultrastable photo-
of −19.3°C, so only moderate pressure (~5 atm) is needed to liquefy it; catalyst for hydrogen production from methanol. We can mass pro-
furthermore, it exhibits 37 weight percent solubility in liquid water. duce monodispersed, porous MgO nanoparticles (NPs) with diameters
Reaction (1) in a closed loop releases no carbon into the atmosphere ranging from 40 to 170 nm that demonstrate stable COx-free H2 pro-
(2, 3). The difficulty in reaction (1) lies in efficient methanol de- duction from liquid methanol near room temperature.
hydrogenation to produce H2 at the site of end use (as opposed to Various wet chemical synthesis strategies have been developed to obtain
hydrogenation, which can be accomplished centrally), and so far, this MgO nanocrystals. Examples include sol-gel processes, hydrothermal/
has been far from economical. The reported dehydrogenation catalysts solvothermal methods, polyol-mediated thermolysis reactions, and
to producing hydrogen from methanol mainly include aqueous meth- microwave-assisted synthesis (26–29). However, most of the current
anol reforming and pure methanol decomposition. Aqueous methanol routes initially yield hydroxide precursors, such as Mg(OH)2 and
reforming, with H2O added for the water-gas (CO) shift reaction, nor- Mg2(OH)2CO3, which must be calcinated at high temperatures to pro-
mally requires high temperatures (≥200°C) and pressures (≥25 bar) duce crystalline MgO. These high-temperature processes are costly and
(4, 5), or mild temperatures (<100°C) but the use of ruthenium usually result in fusion of NPs into aggregates (30–33). To date, only
complexes (6) or lower-stability metal-organic complexes (7). For pure one study focused on the preparation and properties of nearly mono-
methanol decomposition, thermal decomposition is achieved at high dispersed MgO nanocrystals using an organometallic decomposition
temperatures (≥160°C) with noble metals (Pt and Pd) (8–12), al- method (34). However, the raw materials used in this approach are
toxic and expensive. To the best of our knowledge, until now, a facile,
1
Frontier Institute of Science and Technology jointly with College of Science, State environmentally friendly, and inexpensive synthetic route to mass pro-
Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an duce well-defined, porous MgO nanocrystals still remains a challenge,
710049, China. 2Department of Nuclear Science and Engineering, and Materials Sci- and a systematic study on the synthesis and properties of monodispersed,
ence and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139,
USA. 3Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford
porous MgO nanocrystals has yet to be performed.
Street, Cambridge, MA 02138, USA. 4Institute of Materials Research and Engineering, Here, we demonstrate an inexpensive and green approach to synthe-
A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Singa- sizing monodispersed, porous monocrystalline MgO NPs (Scheme 1)
pore 138634, Singapore. using magnesium acetylacetonate dihydrate [Mg(acac)2·2H2O]. The size
*These authors contributed equally to this work.
†Corresponding author. Email: [email protected] (Y.D.); [email protected] (Z.Y.); of the porous MgO nanocrystals can be tuned from ~40 to 170 nm, all
[email protected] (J.L.); [email protected] (D.G.N.) showing ultraviolet (UV) to blue emissions under UV light excitation

Liu et al. Sci. Adv. 2016; 2 : e1501425 2 September 2016 1 of 8

RESEARCH ARTICLE

Sheme 1. Process of synthesis of MgO NPs and activity in H2 pro-

duction from methanol photodecomposition.

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that indicates high density of mid-gap surface electronic states. After
oxygen plasma treatment, we modified the surfaces of as-obtained
MgO NPs, improving their surface purity and hydrophilicity. The supe-
rior activity in COx-free H2 production from MgO NPs was associated
with the local photoexcitation and charge separation among MgO de-
fect energy levels, where excited holes oxidize methanol to generate pro-
tons that subsequently get reduced by hot electrons to produce H2.

RESULTS
Synthesis and characterization of monodispersed porous
MgO nanocrystals
The synthesized MgO NPs have an exclusively face-centered cubic
phase [periclase type, space group: Fm3m, JCPDS (Joint Committee
on Powder Diffraction Standards): 45-0946], as confirmed by powder
x-ray diffraction (XRD) analysis (Fig. 1A) for various-sized MgO NPs,
with the calculated crystal parameters a = b = c = 4.211 Å. No diffrac- Fig. 1. Composition and morphology characterization of MgO NPs.
tion peaks from other chemical species, such as Mg(OH)2 or MgCO3, (A) XRD pattern of various-sized MgO NPs. (B) TEM image of 85-nm-sized
are detectable in all the samples. The average particle sizes of MgO porous MgO NPs, with a plane size distribution analysis (inset). (C to F) Tem-
perature effect on NP size. TEM images of MgO NPs with different sizes ob-
NPs determined by XRD using the Debye-Scherrer equation to the
tained from the thermolysis of 2 mmol of Mg(acac)2·2H2O in OM/OA/ODE =
(200) reflection were around 40, 85, 115, and 170 nm, respectively. 4:1:5 (molar ratio) at different temperatures for the same reaction time of
Sharpening of the diffraction peaks indicates the increased crystallinity 30 min: 265°C (C), 280°C (D), 300°C (E), and 320°C (F). From the TEM images,
of MgO NPs with increasing size. the average sizes of MgO NPs can be estimated to be ~40 nm (C), ~85 nm
Figure 1B shows a transmission electron microscopy (TEM) image (D), ~115 nm (E), and ~170 nm (F), respectively.
of as-synthesized MgO nanocrystals; the MgO NPs are relatively
monodispersed with an average size of ~85 nm (inset for a histogram
of particle diameters). This suggests retention of capping ligands on XRD analysis (Fig. 1A). Moreover, as indicated by the TEM images
the nanocrystal surfaces, as validated by Fourier transform infrared in Fig. 1, the as-obtained MgO NPs gradually became smooth as the
(FTIR) spectroscopy (fig. S1). The scanning electron microscopy reaction temperature was elevated. Under a fixed reaction tempera-
(SEM; fig. S2A) image shows that the MgO NPs are spherically shaped. ture of 265°C, the thermolysis of 2 mmol of Mg(acac)2·2H2O in
Energy-dispersive x-ray (EDX) spectroscopy (fig. S2B) confirms that OM/OA/ODE = 4:1:5 (molar ratio) for 60 min produces MgO
stoichiometric MgO is formed with an atomic ratio of Mg/O = 1:1. NPs with a size of ~60 nm (fig. S3A). When the reaction tempera-
The size of the MgO NPs was readily controlled by varying ture was raised to 280°C with all other conditions unchanged, the
the reaction temperature and time. For instance, with 2 mmol of size of MgO NPs increased to ~100 nm (fig. S3B). Our results show
Mg(acac)2·2H2O as the precursor in oleylamine/oleic acid/1-octadecene that the size of the as-obtained MgO NPs did not significantly
(OM/OA/ODE) = 4:1:5 (molar ratio), a reaction time of 30 min at change with the reaction time (30 to 60 min) and when the tem-
265°, 280°, 300°, or 320°C produced MgO NPs with an average di- perature was kept constant at 300° or 320°C (Fig. 1E versus fig. S3C
ameter of ~40 nm (Fig. 1C), ~85 nm (Fig. 1D), ~115 nm (Fig. 1E), and Fig. 1F versus fig. S3D). This suggests a temperature-driven
or ~170 nm (Fig. 1F), respectively, which is well consistent with the “size-focusing” process with increasing reaction temperature (35).

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The crystal structure of the individual MgO NPs was determined cause of a well-maintained balance between nucleation and growth
with high-resolution TEM (HRTEM) imaging and selected-area elec- during synthesis.
tron diffraction (SAED), as shown in Fig. 2. Figure 2A represents a typ- Through manipulation of capping ligands, solvents, and their rela-
ical TEM image for a single MgO NP; an amorphous surface layer can tive ratios, we have successfully synthesized size-controlled mono-
be clearly observed at the edge of the MgO NPs (inset of Fig. 2A). This dispersed porous MgO NPs. One unique characteristic of MgO is
amorphous surface layer may result from the applied capping ligands its chemical stability, which is essential for long-term performance un-
(OM and OA), which is consistent with the FTIR spectroscopy (fig. S1). der strong illumination. To remove surface capping ligands, we used
The enlarged TEM image in the inset of Fig. 2A and the high-angle an- an oxygen plasma treatment on dried MgO powders. As an example,
nular dark-field scanning TEM (HAADF-STEM) image in Fig. 2B dem- fig. S1 shows a comparison between the FTIR spectrum of the 85-nm
onstrate the local variation in density due to the porous nature of the MgO NPs before (black) and after (red) treatment. The oxygen plas-
MgO NPs. As seen in Fig. 2C, the HRTEM images taken from Fig. 2A ma treatment thus efficiently modifies the nanomaterial surface by re-
show clear rock salt crystal lattice along the [100]. The observed inter- moving the organic capping ligands.
planar distances between the lattice fringes are 0.21 and 0.15 nm, Figure 3 shows the room temperature UV-vis (visible) absorption
corresponding to the (200) and (220) planes of MgO, respectively. and photoluminescence (PL) spectra for MgO NPs. Figure 3A shows
The SAED pattern acquired on a single MgO NP displays a single set the UV-vis absorption spectra for MgO NPs of different sizes. All of
of clear diffraction spots (Fig. 2D), confirming the monocrystalline na- the colloidal MgO NPs exhibited continuous absorption across the
ture of the porous MgO NPs (36). UV wavelength range, with two broad absorption peaks centered
In the present synthesis, the combination of different capping li- around 220 nm (5.6 eV) and 270 nm (4.6 eV). These peaks arise from

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gands was found to play a key role in obtaining monodispersed po- the excitation of O2− surface anions on the edge (fourfold coordi-
rous MgO nanocrystals. For example, aggregated MgO NPs (fig. S4A) nated) and on the corner (threefold coordinated) of the nanocrystal
were produced when 2 mmol of Mg(acac)2·2H2O was used as a pre- (37, 38), respectively. Although MgO is a wide–band gap insulator
cursor for a reaction at 280°C for 30 min, with the sole use of OM as (Eg = 7.8 eV) (39, 40), optical transitions in the visible range were ob-
the capping ligand and ODE as the solvent. In pure OA and ODE, served for our porous MgO NPs. Figure 3B shows PL spectra of MgO
almost no solid matter appeared after the precipitation treatment. In NPs at an excitation wavelength of 270 nm. The broad spectra
addition, we found that different ratios of solvents had great influence covering from 300 to 450 nm indicate the presence of structural de-
on the dispersibility of the porous MgO nanocrystals (fig. S4, B to D). fects, such as oxygen vacancies (41–43), in the insulating MgO. All of
High yields of monodispersed porous MgO nanocrystals were only the various sizes of the MgO NPs exhibited a strong visible blue emis-
obtained at an optimized OM/OA/ODE ratio of 4:1:5 (Fig. 1B) be- sion if under 365-nm UV irradiation (fig. S5).

Stable H2 production from liquid-methanol

photodecomposition near room temperature
The photocatalytic activity for hydrogen production from high-purity
liquid methanol at room temperature was examined for the MgO NPs
(see Materials and Methods for details). The excitation wavelength
dependence was studied by using various long-pass filters. As shown
in Fig. 4A, there is no H2 production when 530- or 380-nm long-pass
filters are used. However, full-wavelength illumination (200 to 2500 nm)
resulted in the production of H2. This result is consistent with photo-
activity arising from 220- and 270-nm excitation of the MgO nano-
crystals (Fig. 3A). Hydrogen production was sensitive to MgO
concentration in methanol. Figure 4B shows that suspensions of

Fig. 2. Crystal structure analysis of MgO NP. (A and B) TEM (A) and
HAADF-STEM (B) image of a single porous MgO NP with a diameter of
~85 nm. Inset of (A): Enlarged TEM images for the edge and center of the Fig. 3. Optical properties of MgO nanocrystals. (A and B) Room tempera-
MgO NPs. (C and D) HRTEM image (C) and the corresponding SAED pattern ture UV-vis absorption (A) and PL (lex = 270 nm) spectra (B) of differently
(D) recorded from (A). sized porous MgO NPs. a.u., arbitrary units.

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~0.38 mg ml−1 exhibit the best performance. Lower concentrations The H2 production yields for various sizes of MgO nanocrystals
likely dilute the concentration of intermediate products, radicals, are presented in fig. S6. Among the different sizes, the highest H2
and/or protons because of the lower availability of surface active sites production rates (~55 mmol g−1 hour−1) occur from 85-nm MgO
or photoexcited charges from MgO, resulting in a lower performance. NPs. The higher surface area of the smaller-sized MgO nanocrystals
On the other hand, high concentrations can cause light blocking/ (85 nm), as compared to the larger-sized MgO nanocrystals (115 and
screening between the adjoining MgO nanocrystals, thus lowering 170 nm), leads to an enhanced photocatalytic reaction with metha-
light-harvesting efficiency. This is further supported by the fact that nol. The surface area was verified using the Brunauer-Emmett-Teller
MgO’s absorbance of light rises much slower compared with its con- (BET) method: the 40-, 85-, 115-, and 170-nm-sized MgO NPs have
centration increase (fig. S6A). surface areas of 28.5, 19.7, 17.4, and 13.9 m2 g−1, respectively (fig. S7).

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Fig. 4. H2 production from methanol photodecomposition based on ~85-nm MgO nanocrystals. (A) Illumination wavelength effect using the
long-wave pass filters with different cut-on wavelengths. (B) MgO concentration effect with constant 3 mg of MgO powder dispersed in different
volumes of methanol. (C) Performance endurance of H2 production by continuing to use the same MgO (3 mg)/methanol (8 ml) reaction materials
for the whole three-cycle testing. (D) XRD pattern for MgO after a total 48-hour photocatalytic reaction.

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The smallest-sized MgO nanocrystals (40 nm), with the largest BET
surface area, did not yield the highest H2 production rate per weight.
This is most likely the result of the lower crystal quality of 40-nm-
sized MgO nanocrystals (fig. S8) as compared to the 85-nm-sized
MgO nanocrystals (Fig. 2D). The production of H2 from pure MgO
nanocrystals indicates that photoexcited electrons and holes in the
surface defect energy levels of MgO can be harvested to oxidize meth-
anol and reduce the generated protons (H+) for H2 production. At the
same time, this result demonstrates that an oxygen plasma treatment
is an effective method to remove the organic surfactants from nano-
materials synthesized via this oil phase strategy. After oxygen plasma
treatment, MgO crystals have hydrophilic surfaces and become dis-
persible in polar liquids, such as methanol and water. This method
enhances the direct contact between the MgO nanocrystal surface
and methanol, enabling a more efficient photoreaction.
The H2 production from MgO NPs is stable, and the rate actually
improves with time (Fig. 4C and fig. S9). This is in contrast to many
H2 production systems, which often deteriorate in performance over Fig. 5. Schematic diagram of proposed hydrogen production mecha-

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time (5, 7, 15, 44, 45). To test MgO’s performance stability, we nism for MgO nanocrystals. On the basis of the UPS results (fig. S11), the
monitored product analysis of the same MgO/methanol system under valence band maximum for MgO, that is, Ev, is ~−10.5 eV relative to vacuum.
photocatalytic reaction over the course of 2 days. To avoid undesirable Combined with the 7.8-eV band gap of MgO, we infer a conduction band
gas leakage from the capped septum of a reactor during periodic sy- minimum, Ec, of −2.7 with respect to the vacuum energy level (Evac = 0). The
ringe removal of products from the cell, the reaction system was energy levels of the absorption at 4.6 eV arise from surface excitons, as de-
scribed in the main text. The energy levels of the emission in MgO are
interrupted and then vented in fume hood between testing cycles.
derived from the PL spectrum of 85-nm-sized MgO in Fig. 3B, that is, an emis-
During the first cycle, the produced H2 rises steadily, increasing with
sion peak at 330 nm with a broad shoulder at around 400 nm. NHE, normal
time. After the interruption following cycle 1, the production of H2 hydrogen electrode.
continues and its rate increases with time in cycle 2. Hydrogen pro-
duction continues in cycle 3, although to a lesser extent in rate in-
crease. Notably, the rate reaches ~320 mmol g−1 hour−1 at the end methanol lies between the energy levels of excitonic electrons and
of a 2-day photocatalytic reaction. The local temperature induced holes in the absorption region of MgO. Surface-bound electron-hole
by the lamp illumination around the photoreactor was observed to pairs from threefold/low-coordinate surface sites of MgO NPs are
vary from 25° to 37°C over the 2-day reaction period. Note here that ionized after absorption of UV light mainly at 220 nm (5.6 eV) and
the temperature does not rise with illumination time strictly linearly: 270 nm (4.6 eV) (see Fig. 3A) (37, 38, 43). For simplicity, only the
the temperature is relatively high, ~37°C, around noon and does not energy levels in the absorption region relating to the 270-nm peak
surpass 33°C during other times. The temperature therefore did not are illustrated in Fig. 5. The energy level of the photogenerated holes
affect the performance, and the rising performance during the first of MgO is over −8 eV, negative to the oxidation potential of methanol
24-hour reaction (Fig. 4C and fig. S9) occurred as the surface sites at ~−4.3 eV versus the vacuum energy level Evac at pH 7 (48). This
on MgO NPs were gradually activated while the reaction was on- enables photogenerated holes to oxidize CH3OH and generate
going. On the basis of our experimental results, MgO nanocrystals intermediate hydroxyalkyl radical, ·CH2OH. These dynamically un-
are extremely stable under operating conditions for H2 production stable radicals are easily oxidized to formaldehyde (CH2O) (3, 49).
near room temperature. This is attributed not only to the large During the two-step oxidation, two protons are generated and reduced
band gap and high chemical stability of MgO (the heat of formation to H2 from the electrons residing in surface states of MgO. This H2
is 601.24 kJ mol−1 of oxygen, in contrast to 469.36 kJ mol−1 of oxygen production behavior is closely correlated with the unique structure of
for TiO2) but also to photocatalytic surface states. To our knowledge, our synthesized MgO nanocrystals. As shown in fig. S10, we com-
this work is the first to demonstrate catalytic methanol photo- pared time-dependent H2 production between MgO in this work,
decomposition using the surface states of a dielectric oxide nanoma- commercial MgO, commercial SiO2, and commercial TiO2 (P25)
terial synthesized with a low-cost, high-throughput, green process. NPs. The sizes of commercial MgO, SiO2, and TiO2 are about 80 to
100 nm, 30 to 60 nm, and 20 to 40 nm, respectively. Before H2 pro-
Insight into H2 production from MgO/methanol duction, all samples are treated with the same O2 plasma. With the
Figure 5 proposes a mechanism for the H2 production of MgO in continuous light illumination time for 24 hours, H2 produced from
methanol (46, 47). In this figure, the black dotted lines close to the commercial SiO2 is only 0.4 mmol, and that from commercial MgO
central solid line represent the broad emission feature of MgO. For reaches 1.1 mmol. However, MgO in this work can reach 2.4 mmol,
comparison, the energy scale versus Evac is scaled to the redox which is 2.2 and 6.0 times of that from commercial MgO and SiO2,
potential versus the normal hydrogen electrode (46, 47). The oxidation respectively. Compared with SiO2 and MgO, commercial TiO2 (P25)
potential for methanol, ~−4.3 eV versus Evac at pH 7, is indicated by produced H2 more efficiently at first but slowed down after 12-hour
the dashed pink line. Absolute energy levels for emission and absorp- reaction and was surpassed by MgO in this work after 16 hours. This
tion are set on the basis of the fact that MgO NPs have photocatalytic indicates an unendurable performance from commercial TiO2 (P25).
activity in H2 production. This requires that the oxidation potential of The low performance of commercial SiO2 implies that O2 plasma

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RESEARCH ARTICLE

treatment itself does not make a notable contribution to H2 produc- MATERIALS AND METHODS
tion in this work; O2 plasma treatment is mainly used to make MgO Chemicals
nanocrystals hydrophilic. The obviously more H2 produced from the Magnesium 2,4-pentanedionate hydrate [Mg(acac)2·2H2O, >98%, Alfa
MgO in this work, as compared with commercial MgO, demonstrates Aesar], OM (70%, Sigma-Aldrich), OA (90%, Sigma-Aldrich), ODE
that the unique structure with low-coordinate surface sites of our (>90%, Sigma-Aldrich), ethanol [analytical reagent (AR)], acetone
MgO directly contributes to efficient H2 production from methanol (AR), glycerin (AR), and cyclohexane (AR) were used as received
under photocatalytic reaction. without further purification.
Aqueous methanol reforming, one of the methanol dehydro-
genation reactions, produces carbon dioxide (CO2) via the water-gas Synthesis of porous MgO NPs
shift reaction. Conversely, complete decomposition of methanol gen- The synthesis of the 85-nm-sized porous MgO NPs was used as an
erates carbon monoxide (CO) and H2 (5). In our MgO/methanol re- example. A slurry containing 2 mmol (0.445 g) of Mg(acac)2·2H2O,
action system, neither CO2 (fig. S11, A and C) nor CO (fig. S12, A and 16 mmol (4.288 g) of OM, 4 mmol (1.128 g) of OA, and 20 mmol
B) was observed in the products. On the basis of this observation, the (5.05 g) of ODE in a three-necked flask (100 ml) was heated to 140°C
two main products from MgO/methanol after photodecomposition to remove water and oxygen, thus forming a homogeneous light yel-
are H2, as observed from the chromatogram of fig. S11A, and low solution. The resulting mixture was heated to 280°C under N2 and
CH2O. This indicates that methanol, catalyzed by MgO, is not com- kept at that temperature for 30 min. Upon cooling to room tempera-
pletely photodecomposed. Although this partial decomposition of ture, the nanocrystals were precipitated by adding an excess of ethanol
methanol is not ideal in terms of H2 production capacity, the CH2O and glycerin (volume ratio of 4:1) and separated from the solution by

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product is a convenient liquid in a closed loop (under ~5-atm pres- centrifugation (10,000 rpm, 10 min), followed by drying in an oven at
sure), as opposed to CO2 or CO gases. Note here that there is a trace 60°C. The glycerin was used to remove impurities, such as NaCl. The
of unknown gaseous component (fig. S11A), which is attributed to the as-prepared dried nanocrystals could be dispersed in various nonpolar
impurities in methanol because this component is also produced after organic solvents, such as cyclohexane and toluene. The average yield
illumination of pure methanol (fig. S11B). Additionally, negligible of nanocrystals was around 55%.
amounts of oxygen are also present because of the manual injection
of gas into the gas chromatograph. Furthermore, to check whether Characterization
methanol itself produces H2 under UV light illumination (50), H2 TEM images were acquired with a Hitachi HT7700 transmission elec-
production was monitored from 8 ml of methanol in the absence tron microscope operated at 100 kV. HRTEM micrographs and STEM
of the MgO photocatalyst. As shown in fig. S5B, the amount of H2 images were obtained with a Philips Tecnai F20 FEG (field emission
produced is only ~0.1 mmol after 10-hour reaction, which is only gun)–TEM operated at 200 kV. SEM images were characterized
2.5% of that (~4 mmol) produced from the MgO/methanol (3 mg through a Quanta F250. Samples for TEM analysis were prepared by
of MgO dispersed in 8 ml of methanol). The negligible H2 produced drying a drop of cyclohexane solution containing the nanocrystals on
from pure methanol starts to saturate after a 9-hour reaction (fig. the surface of a carbon-coated copper grid. The XRD patterns were
S6B), which implies that the hydrogen is probably produced from obtained using Rigaku D/MAX-RB with monochromatized Cu Ka ra-
the impurities in methanol that eventually decomposed to the inactive diation (l = 1.5418 Å) and 2q ranging from 20° to 80°C. Infrared
species. This saturation in H2 production is in contrast to the spectra were recorded on a Nicolet 6700 FT-IR spectrometer. UV-vis
increasing H2 production for MgO/methanol (Fig. 4C and fig. S9). absorption spectra were measured on a PerkinElmer Lambda 35 UV-vis
MgO not only exhibited stable performance; its crystal structure was spectrophotometer. PL spectra were recorded on a Hitachi F-4600 spec-
well maintained after the 48-hour photocatalytic reaction. This is con- trofluorophotometer at room temperature. Nitrogen adsorption-
firmed by the XRD taken after 48 hours of operation, which is still desorption isotherms were measured on a Micromeritics TriStar 3000
well matched to the standard pattern of JCPDS: 45-0946, as shown porosimeter (mesoporous characterization) and Micromeritics ASAP
in Fig. 4D. 2020 (microporous characterization) at 77 K. All MgO NPs samples
were outgassed at 160°C for 6 hours under vacuum before measure-
ments. The specific surface areas were calculated on the basis of the
DISCUSSION BET method. Ultraviolet photoelectron spectroscopy (UPS) measure-
ments were carried out with a Shimadzu/Kratos AXIS Ultra DLD
Here, we demonstrate to have successfully synthesized porous, mono- spectrometer, using the HeI radiation (21.21 eV) from a He discharge
crystalline MgO NPs via a green and cheap thermolysis process with lamp. Peaks were recorded with a constant energy of 5 eV and a step
high yields. The diameter of the MgO nanocrystals can be well size of 0.05 eV. The pressure in the analysis chamber was maintained
controlled from 40 to 170 nm, and these nanocrystals exhibit intense at 4.3 × 10−9 torr.
defect-induced blue luminescence under UV excitation. To widen the
application of MgO synthesized via an oil phase solution process, we Measurement of H2 production
successfully used an oxygen plasma treatment to remove the capping Here, four kinds of materials/powders were tested for the photo-
ligands and increase hydrophilicity and dispersion in polar liquids, catalytic hydrogen production, including MgO nanocrystals with sizes
such as methanol and water. The resulting MgO NPs are photocata- of 40, 85, 115, and 170 nm. Note here that, before the photocatalytic
lysts for liquid-methanol photodecomposition, resulting in fast COx- experiments, all the MgO powders were treated with the same oxygen
free H2 production. The ultrastable catalytic activity for COx-free H2 plasma for 1 hour to generate hydrophilic surfaces by removing the
production demonstrated herein points to new paths to develop envi- hydrophobic organic ligands. The photocatalytic hydrogen produc-
ronmentally friendly and scalable photocatalysts. tion experiments were performed in a ~16-ml quartz flask under

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Liu et al. Sci. Adv. 2016; 2 : e1501425 2 September 2016 8 of 8

Room temperature stable COx-free H2 production from methanol with magnesium oxide
nanophotocatalysts
Zhengqing Liu, Zongyou Yin, Casandra Cox, Michel Bosman, Xiaofeng Qian, Na Li, Hongyang Zhao, Yaping Du, Ju Li and
Daniel G. Nocera

Sci Adv 2 (9), e1501425.

DOI: 10.1126/sciadv.1501425

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