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2022 Charge Transfer Observed in Light Activated Catalyst Particles

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of the immune protein interferon regula- an accessory protein and histone mimicry as

tory factor  3 to the nucleus 13, promotes part of their interference strategies.
stress responses in an organelle called the From the archive
endoplasmic reticulum13 and mediates deg- Lisa Thomann and Volker Thiel are at the
radation of immune proteins called MHC Institute of Virology and Immunology, Bern Detecting counterfeit whisky using
proteins11. and Mittelhäusern 3012, Switzerland, and in nuclear technology, and the legendary
Kee and colleagues’ work adds another the Department of Infectious Diseases and origins of Scottish boulders.
layer to our understanding of how SARS-CoV-2 Pathobiology, Vetsuisse Faculty, University of
interacts with host cells. It will be important Bern. V.T. is also in the Multidisciplinary Center
to investigate further how Orf8 activity can for Infectious Diseases, University of Bern. 50 years ago
alter virus infection and spread, and the e-mails: lisa.thomann@vetsuisse.unibe.ch; Some of the most useful … benefits of
development of disease in humans. A natu- volker.thiel@vetsuisse.unibe.ch nuclear technology have come from the
rally occurring deletion in the SARS CoV-2 application of activation analysis to forensic
1. Kee, J. et al. Nature 610, 381–388 (2022).
gene encoding Orf8 that was found in 2020 2. Tarakhovsky, A. & Prinjha, R. K. J. Exp. Med. 215, 1777–1787 problems … The forensic uses of activation
in Singapore was associated with less severe (2018). analysis depend mainly on the detection
3. Frieman, M. B. et al. in The Nidoviruses: Toward Control of
disease14 and might provide the first hints. It and estimation of trace elements in material
SARS and Other Nidovirus Diseases (Adv. Exp. Med. Biol.
remains unclear whether the decreased sever- 581) (eds Perlman, S. & Holmes, K. V.) 149–152 (Springer, gathered from the scene of a crime or from
ity of this variant was directly linked to changes 2006). a suspect … F. W. Lima … told of studies
4. Rohaim, M. A., El Naggar, R. F., Clayton, E. & Munir, M.
in histone mimicry, but the association shows Microb. Pathog. 150, 104641 (2021).
on counterfeit whisky. The bottles, labels,
that coronavirus accessory proteins can have 5. Asthana, A., Gaughan, C., Dong, B., Weiss, S. R. & corks — and even the contents — were
roles in disease severity. Silverman, R. H. mBio 12, e01781-21 (2021). not distinguishable chemically from the
6. Lee, S. et al. Nature 599, 283–289 (2021).
The study raises questions about virus 7. Zazhytska, M. et al. Cell 185, 1052–1064 (2022).
genuine articles, but the lead foil caps were
evolution and adaptation to humans. Most 8. Hadjadj, J. et al. Science 369, 718–724 (2020). found, by anomalies in tin and antimony
of the proteins in SARS-CoV-2 and the related 9. Blanco-Melo, D. et al. Cell 181, 1036–1045 (2020). content, to be of local manufacture. The
10. Josefowicz, S. Z. et al. Mol. Cell 64, 347–361 (2016).
virus SARS-CoV, which was responsible for 11. Zinzula, L. Biochem. Biophys. Res. Commun. 538, 116–124
object of the well-planned counterfeiting
a smaller coronavirus pandemic in 2003, (2021). was to sell Brazilian whisky (of its kind, quite
are highly evolutionarily conserved, except 12. Hasan, M. Z., Islam, S. & Matsumoto, K. Sci. Rep. 11, 16814 good) as a genuine Scottish product at an
(2021).
for Orf3b and Orf8, with the Orf8 protein of 13. Rashid, F., Dzakah, E. E., Wang, H. & Tang, S. Virus Res. inflated price.
SARS-CoV lacking an ARKS motif. By contrast, 296, 198350 (2021). From Nature 13 October 1972
some SARS-related coronaviruses in bats 14. Young B. E. et al. Lancet 396, 603–611 (2020).

exhibit the motif. This might indicate that The authors declare no competing interests.
150 years ago
SARS-related coronaviruses are evolving to use This article was published online on 5 October 2022. The first Report of the Committee
appointed to collect statistics as to
boulders … contains much that is
Physical chemistry
interesting both to the geologist and

Secrets of light-activated archaeologist … Great numbers of boulders


have legends attached to them, one of the
commonest being that the boulder was

catalyst particles revealed thrown to the spot where it lies by some


giant, demon, or even by “Auld Nickie Ben”
himself … [A]lmost invariably, the place
from which the legend says the huge stone
Ulrich Aschauer
was thrown, is the nearest spot containing
The movement of electric charges in light-activated catalyst the formation to which the boulder belongs
particles is key to the water-splitting reaction, which could … [B]oulders differ from the formation on
or in which they are found, and in reference
be used to generate hydrogen as a renewable fuel. Such
to what we have just mentioned, the place
movement has now been observed in exquisite detail. See p.296 from which the giant or devil took his throw
is often at a very considerable distance …
For example there is a large conglomerate
Renewable energy sources are of great inter- and length scales involved. On page  296, boulder near the top of a hill, in the island
est for reducing our dependence on fossil Chen et al.1 report an impressive advance in the of Edag, one of the Orkneys, which goes
fuels. Light-activated catalysts — known as spatio-temporal monitoring of excited charge under the name of the “Giant’s Stone.”
photo­catalysts — are promising in this regard, carriers on single photocatalyst particles; the The legend says it was flung by a giant
because they convert solar energy to chemi- findings could provide much-needed detail on from the island of Stronsay; now there is
cal energy that is stored in the bonds of fuel photo­catalytic processes. no conglomerate rock which could have
molecules. Progress in this field will require The Sun has great potential as a renewable supplied the boulder in Edag, though there
the development of new photo­catalytic mater­ energy source — the solar radiation that strikes is in Stronsay.
ials. But future advances will also hinge on Earth in just one hour is equivalent to the From Nature 10 October 1872
an improved understanding of how electric amount of energy currently used annually by
charges are generated and transferred within humans2. The only requirement is that the radi-
photo­catalyst particles, so that the particles ation’s energy must be converted to a usable
can be rationally tuned for solar-to-fuel con- form, such as electrical, chemical or thermal
version. Such insight is challenging to obtain, energy. Solar cells are commercially available
given the extremely wide range of timescales to convert sunlight to electricity, but for some

Nature | Vol 610 | 13 October 2022 | 263


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the dynamics of electron and hole transfer in
Photocatalyst Light the photocatalysts.
particle
The ability to track electron populations
{001} facet
with high resolution in both space and time on
a single particle establishes an experimental
approach that will extend our understanding
0.5 ps
of the fundamental microscopic mecha-
nisms underlying photo­catalytic function.
In particular, being able to resolve electron
Hole and hole accumulation with sub­picosecond
{111} facet Excited resolution yields unprecedented insight into
electron charge-transfer processes that occur immedi-
ately after particles have been excited by light.
Figure 1 | Rapid charge separation observed in photocatalysts. Light-activated catalysts, known as Previously, measurements could be taken only
photocatalysts, can be used to promote a variety of chemical reactions. This requires the separation of at microsecond timescales, or after the charge
electric charges and their transfer to the surfaces of photocatalyst particles. Chen et al.1 report using a carriers had reached equilibrium (that is, once
combination of techniques to observe charge transfer on single particles of a photocatalyst (cuprous oxide; charge transfer had finished)9.
Cu2O), across a wide range of timescales and length scales. The particles have two types of facet, known as Chen and colleagues’ approach holds great
{001} and {111} facets. Irradiation with light initially produces negatively charged, excited electrons paired
promise for diagnosing bottlenecks in photo-
with positively charged electron vacancies (known as holes) on all facets. The excited electrons then migrate
catalytic processes and for determining the
to the {001} facets, whereas holes accumulate on the {111} facets. The authors observed that this process
success of particle-engineering strategies —
occurs surprisingly quickly, in less than 1 picosecond (1 ps is 10–12 seconds).
such as defect engineering, coating particles
with layers of other materials and the addition
applications it is preferable for energy to be technique called surface photo­voltage micro­ of co-catalysts — in maximizing the efficiency
stored in the bonds of fuel molecules. This is scopy4 (SPVM). More importantly, these parti- of hydrogen generation from water splitting.
especially the case for long-distance vehicles, cles contain intrinsic electric fields across the A current limitation of this approach is that it
for which refuelling is likely to be much quicker interfaces between the two facet types; such relies on a combination of highly advanced,
than recharging a battery. fields are key to the process that separates specialist techniques. But if these methods can
The most desirable strategy for converting electrons and holes in photocatalysts after be developed into routine and widely available
sunlight into chemical energy is direct solar- excitation by light5,6. tools, the resulting data will be substantially
to-fuel photocatalysis. In this process, a semi­ The main advance in Chen and colleagues’ more valuable for fundamental science than
conductor photocatalyst absorbs sunlight, study is their use of time-resolved meas- are oxygen or hydrogen production rates,
which excites some of the material’s electrons urements to track changes in the electron which are currently often reported.
from a low-energy band (the valence band) to a population on individual facets with high tem- The authors’ approach should be readily
high-energy band (the conduction band). The poral resolution, using a technique known as applicable to photocatalysts other than
resulting high-energy electrons can then be time-resolved photo­emission electron micro­ cuprous oxide, and will therefore allow com-
transferred from the semiconductor to a mol- scopy7. The authors observed surprisingly parisons of the inner workings of a variety
ecule adsorbed on the photocatalyst’s surface. rapid electron transfer from the {111} to the of materials, deepening our understand-
At the same time, electron vacancies in the {001} facets after light irradiation: it occurred ing of the mechanisms that underlie good
valence band, known as holes, can attract in less than 1 picosecond (1 ps is 10–12 seconds), photo­catalytic performance. Such detailed
electrons from the molecule. This addition knowledge of microscopic processes will
and subtraction of electrons allows the photo­ “The combustion of be indispensable for rational design of the
catalyst to promote complex redox reactions high-performance catalysts needed to make
of molecules adsorbed at its surface.
hydrogen produces only direct solar-to-fuel conversion an economi-
One particularly appealing such reaction water as a by-product, cally viable technology.
is water splitting, which converts water into thus enabling its use in an
oxygen and hydrogen. The combustion of Ulrich Aschauer is in the Department of
hydrogen produces only water as a by-product,
environmentally neutral Chemistry, Biochemistry and Pharmaceutical
thus enabling its use as a fuel in an entirely envi- conversion cycle.” Sciences, University of Bern, CH-3012 Bern,
ronmentally neutral conversion cycle. Chen Switzerland.
et al. investigated particles of cuprous oxide e-mail: ulrich.aschauer@unibe.ch
(Cu2O), which promote water splitting when a time frame that was previously inaccessible
used in conjunction with a suitable co-catalyst3. to single-particle measurements. This obser- 1. Chen, R. et al. Nature 610, 296–301 (2022).
Crystals of cuprous oxide are bounded by vation suggests that electron transport is 2. Lewis, N. S. & Nocera, D. G. Proc. Natl Acad. Sci. USA 103,
15729–15735 (2006).
two types of facet, known as {001} and {111} only weakly affected by imperfections in the 3. de Jongh, P. E., Vanmaekelbergh, D. & Kelly, J. J.
facets, which correspond to distinct planes in photocatalyst material, and that the electrons J. Electrochem. Soc. 147, 486–489 (2000).
the material’s crystal lattice (Fig. 1). The authors encounter very low resistance to their move- 4. Spadafora, E. J., Demadrille, R., Ratier, B. & Grévin, B.
Nano Lett. 10, 3337–3342 (2010).
engineered their particles by altering the ratio ment. By contrast, using a technique called 5. Li, R. et al. Nature Commun. 4, 1432 (2013).
of the surface areas of the two facet types, and transient surface photovoltage spectroscopy8, 6. Li, L., Salvador, P. A. & Rohrer, G. S. Nanoscale 6, 24–42
by controlling the types of lattice defect that the authors observed that charge-carrier trap- (2014).
7. Schmidt, O. et al. Appl. Phys. B 74, 223–227 (2002).
form on the different facets. In this way, they ping at surface defects occurs on the micro- 8. Dittrich, T., Fengler, S. & Franke, M. Rev. Sci. Instrum. 88,
produced particles that preferentially accumu- second scale. Finally, Chen et al. showed that 053904 (2017).
late negatively charged electrons on the {001} the rate at which hydrogen is generated by the 9. Hesari, M., Mao, X. & Chen, P. J. Am. Chem. Soc. 140,
6729–6740 (2018).
facets and positively charged holes on the {111} cuprous oxide photocatalysts in the presence
facets when irradiated by light, as revealed by a of a gold co-catalyst can be directly related to The author declares no competing interests.

264 | Nature | Vol 610 | 13 October 2022


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