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Making electrocatalytic them in stability.1,2 However, this

favorable comparison only holds for
materials from performance tests carried out in ideal
conditions, often in solution or on flat,
molecular catalysts small electrodes. On the device scale,
the electrocatalytic performance of syn-
Huaiguang Li1 and Nicolas Plumeré1,* thetic molecular catalysts is typically
lower by orders of magnitude when
compared with that of state-of-the-art
The implementation of earth-abundant metal catalysts in hydrogen precious-metals-based fuel cells.
fuel cells is necessary in developing sustainable energy schemes.
Recently in Chem Catalysis, Chenevier and co-workers investigate The cause for the discrepancy between
the effect of ionomers on the assembly of catalytic layers based intrinsic properties of molecular
on molecular catalysts. They highlight the importance of under- catalysts and their device scale perfor-
standing the layer structuration at the molecular scale to maximize mance is that research endeavors
catalytic efficiency at the device-scale. for catalyst integration have almost
entirely focused on precious metals
whereas the specific requirements for
The ‘‘terawatt challenge’’ for global en- zymes evolved toward unique elec-
molecular catalysts have received only
ergy consumption necessitates new tronic structure, thermochemistry, and
little attention.
catalysts for sustainable energy conver- kinetics; their exceptional catalytic
sions. Besides meeting the require- properties have inspired the design of
Generally, electron, proton, and H2
ments of stability and efficiency, the numerous synthetic catalysts based on
transport need to be considered
catalysts should be scalable, i.e., based earth-abundant metals. The high crus-
when designing the catalytic layer to
on cost-effective and readily accessible tal abundance of these metals would
maximize efficiency (Figures 1A and
metals.1 Although precious-metal cata- reduce cost and environmental foot-
1B). Along with controlling the envi-
lysts exhibit excellent catalytic activity print for developing sustainable energy
ronment of the catalyst to promote
and stability, their reserves and costs systems.
high intrinsic activity, choosing the
limit their use in large-scale applica-
tions in fuel cells and electrolyzers. Recently, remarkable progress has
been achieved in bio-inspired synthetic
1Campus Straubing for Biotechnology and
In nature, most of the redox transforma- catalysts, which now rival and even
Sustainability, Technical University Munich,
tions converting energy and sustaining exceed their precious metal catalysts’ Schulgasse 22, 94315 Straubing, Germany
life are catalyzed by enzymes based counterparts in selectivity and activity, *Correspondence: [email protected]
on earth-abundant elements. These en- while also becoming competitive with https://doi.org/10.1016/j.chempr.2021.02.010

Chem 7, 547–554, March 11, 2021 ª 2021 Published by Elsevier Inc. 549
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layer embedding the catalysts influ-

ences its structuration and thus its
performance.5

They specifically studied layers assem-

bled from three distinct DuBois cata-
lysts that differ in their linking unit, but
are identical in their catalytic center
(Figures 1B and 1D). First, a previously
reported pyrene functionalization of
the DuBois catalyst was used for teth-
ering to bare carbon nanotubes via
p-stacking. Second, a DuBois catalyst
functionalized with activated esters
was used for covalent amide linkage
to amine-modified carbon nanotubes.
Third, a positively charged arginine-
modified DuBois catalyst was immobi-
lized via electrostatic interactions
on carboxylate functionalized carbon
nanotubes. Surprisingly, these three
systems, despite differing only in their
attachment chemistry, greatly differ in
their catalytic performance when
formulated into a catalytic layer:

(1) p-stacking on bare carbon nano-

Figure 1. Assembly of the catalytic layer from molecular catalysts
tubes. Excessive interactions be-
(A–D) Schematic representation of a fuel cell setup (A); the catalytic layer (B) is composed of a
carbon nanotube, ionomers, and the DuBois catalyst (C). The three attachment strategies are
tween the Nafion ionomer and
based on the DuBois catalyst functionalized with a pyrene moiety, an activated ester, and an the bare carbon nanotubes
arginine group. The three Dubois catalysts are combined with the corresponding carbon induced the displacement and
nanotubes (bare, amine functionalized, or carboxylate functionalized) and with a Nafion ionomer to detachment of the DuBois cata-
form the catalytic layer, resulting in different structures (D).
lysts immobilized via p-stacking.
As a result, the electron transfer
proper support materials with excel- oxidation (up to around 2 A cm
2 at between the catalyst and the
lent conductivity is needed to improve minimal overpotential). support was cut off, preventing
electron transfer.3 Designing a porous catalysis of the H2 oxidation re-
gas diffusion layer with high gas Recently in Chem Catalysis, Artero, action. These new insights
permeability is also needed for maxi- Chenevier, and co-workers propose explain the low performance of
mizing H2 transport. the first systematic study for the integra- previously reported fuel cells
tion of bio-inspired molecular catalysts based on pyrene-DuBois cata-
In the field of hydrogen fuel cells based based on earth-abundant elements in lysts.
on Pt, porous carbon materials have a catalytic layer for hydrogen fuel cells. (2) Covalent attachment on amine-
been developed and widely used as Nickel(II) bisdiphosphine complexes modified carbon nanotubes.
conductive support for electrically wir- (the so-called DuBois catalysts) (Fig- The amine-modified carbon
ing the catalysts. Precious metal cata- ure 1C) for H2 oxidation were mixed nanotubes were intended for
lysts supported on carbon black were with Nafion and multi-walled carbon robust covalent tethering of the
additionally combined with Nafion as nanotubes and drop cast on a gas diffu- catalysts. However, the nega-
an ionomer to accelerate proton trans- sion layer. The authors then used a tively charged Nafion ionomer
port.4 Intense efforts in the optimiza- combination of electrochemical, scan- densely wraps via electrostatic
tion over the past decades established ning-electron microscopy, and small- interaction around the positively
Pt-based catalytic layers showing angle neutron scattering methods, charged carbon nanotubes
exceptional catalytic properties for H2 to reveal how the formulation of the modified with the DuBois

550 Chem 7, 547–554, March 11, 2021

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catalyst. The coverage of the cat- This work will be of great interest for support by Nafion. Ultimately, the
alysts by the Nafion film severely those working on the implementation design principle of the catalysts might
hinders the gas diffusion to the of other molecular catalysts in electro- need to consider the requirement for
active center and decreases the catalysis for which material-based catal- the catalytic layer to avoid extensive
overall performance of the cata- ysis holds the current benchmark in research investment eventually leading
lytic layer. device performances. In particular, mo- to a dead end at the catalyst integration
(3) Electrostatic adsorption on nega- lecular catalysts made impressive prog- stage. The Chem Catalysis paper also
tively charged carbon nanotubes. ress for CO2 reduction6 and for N2 exposes that catalytic layer technology
In the case of carboxylate modi- reduction7 whereby the selectivity will developed for Pt catalyst is not neces-
fied carbon nanotubes, the nega- need to be maintained or even sarily compatible with the emerging
tively charged Nafion ionomer improved upon device integration. new classes of sustainable catalysts.
imposes marginal influence on Future development of ionomers,
the anchoring of the catalysts. This study is also instructive for wiring electrode materials, and membranes
The efficiency of the electron other highly active but potentially frag- specifically designed for molecular
transfer remains unaffected. ile catalysts such as enzymes. For and biological catalytic systems will
Meanwhile, the ionomer forms a instance, hydrogenase shows higher become an important field of research.
relatively independent water-rich activity per active site than platinum
matrix network that facilitates even when immobilized on carbon ma- Further efforts toward optimized cata-
proton transport. The resulting terials suitable for high performance lyst integration, as opened in the
porous structure further benefits fuel cells.8 Nevertheless, additional Chem Catalysis paper, will be essential
gas and electrolyte diffusion. considerations are necessary for pre- because industrial interest will not be
Altogether, the use of this cata- venting the denaturation of the enzyme reached before the device-scale perfor-
lytic layer composite in a fuel cell during immobilization on the support mance compare or outperform existing
led to an open circuit voltage of and for achieving long-term stability in technology. Unless niche markets
820 G 5 mV, a maximum current the aggressive environments of an rapidly appear to motivate the engi-
density of 28 mA cm
2 and an operating fuel cell. Previously reported neering of the catalytic layer, funda-
impressive maximum power protection strategies using a redox ma- mental research will be a much needed
output of 325 G 2 mW cm
2 at trix can effectively stabilize the hydrog- driver to better understand the require-
415 mV. This performance is an enase and significantly increase its ments for integrating sustainable cata-
enhancement by a factor of 15 in operational life-time (up to weeks).9,10 lysts and enable their global use in
comparison to the state-of-the- However, mass transport and electron fuel cells and electrolyzers.
art bio-inspired Ni-based cata- transfer limitations emerge as trade-
lysts integrated into an opera- offs when increasing film thickness for
1. Bullock, R.M., Chen, J.G., Gagliardi, L., Chirik,
tional proton-exchange mem- protection considerations.10 Satisfying P.J., Farha, O.K., Hendon, C.H., Jones, C.W.,
brane fuel cell. the catalyst protection criterium while Keith, J.A., Klosin, J., Minteer, S.D., et al.
(2020). Using nature’s blueprint to expand
achieving efficient transport and wiring catalysis with Earth-abundant metals. Science
This breakthrough exposes how fea- is the next challenge in engineering 369, eabc3183.
tures that are apparently unrelated the catalytic layer to enable practical 2. Artero, V. (2017). Bioinspired catalytic
to catalysis, such as the linking implementation of a variety of bio- materials for energy-relevant conversions.
Nat. Energy 2, 17131.
unit, have tremendous effect on the electrochemical reactions for energy
structuration of the catalytic layer. conversion and electrosynthesis. 3. Shi, Y., Lyu, Z., Zhao, M., Chen, R., Nguyen,
Q.N., and Xia, Y. (2021). Noble-Metal
This means that the catalytic layer Nanocrystals with Controlled Shapes for
might require re-engineering for each In conclusion, the results in the Chem Catalytic and Electrocatalytic Applications.
Chem. Rev. 121, 649–735.
type of molecular catalyst. Although Catalysis paper present a step change
the optimization of the layer formula- in understanding the requirement for 4. Hou, J., Yang, M., Ke, C., Wei, G., Priest, C.,
Qiao, Z., Wu, G., and Zhang, J. (2020).
tion seems a challenging task, progress the catalytic layer and the potential for Platinum-group-metal catalysts for proton
in the general understanding of its its optimization toward order of magni- exchange membrane fuel cells: From catalyst
design to electrode structure optimization.
design principle, as pioneered in the tude enhancement in performance. In EnergyChem 2, 100023.
paper by Chenevier and co-workers, particular, requirements for catalyst
5. Coutard, N., Reuillard, B., Huan, T.N.,
will guide and greatly simplify future tethering and catalytic layer assembly Valentino, F., Jane, R.T., Gentil, S.,
engineering for targeted reactions might be mutually exclusive as illus- Andreiadis, E.S., Le Goff, A., Asset, T.,
Maillard, F., et al. (2021). Impact of ionomer
and for specific features of a given trated by the displacement of the pyr- structuration on the performance of bio-
catalyst. ene-bound catalyst from the carbon inspired noble-metal-free fuel cell anodes.

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Chem Catalysis. https://doi.org/10.1016/j. Understanding and Catalyst Design. Chem. 9. Li, H., Münchberg, U., Oughli, A.A.,
checat.2021.01.001. https://doi.org/10.1016/j.chempr.2021.01. Buesen, D., Lubitz, W., Freier, E., and
009. Plumeré, N. (2020). Suppressing
6. Boutin, E., Merakeb, L., Ma, B., Boudy, B., hydrogen peroxide generation to achieve
Wang, M., Bonin, J., et al. (2020). Molecular 8. Mazurenko, I., Monsalve, K., Infossi, P., oxygen-insensitivity of a [NiFe]
catalysis of CO2 reduction: recent advances Giudici-Orticoni, M.-T., Topin, F., Mano, N., hydrogenase in redox active films. Nat.
and perspectives in electrochemical and and Lojou, E. (2017). Impact of substrate Commun. 11, 920.
light-driven processes with selected Fe, Ni diffusion and enzyme distribution in
and Co aza macrocyclic and polypyridine 3D-porous electrodes: a combined 10. Li, H., Buesen, D., Dementin, S., Léger, C.,
complexes. Chem. Soc. Rev. 49, 5772–5809. electrochemical and modelling study Fourmond, V., and Plumeré, N. (2019).
7. Shen, H., Choi, C., Masa, J., Li, X., Qiu, J., of a thermostable H2/O2 enzymatic Complete Protection of O2-Sensitive
Jung, Y., and Sun, Z. (2021). Electrochemical fuel cell. Energy Environ. Sci. 10, 1966– Catalysts in Thin Films. J. Am. Chem. Soc.
Ammonia Synthesis: Mechanistic 1982. 141, 16734–16742.

Intercepting a labile unconventional case,4 the AAA reac-

tions of Z-allyl donors always afford chi-
anti-p-allyl-iridium complex ral E-olefinic products through the
isomerization of the originally gener-
before its isomerization ated anti-p-allyl-metal intermediate
into its thermodynamically more stable
Bao-Le Qu,1 Mao-Mao Zhang,1 Liang-Qiu Lu,1,2,* syn-variant. Therefore, the selective for-
mation of chiral Z-olefins from Z-allyl
and Wen-Jing Xiao1
precursors remains a challenge in tran-
sition-metal-catalyzed AAA reactions.
The stereodefined installation of chiral centers adjacent to thermo-
dynamically unstable Z-olefins is a challenge in synthetic chemistry. Very recently, You and coworkers5 re-
In a recent work published in Science, You and coworkers reported ported the first iridium (Ir)-catalyzed
an iridium-catalyzed, Z-retentive asymmetric allylic allylation with a Z-retentive AAA reactions of indole-
variety of Z-allyl esters, providing elegant access to important chiral type nucleophiles and aldimine esters
Z-olefins. with Z-allyl esters, providing an efficient
and practical method for synthesizing
chiral Z-olefins (Figure 1B). With the
Transition-metal-catalyzed allylic allyla- mechanism, delivering alkene products
combination of [Ir(COD)Cl]2 (COD =
tions are among the most powerful I–III. Regarding the selectivity of AAA
1,5-cyclooctadiene) and a Carreira-
tools for forging carbon-carbon and reactions, three major aspects must be
type chiral P,olefin-ligand as the
carbon-heteroatom bonds in modern considered: (1) the regioselectivity,
chiral catalyst (Ir-Cat. A, R0 = I),6 an
synthetic chemistry.1 In particular, which usually controls whether an inner
asymmetric dearomatization-cycliza-
their asymmetric counterparts, termed carbon (C3, branch selectivity [B]) or the
tion cascade of 3-nucleophile-subsi-
asymmetric allylic allylations (AAAs), terminal carbon (C1, linear selectivity
titued indoles took place in the
can selectively install stereogenic cen- [L]) in the p-allyl-metal complex reacts
presence of stoichiometric In(OTf)3
ters adjacent to alkene units, thus with nucleophiles; (2) the enantioselec-
(OTf = trifluoromethesulfonate), pro-
providing versatile chiral building tivity, which defines the spatial orienta-
ducing a diverse range of
blocks for accessing natural products, tion of nucleophiles, as well as the inner
drugs, and perfumes.2 As exemplified carbon in the branch-selective AAA re-
in allylic allylation with carbon nucleo- action; and (3) the geometric selec- 1CCNU-uOttawa Joint Research Centre, Key
philes, a general reaction pathway is tivity, which results in the E- or Z-olefinic Laboratory of Pesticide and Chemical Biology,
Ministry of Education, College of Chemistry,
briefly illustrated in Figure 1A: first, an products. By continuous endeavors, the Central China Normal University, 152 Luoyu
oxidative addition of low-valent metals synthetic communities have success- Road, Wuhan 430079, China
with allyl alcohols or their derivatives fully addressed the first two problems 2State Key Laboratory for Oxo Synthesis and
Selective Oxidation, Lanzhou Institute of
generates p-allyl-metal intermediates; by rationally choosing suitable metals Chemical Physics, Chinese Academy of Sciences,
subsequently, these transient species and chiral ligands or by using noncova- Lanzhou 730000, China
react with Csp3- or Csp2-type nucleo- lent interactions between the allyl *Correspondence: [email protected]
philes via an outer- or inner-sphere donors and acceptors.3 Except for an https://doi.org/10.1016/j.chempr.2021.02.022

552 Chem 7, 547–554, March 11, 2021 ª 2021 Published by Elsevier Inc.